Search Results (405)

Conventional polyolefin battery separators are limited by inherent deficiencies in thermal stability, electrolyte wettability, and environmental sustainability, which collectively hinder the advancement of high-energy-density energy storage systems. In this context, biomass macromolecular materials, including cellulose, chitin/chitosan, and lignin, have emerged as promising candidates for next-generation separators owing to their environmental benefits, exceptional hydrophilicity, and superior thermal resistance. This review systematically evaluates the molecular characteristics of these three biomass systems, alongside core gel-state processing and network-forming processes such as electrospinning, solution casting, nonwoven technology, and hydrogel-assisted film formation. It further highlights their cutting-edge applications in lithium-ion, lithium–sulfur, zinc-ion, and solid-state batteries, emphasizing their behavior as polymer gel electrolytes and gel-derived structural matrices. To overcome key challenges associated with mechanical robustness, interfacial compatibility, and network uniformity, advanced modification strategies are critically discussed, including surface chemical functionalization, multicomponent hybrid composite formulation, and rational three-dimensional structural engineering. Overall, current research evidence demonstrates that rationally designed biomass-based gel networks and membranes can effectively suppress metal dendrite growth, immobilize soluble polysulfide intermediates via supramolecular interactions, and reduce interfacial impedance in solid-state systems, thereby offering a viable pathway toward safer, more sustainable, and commercially competitive high-energy-density batteries. Full article

The clinical success of cisplatin has significantly spurred the exploration of new organometallic complexes in oncology. In this quest, repurposing of auranofin as an anticancer agent has diverted the research interest from platinum to gold complexes, as gold offers unique chemical features; among them, thioredoxin reductase (TrxR) inhibition is one of the most extensively studied anticancer pathways. In this study, we have compiled the major ligand modifications reported for gold(I) complexes and categorized them into various groups, which include sulfur-based ligands, nitrogen-containing heterocyclic ligands, carbon-derived ligands, and N-heterocyclic carbene-based ligands. Also, a few structurally distinct ligands, including propargyl-, allene-, tricarbene-, and urea-functionalized NHC frameworks, have further extended structural diversity and functional potential. The in vitro evaluation of these newly synthesized gold complexes against various cancer cell lines exhibited enhanced biological potential compared to conventional metal complexes. Comparative evaluation of the reported cytotoxicity data revealed distinct structure–activity relationships among different ligand classes, with phosphine-carbon donor and bis-NHC frameworks emerging as the most promising ligand for achieving potent anticancer activity, highlighting the critical role of ligand design in modulating anticancer activity. In addition, the use of bioactive pharmacophores derived from natural products and active pharmaceuticals has emerged as a promising design strategy for developing multitarget gold(I) complexes with enhanced therapeutic efficacy. Among the reviewed compounds, complex 68 containing a bis-NHC ligand exhibited the highest potency against HL-60 leukemia cells (GI₅₀ = 0.017 μM), while complex 49 bearing a carbon-donor ligand demonstrated remarkable activity against A549 lung cancer cells (IC₅₀ = 0.02 μM). Several other gold(I) complexes also exhibited submicromolar activity against diverse cancer cell lines, further emphasizing the importance of rational ligand engineering in enhancing anticancer efficacy. Collectively, gold(I) complexes have emerged as a promising class of anticancer agents, and the comparative evaluation presented herein provides a valuable framework for identifying potent ligand scaffolds and guiding the rational development of next-generation gold-based therapeutics. Future advances in ligand engineering may facilitate targeted drug delivery, controlled release, and multi-mechanistic therapeutic strategies to overcome toxicity and drug resistance while enhancing therapeutic efficacy. Full article

