Search Results (81)

It has been proven that silica fume (SF), which is a by-product from the manufacturing of single-crystal silicon, is beneficial for enhancing the mechanical properties, durability, and workability of geopolymers, as it can be quickly dissolved and form silicate-based cementitious phases in alkaline environments. However, the reinforcement mechanism of SF on geopolymer remains unclear due to the chemical complexity of geopolymer and the variety of SF types. Additionally, the solubility of calcite in an alkali environment is quite limited, and thus the formation of the amorphous calcium-based gels will be thwarted due to the lack of soluble calcium ions. Most importantly, with the development of the single-crystal industry, the amorphous silica content, crystallinity, and trace elements of SF itself have changed, which blocks the understanding of the activation mechanism of geopolymers combined with SF and insoluble calcite. To unveil the underlying modification mechanisms of SF on geopolymer materials along with insoluble calcite, in this study, two types of SF were used as the fly ash replacement in a fly ash/limestone system to prepare geopolymer materials. The reinforcement effect significantly depends on the SF types even with similar particle size and chemical compositions. The results indicate that the mechanical properties of geopolymer materials modified with SFs are not only governed by the ratio and contents of Si, Ca, Al, and Mg in SFs but also depend on the crystallinity and activity of the SFs. The hydration products could be varied according to the reaction environment. The research results not only contribute to the optimization design and application of geopolymer materials but also pave new pathways for the upcycling use of solid wastes such as SF, low-grade fly ash, or even other aluminosilicate solid wastes to achieve sustainable development. Full article

The development of eco-friendly surfactants is pivotal for enhanced oil recovery (EOR). In this study, a novel lignin-derived zwitterionic surfactant (DMS) was synthesized through a two-step chemical process involving esterification and free radical polymerization, utilizing renewable alkali lignin, maleic anhydride, dimethylamino propyl methacrylamide (DMAPMA), and sulfobetaine methacrylate (SBMA) as precursors. Comprehensive characterization via ¹H NMR, FTIR, and XPS validated the successful integration of amphiphilic functionalities. Hydrophilic–lipophilic balance (HLB) analysis showed a strong tendency to form stable oil-in-water (O/W) emulsions. The experimental results showed a remarkable 91.6% viscosity reduction in Xinjiang heavy crude oil emulsions at an optimum dosage of 1000 mg/L. Notably, DMS retained an 84.8% viscosity reduction efficiency under hypersaline conditions (total dissolved solids, TDS = 200,460 mg/L), demonstrating exceptional salt tolerance. Mechanistic insights derived from zeta potential measurements and molecular dynamics simulations revealed dual functionalities: interfacial modification by DMS-induced O/W phase inversion and electrostatic repulsion (zeta potential: −30.89 mV) stabilized the emulsion while disrupting π–π interactions between asphaltenes and resins, thereby mitigating macromolecular aggregation in the oil phase. As a green, bio-based viscosity suppressor, DMS exhibits significant potential for heavy oil recovery in high-salinity reservoirs, addressing the persistent challenge of salinity-induced inefficacy in conventional chemical solutions and offering a sustainable pathway for enhanced oil recovery. Full article

CO₂ electrochemical reduction is a promising way to convert CO₂ to valuable fuels and chemicals. This study presents a porous Cu@Zn foam catalyst with a tailored hydrophobic surface for enhanced CO₂ reduction. The catalyst is synthesized via a modified dynamic hydrogen bubble template method, incorporating polytetrafluoroethylene (PTFE) during electrodeposition to control wettability. This strategy creates a hydrophobic microenvironment that significantly increases the three-phase (gas–liquid–solid) contact area, promoting CO₂ mass transfer and suppressing the competing hydrogen evolution reaction. The optimized Cu@Zn-8PTFE catalyst achieves a CO Faraday efficiency (FE_CO) of 87.53% at −35 mA cm⁻², a 40% improvement over the unmodified Cu@Zn. Furthermore, it also exhibits excellent stability, maintaining FE_CO > 90% for 64 h at −15 mA cm⁻². While hydrophobic modification is beneficial, excess PTFE loading reduces performance by covering active sites and diminishing the three-phase interface. This work highlights the importance of controlling catalyst wettability to optimize the three-phase interface for enhanced CO₂ electroreduction. Full article