This study investigated the production of spodumene concentrate and lithium carbonate from a low-grade pegmatite ore containing approximately 0.26 wt.% Li₂O. The ore consisted predominantly of a quartz–feldspar aluminosilicate matrix with dispersed spodumene mineralization, which complicates conventional processing approaches. Preliminary lithium concentration was performed by dense media separation (DMS) using an industrially applicable ferrosilicon-based suspension. The highest separation efficiency was achieved for the −4.0/+2.8 mm fraction, producing a DMS concentrate containing 5.77 wt.% Li₂O with 98% lithium recovery. The obtained spodumene concentrate was subjected to decrepitation at 1000–1100 °C to convert α-spodumene into the more reactive β-modification, followed by sulfation roasting with concentrated sulfuric acid at 250–270 °C. The productive leach solution obtained after water leaching contained up to 12.1 g/L Li₂O. After purification from iron-bearing impurities and precipitation with sodium carbonate, a lithium carbonate product containing at least 98.8 wt.% Li₂CO₃ was obtained. Approximately 53% of the lithium contained in the original ore was recovered into the DMS feed fraction, whereas the overall lithium recovery into lithium carbonate reached about 45% relative to the ore and approximately 70% relative to the concentrate. Full article

Severe traumatic brain injury (TBI) is one of the leading causes of mortality and disability worldwide. To date, there are no clinically effective neuroprotective agents. Biomaterials that combine structural support for damaged tissue with a depot for therapeutic agents may represent a key solution to this problem. To evaluate the neuroprotective potential of a collagen matrix derived from the jellyfish Rhizostoma pulmo (R. pulmo) and modified with sodium thiosulfate (Na₂S₂O₃) as an hydrogen sulfide (H₂S) donor in a bioengineered platform for the treatment of severe TBI. Comprehensive characterization of the collagen matrix (electrophoresis, fluorescence microscopy), its implantation in a mouse model of severe TBI, and subsequent morphological, histological, ultrastructural, and immunohistochemical analyses of connexin 43 (Cx43) and p53 protein (p53) were performed. In addition, molecular dynamics simulations of the interactions between sulfur-containing compounds and target proteins were conducted. The effects were compared with inhibition of endogenous H₂S synthesis using aminooxyacetic acid (AOAA). The collagen matrix retains the properties of type I collagen and forms a three-dimensional porous structure with high hydrophilicity and biocompatibility. Implantation ensures effective defect filling, reduces cystic degeneration, and preserves cortical structure. Modification with Na₂S₂O₃ results in a significant reduction in both nuclear and cytoplasmic accumulation of p53, prevention of Cx43 dysregulation, a decrease in the proportion of damaged neurons and inflammatory infiltration, and preservation of tissue ultrastructure. In contrast, inhibition of CBS with AOAA exacerbates pathological changes. Molecular modeling demonstrated that S₂O₃²⁻ is capable of forming stable electrostatic interactions with domains of p53 and Cx43 under conditions of acidosis and elevated Ca²⁺. A collagen matrix derived from R. pulmo and modified with Na₂S₂O₃ represents a promising biodegradable platform that combines structural support with local H₂S-dependent regulation of key mechanisms of secondary brain injury. This approach provides a multilevel neuroprotective effect and opens new opportunities for the development of therapeutic implants for severe TBI. Full article

Sulfane sulfur species are increasingly recognized as integral cellular components involved in signaling pathways and cytoprotection against oxidative stress in mammals. While their production in bacteria has been extensively studied, their functional role in bacterial oxidative stress defense remains poorly understood. Here, we demonstrate that sulfane sulfur generated by sulfide: quinone oxidoreductase decreases H₂O₂ sensitivity in Pseudomonas aeruginosa PAO1. Notably, this protective mechanism does not depend on sulfane sulfur acting as a direct H₂O₂ scavenger via nucleophilic reactions. Through persulfidation proteomic profiling, we reveal that persulfidation is a prominent post-translational modification in P. aeruginosa, reflecting the prevalence of deprotonated sulfane sulfur species. These species modify cysteine residues in proteins, including the well-known oxidative stress regulator OxyR. Specifically, sulfane sulfur modifies OxyR at Cys199 to form persulfidated OxyR C199-SSH, contributing to a single-Cys activated state that modulates promoter activity and DNA-binding affinity. Furthermore, sulfane sulfur-mediated persulfidation protects the critical cysteine residue of LpdG, a ROS-vulnerable dihydrolipoamide dehydrogenase, from irreversible overoxidation. Although LpdG is not part of the canonical H₂O₂-scavenging system, its preservation is essential for cell viability under oxidative stress. These findings establish endogenous sulfane sulfur species as key mediators of antioxidant defense in P. aeruginosa. Full article

Faced with a global energy crisis and ecological degradation, overall water splitting (OWS) is a pivotal approach for renewable energy conversion and storage. However, its industrial application is hindered by the high energy barriers/sluggish kinetics of the anodic oxygen evolution reaction (OER), as well as the scarcity of precious metal catalysts limiting large-scale deployment. Herein, a cobalt-based layered double hydroxide (Co-LDH) was used as the precursor, and a multi-strategy synergistic modification (hydrothermal synthesis, Fe doping, sulfurization, and external magnetic field magnetization) was applied to fabricate the Fe-Co₃S₄-MS-20 min electrocatalyst. This strategy establishes Fe-Co bimetallic synergistic active centers, and magnetic treatment modulates the electron configuration of Fe 3d orbitals without changing the material’s lattice spacing or morphology. Structural characterizations and electrochemical measurements were used to investigate the effects of combined modifications on the catalyst’s phase structure, morphology, electronic structure, and trifunctional catalytic performance toward the hydrogen evolution reaction (HER), OER, and urea oxidation reaction (UOR). The Fe-Co₃S₄-MS-20 min catalyst exhibits a larger electrochemical active surface area, lower charge transfer resistance, and smaller Tafel slope in 1 M KOH, it achieves overpotentials of 165 mV for HER (10 mA·cm⁻²) and 310 mV for OER (100 mA·cm⁻²), along with superior UOR performance and long-term stability. In situ impedance and Raman spectroscopy confirm that magnetization accelerates charge transfer and promotes in situ reconstruction. Synergistic multi-strategy regulation optimizes the electronic structure of active centers, reducing electrocatalytic energy barriers. This work provides new insights into designing high-performance non-precious metal electrocatalysts and offers experimental support for external magnetic field regulation in electrocatalyst modification. Full article

In this study, polyhedral self-assembled spherical titania (TS) photocatalyst was successfully synthesized via a one-step hydrothermal method from titanium chloride, sodium dodecyl sulfate and sulfuric acid. Titania modification with iron was carried out through the same procedure by the addition of different amounts of iron(III) chloride to the substrate mixture. Various methods were applied for sample characterization, e.g., XRD, SEM, TEM, XPS, UV-vis DRS, and photo-electrochemical measurements, such as EIS, CV, transient photocurrent, whereas photocatalytic activity was investigated for hydrogen evolution under UV/vis and oxidative decomposition of antibiotics under UV and/or vis, including also tests with scavengers. It has been found that iron was both incorporated in the titania structure (doping) and adsorbed on its surface. Although iron presence has hardly influenced the properties (slight changes in morphology, bandgap energy, and crystallite size), the photocatalytic activity has increased significantly. Therefore, it is proposed that iron might work as an electron sink, hindering the charge carriers’ recombination. Linear evolution of hydrogen, recycling experiments and characterization of samples after recycling have confirmed a good stability of iron-modified titania. Full article