Lithium metal negative electrodes are pivotal for next-generation batteries because of their exceptionally high theoretical capacity and low redox potential. However, their commercialization is constrained by critical challenges, including dendrite formation, volumetric instability, and the fragility of the solid electrolyte interphase (SEI). In this context, this review highlights the transformative potential of ex situ surface treatments, which stabilize lithium metal electrodes before cell assembly. Key advancements include inorganic and polymer-based coatings that enhance SEI stability and mitigate dendrite growth, three-dimensional host architectures that manage volumetric changes and improve lithium diffusion, and liquid-phase chemical modifications that enable uniform lithium deposition. These strategies are critically evaluated for their scalability, environmental sustainability, and long-term stability, paying particular attention to cost, complexity, and ecological considerations. In addition, their potential contributions to the development of advanced battery technologies are discussed, providing insights into pathways toward enhanced commercial viability. By synthesizing cutting-edge research and identifying unresolved challenges, this review provides a comprehensive roadmap for advancing safer, more efficient, and more durable lithium metal batteries, thereby bridging the gap between laboratory research and commercial adoption. Full article

Background: Glutathione (GSH) is an essential antioxidant that protects against oxidative stress, but its oral bioavailability is below 1% due to enzymatic degradation and poor gastrointestinal absorption. Improving the oral bioavailability of GSH could significantly enhance its therapeutic efficacy. Methods: This study synthesised GSH analogues with chemical modifications to improve bioavailability. Seven GSH derivatives were designed: three analogues with altered stereochemistry (1.62, 1.63, and 1.64) and three N-methylated derivatives (1.65, 1.70, and 1.71), alongside a native GSH (1.61). The analogues were synthesised via Fmoc-solid-phase peptide synthesis, and they were characterised using reverse-phase high-performance liquid chromatography (RP-HPLC), electrospray ionisation mass spectrometry (ESI-MS), Fourier-transform infrared spectroscopy (FTIR), and nuclear magnetic resonance (NMR) spectroscopy. Their toxicity was assessed on Caco-2 cells for viability, and their antioxidant activity was assessed on UVA-irradiated fibroblast cells, enzymatic resistance, and interactions with GSH-metabolising enzymes. Results: Among the tested analogues, the N-methylated cysteine Compound (1.70) emerged as the most promising candidate. Compound 1.70 demonstrated superior resistance to enzymatic degradation, as well as showing enhanced cell viability and improved antioxidant activity. In vivo studies revealed a 16.8-fold increase in plasma half-life (t½) and a 16.1-fold increase in oral bioavailability compared to native GSH. Conclusions: Chemical modification strategies, particularly the N-methylation of GSH, present a viable approach to enhancing oral bioavailability. Compound 1.70 showed significant potential for therapeutic applications, warranting further investigation and development in clinical settings. Full article

The safety-catch concept involves a protecting group that remains stable under a range of chemical conditions and subsequently becomes labile under one of those conditions upon a chemical modification of the protecting group. The safety-catch approach introduces flexibility into the scheme, enabling the use of the same reagent in two distinct steps of the chemical process. For example, it facilitates α-amino deprotection and final cleavage in a solid-phase peptide synthesis scheme. Herein, we developed a safety-catch linker based on sulfinyl designed to enable peptide elongation via fluorenylmethoxycarbonyl (Fmoc) chemistry. Subsequently, upon chemical modification (oxidation of the sulfinyl group into the corresponding sulfone), the peptide is released using a secondary amine via a β-elimination reaction, which also serves to remove the Fmoc group in each step. The optimization of both key reactions, oxidation of the linker, and peptide release were achieved using a multi-detachable system, which allows specific control of both reactions. The use of this linker opens the possibility of cleaving peptides from the solid support without trifluoroacetic acid. Full article