Electrochemical water splitting stands as a feasible approach for sustainable hydrogen production, but its industrial implementation is restricted by sluggish oxygen evolution reaction (OER) kinetics and excessive dependence on freshwater resources. As a widely existing alternative, seawater contains a high concentration of chloride ions (Cl⁻), which give rise to serious electrode corrosion and catalyst deactivation, bringing great challenges to actual electrolysis applications. Herein, we report a facile room-temperature two-step soaking strategy to fabricate sulfur-modified NiFe layered double hydroxide (S-NiFe-LDH) catalysts for efficient OER in both alkaline freshwater and seawater electrolytes. The introduction of sulfur not only optimizes the electronic structure of NiFe-LDH to strengthen intrinsic catalytic activity and speed up charge transfer, but also promotes the formation of a Cl⁻-resistant layer, thus significantly improving corrosion resistance. In addition, DFT calculations show sulfur modification in NiFe layered double hydroxide upshifts the O 2p-band center to activate lattice oxygen, switches the oxygen evolution reaction pathway to the lattice oxygen mechanism with reduced thermodynamic barriers, and realizes the selective adsorption of OH⁻ over Cl⁻. As a result, the as-prepared S-NiFe-LDH catalyst exhibits exceptional OER performance, requiring overpotentials (η) of 250, 270, and 290 mV to reach current densities of 50, 100, and 200 mA·cm⁻² in 1 M KOH, respectively, with a Tafel slope of 22.3 mV·dec⁻¹. Moreover, it maintains remarkable stability for more than 200 h in alkaline seawater electrolytes and achieves nearly 100% Faradaic efficiency for water splitting, effectively avoiding the parasitic chlorine evolution reaction (CER). This work provides a scalable and energy-efficient synthetic route for designing advanced non-noble metal catalysts, paving the way for industrial-scale hydrogen production from seawater. Full article

Lithium–sulfur (Li–S) batteries hold great promise for next-generation energy storage owing to their ultrahigh theoretical energy density; however, their practical application is severely hampered by the polysulfide shuttle effect and the penetration of lithium dendrites through the separator. In this work, a carboxyl-containing anionic polymer (TPU-DMBA) is synthesized and composited with Ketjen Black (KB), and the resulting mixture is coated onto a commercial polypropylene separator via a simple doctor-blade method. In this design, the porous KB network provides physical adsorption to capture polysulfides, while the dissociated carboxylate groups (–COO⁻) generate strong electrostatic repulsion against negatively charged polysulfide anions (S_n²⁻). This dual-mechanism strategy—adding electrostatic repulsion on the basis of physical adsorption—effectively suppresses the shuttle effect. In addition, the flexible polymer backbone increases the tensile strength of the separator by approximately 30%, enhancing its resistance against dendrite penetration. The carbon material also significantly improves electrolyte wettability (the contact angle decreases from 41.6° to 11.7°) and ionic conductivity (from 0.48 × 10⁻³ to 0.88 × 10⁻³ S cm⁻¹). The polymer itself acts as a binder, eliminating the need for additional binder addition. Benefiting from the synergy of electrostatic repulsion, physical adsorption, and mechanical reinforcement, the prepared modified separator endows the Li–S battery with an initial specific discharge capacity of 1373.15 mAh g⁻¹ at 0.1 C and an initial discharge capacity of 714.46 mAh g⁻¹ at a high rate of 2 C. After 200 cycles at 2 C, the capacity remains 577.93 mAh g⁻¹, with a capacity retention of 80.89%. This work provides a low-cost, scalable, and binder-free separator modification strategy that simultaneously suppresses the polysulfide shuttle and resists dendrite growth, opening a new and effective pathway toward practical high-performance Li–S batteries. Full article

Arundo donax L. is a significant energy crop and perennial grass, with its efficient conversion holding substantial implications for the utilization of agricultural biomass resources. However, the distinct effects of acid and alkali pretreatments on its lignocellulose degradation patterns and structural modifications remain inadequately characterized. This study utilized Arundo donax L. as raw material to compare the effects of dilute sulfuric acid and sodium hydroxide pretreatments on its component degradation and structural modifications. Single-factor experiments were conducted, and the mechanisms were investigated using X-ray diffraction (XRD), Fourier Transform Infrared Spectroscopy (FTIR), and scanning electron microscopy (SEM) analyses. The results indicated that dilute sulfuric acid pretreatment primarily degraded hemicellulose (up to 85.8%) with limited lignin removal (<13%), whereas sodium hydroxide pretreatment effectively removed lignin (66.8%). XRD analysis revealed that crystallinity after dilute acid treatment was significantly higher than that of untreated samples (p < 0.05). Sodium hydroxide treatment induced a concentration-dependent non-monotonic change in crystallinity: the crystallinity index (CrI) peaked at a 1% concentration, was significantly lower at 3% and 4%, and showed intermediate values at 2% and 5%. The apparent crystallite size remained at 3.0–3.3 nm, suggesting that both pretreatments primarily targeted amorphous regions. FTIR analysis confirmed that alkali treatment more thoroughly disrupted ester bonds and lignin. SEM images revealed that alkali-treated fiber bundles were more loosely packed with relatively smoother surfaces. In acid treatment, 100 °C was identified as the critical temperature for a significant increase in crystallinity, whereas in alkali treatment, temperature had no significant effect on crystallinity. Full article

This review explores the biological properties and application potential of native, technical, and modified lignins, with a focus on their antioxidant, antimicrobial, and anti-inflammatory activities. Native lignin generally preserves more of its original phenolic architecture and thus shows stronger intrinsic biological activity. This is likely due to its more homogeneous structure, which makes its physicochemical behavior more predictable compared with highly processed technical lignins. Among technical lignins, organosolv and soda lignin appear the most promising due to their sulfur-free nature, lower condensation, and higher reactivity. At the monomer level, catechol-type phenolics show the highest antioxidant potential, while vanillin remains the most attractive lignin-derived monomer because it combines bioactivity with direct application potential in food, pharmaceutical, and cosmetic systems. Comparison of modification strategies indicates that phenolic grafting, esterification, and carboxylation are more practical for scale-up than complex multistep polymer grafting. In particular, gallic acid grafting produced some of the strongest results, including near-complete 2,2′-azino-bis-(3-ethylbenzothiazoline-6-sulfonic acid) (ABTS) scavenging, 98.7% 2,2-diphenyl-1-picrylhydrazyl (DPPH) radical inhibition, and a fourfold increase in phenolic hydroxyl content, whereas other modified lignins also showed improved antimicrobial and anti-inflammatory effects. Overall, mild and green lignin modification, especially with food-safe phenolic compounds, appears to be the most promising strategy for future food and human health applications. Full article

Three-dimensional concrete printing (3DCP) offers an accurate, formwork-free, and resource-efficient construction process; however, the absence of vibration and compaction often results in increased porosity and reduced durability. This study investigates the influence of nano-calcium carbonate (NC), acting as a nano pore-filler, on the durability and other physical properties of 3DCP. NC was incorporated at dosages of 0–3% by weight of cement, and specimens were fabricated using a laboratory-scale 3D printing machine. Durability performance was evaluated after 120 days under plastic-wrapped curing, sulfuric acid exposure, and magnesium sulfate immersion. In addition, thermal conductivity and sound absorption were measured to identify the effect of pore structure modification by NC. The results show that NC enhances matrix densification and mechanical performance up to an optimal dosage of approximately 2%, beyond which its effectiveness decreases. Under magnesium sulfate immersion, the strength decreased slightly but improved with increasing NC content up to about 2%. In the case of sulfuric acid exposure, the strength decreased significantly after 120 days; however, it still increased with increasing NC content. Incorporating NC into 3DCP appears to provide improved resistance to both magnesium sulfate and sulfuric acid exposure. Thermal conductivity increased with NC addition, indicating improved solid-phase continuity, whereas sound absorption decreased due to the reduction in porosity. These findings demonstrate that nano-calcium carbonate can effectively refine pore structure and improve durability-related performance, contributing to extended service life and more sustainable 3D-printed cementitious materials in the built environment. Full article