Optical spectroscopic methods such as Raman spectroscopy offer several advantages for the analysis of water-soluble polymers (WSPs). There is often no need for complex sample preparation, and measurements are usually rapid, mostly non-destructive and no harmful chemicals are required. In this work, we investigated WSPs and their interaction with bacteria using Raman spectroscopic methods. We analyzed four different WSPs, each with three different molar masses, in solid form using Raman microscopy, and in aqueous solutions using another Raman system designed for measurements in cuvettes, to train predictive models for concentration determination. Thus, we were able to show both the high potential of these approaches, especially for fast and easy investigations both qualitatively and quantitatively, as well as their limitations. Furthermore, we chose one of the molar masses of each tested polymer to carry out extensive Raman spectroscopic investigations with Escherichia coli and Enterococcus faecium, and revealed that bacterial cells exposed to polymers exhibited distinguishable spectral characteristics compared to those not in contact with polymers. Using Raman microscopy combined with partial least squares discriminant analysis (PLS-DA), we effectively distinguished between these groups. Further chemometric analysis indicated potential polymer-induced modifications to the bacterial cell membranes. While this differentiation may partly reflect polymer interactions at the membrane level, it could also correspond to shifts in bacterial growth phases. Together, these findings suggest a complex interplay between polymer exposure and bacterial physiological states. Full article

Nowadays, nucleic acid derivatives capable of modulating gene expression at the RNA level have gained widespread recognition as promising therapeutic agents. A suitable degree of biological stability of oligonucleotide therapeutics is required for in vivo application; this can be most expeditiously achieved by the chemical modification of the internucleotidic phosphate group, which may also affect their cellular uptake, tissue distribution and pharmacokinetics. Our group has previously developed a strategy for the chemical modification of the phosphate group via the Staudinger reaction on a solid phase of the intermediate dinucleoside phosphite triester and a range of, preferably, electron deficient organic azides such as sulfonyl azides during automated solid-phase DNA synthesis according to the conventional β-cyanoethyl phosphoramidite scheme. Polyfluoro compounds are characterized by unique properties that have prompted their extensive application both in industry and in scientific research. We report herein the synthesis and isolation of novel oligodeoxyribonucleotides incorporating internucleotidic perfluoro-1-octanesulfonyl phosphoramidate or 2,2,2-trifluoroethanesulfonyl phosphoramidate groups. In addition, novel oligonucleotide derivatives with fluorinated zwitterionic phosphate mimics were synthesized by a tandem methodology, which involved (a) the introduction of a carboxylic ester group at the internucleotidic position via the Staudinger reaction with methyl 2,2-difluoro-3-azidosulfonylacetate; and (b) treatment with an aliphatic diamine, e.g., 1,1-dimethylethylenediamine or 1,3-diaminopropane. It was further shown that the polyfluoro oligonucleotides obtained were able to form complementary duplexes with either DNA or RNA, which were not significantly differing in stability from the natural counterparts. Long-chain perfluoroalkyl oligonucleotides were taken up into cultured human cells in the absence of a transfection agent. It may be concluded that the polyfluoro oligonucleotides described here can represent a useful platform for designing oligonucleotide therapeutics. Full article

Intermediate temperature solid oxide fuel cell (SOFC) operation provides numerous advantages such as high combined heat and power (CHP) efficiency, potentially long-term material stability, and the use of low-cost materials. However, due to the sluggish kinetics of the oxygen reduction reaction at intermediate temperatures (500–700 °C), the cathode of SOFC requires an efficient and stable catalyst. Significant progress in the development of cathode materials has been made over recent years. In this article, multiple strategies for improving the performance of cathode materials have been extensively reviewed such as A- and B-site doping of perovskites, infiltration of catalytic active materials, the use of core-shell composites, etc. Emphasis has been given to intrinsic properties such as chemical and thermal stability and oxygen transport number. Furthermore, to avoid any insulating phase formation at the cathode/electrolyte interface, strategies for interfacial layer modifications have also been extensively reviewed and summarized. Based on major technical challenges, future research directions have been proposed for efficient and stable intermediate temperature solid oxide fuel cell (SOFC) operation. Full article

Nanocrystalline mullite was synthetized by annealing a highly porous 3D structure consisting of nanofibrous aluminum oxyhydroxides treated with ethoxysilanes. The chemical, structural, and phase transformations in the aluminosilicate nanosystem were studied in the temperature range between 100 and 1600 °C. The features of the solid-phase synthesis of mullite at the interface of crystalline alumina with a liquid silica layer are discussed. It was established that chemical modification of the alumina surface with ethoxysilanes significantly limits the interphase mass transport and delays the phase transformation of the amorphous oxide into γ-Al₂O₃, which begins at temperatures above 1000 °C, while the basic structural nanofibrils are already crystallized at ~850 °C. The formation of mullite was completed at temperatures ≥ 1200 °C, where the fraction of γ-Al₂O₃ sharply decreased. Full article

This paper investigates the interrelated effects of thermomechanical treatments and chemical composition on the phase transformation capabilities of thin sheets made from Cu-Al-Mn shape memory alloys. The transformation capacity and transition temperatures were determined using DSC and DMA testing, while composition measurements were performed using SEM/EDX analysis. The results demonstrate that applying hot-rolling treatments to alloys of reduced thickness leads to manganese oxidation and modifications in chemical composition, adversely impacting the phase transformation performance. This effect can be mitigated by the use of cold rolling. Additionally, the presence of phosphorus impurities can create inclusions that bind manganese, preventing it from remaining in the solid solution and further affecting phase transformation capabilities. Full article

This study examines the effects of La³⁺ doping on (Pb_0.75Ba_0.25)(Zr_0.70Ti_0.30)O₃(PBZT) ceramics, which were synthesized using the conventional solid-state reaction method. X-ray diffraction analysis confirmed that the PBZT structure, including PBZT doped with La³⁺ at concentrations x = 1 at.% and x = 2 at.%, exhibited a rhombohedral (R3c) space group, while higher doping levels of x = 3 at.% and x = 4 at.% led to a dominant cubic (Pm-3m) phase with approximately 30% of a remnant rhombohedral component. Scanning electron microscopy (SEM, JEOL JSM-7100F TTL LV, Jeol Ltd., Tokyo, Japan) and energy dispersive X-ray spectroscopy (EDS) were utilized to investigate the structure and morphology of these ceramics. The findings indicated that the chemical composition of the ceramic samples closely corresponded to the initial stoichiometry of the ceramic powder. An increase in the amount of lanthanum results in a decrease in the average grain size of the ceramics. The electrical properties were further evaluated using complex impedance spectroscopy (IS) over a range of temperatures and frequencies, as well as temperature dependence of DC conductivity. The similarity in the changes in activation energy for DC conductivity and grain boundary conductivity, caused by lanthanum ion modification, allows for the conclusion that grain boundaries are the primary microstructural element responsible for conductivity in these materials. Full article

The scope of this study was to apply advances in materials science, specifically the use of organosilicate nanoparticles as a high surface area platform for passive sampling of chemicals or pre-concentration for active sensing in multiple-phase complex environmental media. We have developed a novel nanoporous organosilicate (NPO) film as an extraction phase and proof of concept for application in adsorbing hydrophobic compounds in water and sediment. We characterized the NPO film properties and provided optimization for synthesis and coatings in order to apply the technology in environmental media. NPO films in this study had a very high surface area, up to 1325 m²/g due to the high level of mesoporosity in the film. The potential application of the NPO film as a sorbent phase for sensors or passive samplers was evaluated using a model hydrophobic chemical, polychlorinated biphenyls (PCB), in water and sediment. Sorption of PCB to this porous high surface area nanoparticle platform was highly correlated with the bioavailable fraction of PCB measured using whole sediment chemistry, porewater chemistry determined by solid-phase microextraction fiber methods, and the Lumbriculus variegatus bioaccumulation bioassay. The surface-modified NPO films in this study were found to highly sorb chemicals with a log octanol-water partition coefficient (K_ow) greater than four; however, surface modification of these particles would be required for application to other chemicals. Full article

The high-temperature composite phase change materials (HCPCMs) were prepared from solid waste blast furnace slag (BFS) and NaCl-KCl binary eutectic salt to achieve efficient and cost-effective utilization. To ensure good chemical compatibility with chlorine salt, modifier fly ash (FA) was incorporated and subjected to high-temperature treatment for the processing of industrial solid waste BFS, which possesses a complex chemical composition. The HCPCMs were synthesized through a three-step process involving static melting, solid waste modification, and mixing–cold pressing–sintering. Then, the influence of the modification method and the amount of SiC thermal conductivity reinforced material on chemical compatibility and thermodynamic performance was explored. The results demonstrate that the predominant phase of the modified solid waste is Ca₂Al₂SiO₇, which exhibits excellent chemical compatibility with chlorine salt. HCPCMs containing less than 50 wt.% chloride content exhibit good morphological stability without any cracks, with a melting temperature of 661.76 °C and an enthalpy value of 108.73 J/g. Even after undergoing 60 thermal cycles, they maintain good chemical compatibility, with leakage rates for melting and solidification enthalpies being only 6.3% and 0.23%, respectively. The equilibrium was achieved when 40 wt.% of chloride salt was encapsulated upon the addition of 10% of SiC, and the incorporation of SiC resulted in an enhancement of thermal conductivity for HCPCMs to 2.959 W/(m·K) at room temperature and 2.400 W/(m·K) at 200 °C, with an average increase of about 2 times. The cost of the prepared HCPCMs experienced a significant reduction of 81.3%, demonstrating favorable economic performance and promising prospects for application. The research findings presented in this article can offer significant insights into the efficient utilization of solid waste. Full article

X-ray irradiation and modified atmospheres (MAs) provide eco-friendly, chemical-free methods for pest management. Although a low-oxygen atmospheric treatment improves the performance of some irradiated insects, its influence on the irradiation of quarantine insects and its impacts on pest control efficacy have yet to be investigated. Based on bioassay results, this study employed direct immersion solid-phase microextraction (DI-SPME) combined with gas chromatography-mass spectrometry (GC-MS) to determine metabolic profiles of late third-instar B. dorsalis larvae under normoxia (CON, Air), hypoxia (95% N₂ + 5% O₂, HY), super-hypoxia (99.5% N₂ + 0.5% O₂, Sup-HY), irradiation-alone (116 Gy, IR-alone), hypoxia + irradiation (HY + IR) and super-hypoxia + irradiation (Sup-HY + IR). Our findings reveal that, compared to the IR-alone group, the IR treatment under HY and Sup-HY (HY + IR and Sup-HY + IR) increases the larval pupation of B. dorsalis, and weakens the delaying effect of IR on the larval developmental stage. However, these 3 groups further hinder adult emergence under the phytosanitary IR dose of 116 Gy. Moreover, all IR-treated groups, including IR-alone, HY + IR, and Sup-HY + IR, lead to insect death as a coarctate larvae or pupae. Pathway analysis identified changed metabolic pathways across treatment groups. Specifically, changes in lipid metabolism-related pathways were observed: 3 in HY vs. CON, 2 in Sup-HY vs. CON, and 5 each in IR-alone vs. CON, HY + IR vs. CON, and Sup-HY + IR vs. CON. The treatments of IR-alone, HY + IR, and Sup-HY + IR induce comparable modifications in metabolic pathways. However, in the HY + IR, and Sup-HY + IR groups, the third-instar larvae of B. dorsalis demonstrate significantly fewer changes. Our research suggests that a low-oxygen environment (HY and Sup-HY) might enhance the radiation tolerance in B. dorsalis larvae by stabilizing lipid metabolism pathways at biologically feasible levels. Additionally, our findings indicate that the current phytosanitary IR dose contributes to the effective management of B. dorsalis, without being influenced by radioprotective effects. These results hold significant importance for understanding the biological effects of radiation on B. dorsalis and for developing IR-specific regulatory guidelines under MA environments. Full article