Rechargeable magnesium batteries are promising candidates for next-generation energy storage systems due to their intrinsic safety, natural abundance, and high volumetric capacity. However, their practical application remains limited by sluggish Mg²⁺ transport, electrolyte instability, and low cathode utilization. In this work, a halogen-free electrolyte (HFE) based on Mg(NO₃)₂ in an acetonitrile/tetraethylene glycol dimethyl ether (ACN/G4) solvent system is modified using the ionic liquid 1-ethyl-3-methylimidazolium acetate ([EMIM][OAc]) to form HFE_IL, with the aim of enhancing ionic transport and interfacial stability. In parallel, a sustainable sulfur cathode integrated with microalgae-derived hard carbon (S_C) is developed to improve electronic conductivity and suppress polysulfide shuttling. Structural and spectroscopic analyses confirm that the incorporation of the ionic liquid preserves the electrolyte framework while tuning the solvation environment. Electrochemical characterization (EIS, CV, LSV, GCD, and Mg stripping/plating measurements) reveals that HFE_IL exhibits reduced bulk and interfacial resistances, a significantly lower activation energy (0.0173 eV compared to 0.14 eV), and an increased Mg²⁺ transference number (~0.8). Furthermore, enhanced Mg²⁺ diffusion (~10⁻¹³ cm² s⁻¹) and improved charge-transfer kinetics are achieved compared to the pristine electrolyte. Symmetric Mg‖Mg cells demonstrate stable stripping/plating behavior with reduced polarization over 100 h. In full Mg‖electrolyte‖S_C cells, the HFE_IL system delivers a higher discharge capacity (~575 mAh g⁻¹) compared to the pristine electrolyte (~437 mAh g⁻¹), indicating improved reversibility and Mg²⁺ utilization. This study demonstrates that ionic-liquid modification of halogen-free electrolytes, combined with sustainable carbon–sulfur cathodes, provides an effective strategy to enhance Mg²⁺ transport, interfacial stability, and overall electrochemical performance in magnesium batteries. Full article

The increasing scarcity of freshwater in mining regions of Chile has promoted the use of low-quality water as an alternative in flotation processes, significantly modifying their operating conditions. In particular, high salt concentrations and the presence of dissolved ionic species may interfere with the adsorption of collectors on chalcopyrite, thereby reducing its hydrophobicity. In this context, the present study analyzes the adsorption characteristics and the mechanistic role of selected representative ionic species on the chalcopyrite surface. To this end, simulations based on density functional theory (DFT) were employed to describe the interaction between the chalcopyrite (112) surface and Na⁺, Ca²⁺, Mg²⁺, and OH⁻ ions. After geometric convergence of the optimized structures was achieved, adsorption energies, charge redistribution based on Mulliken population analysis, and the final structural configurations were evaluated for each case. The results revealed clearly differentiated behaviors among the ionic species considered. The OH⁻ ion exhibited a localized and specific interaction with metal-centered sites. By contrast, Ca²⁺ and Mg²⁺ show stable adsorption near sulfur atoms, indicating a higher affinity that may lead to the occupation or blocking of active surface sites. Meanwhile, Na⁺ displays a weak interaction without inducing significant structural modifications. Overall, these findings provide an atomistic-level interpretation of how ionic species present in low-quality water can influence the surface reactivity of chalcopyrite under flotation operating conditions. Full article

Graphitic carbon nitride (CN) is a promising photocatalytic material, but its practical application is limited by small specific surface area, narrow light absorption range, and high photogenerated carrier recombination rate. To address these issues, this study synthesized boron-doped carbon nitride (BCN) and sulfuric acid-exfoliated boron-doped carbon nitride (BCND). X-ray diffraction (XRD) and X-ray photoelectron spectroscopy (XPS) results confirmed that boron was successfully doped into the CN skeleton via B-N bonds. Scanning electron microscopy (SEM) and N₂ adsorption–desorption (BET) characterizations showed that acid exfoliation significantly increased the specific surface area of BCND to 68.80 m²·g⁻¹, much higher than that of CN (9.54 m²·g⁻¹) and BCN (15.98 m²·g⁻¹). UV–visible diffuse reflectance spectroscopy (UV-Vis DRS) analysis revealed that BCND had the narrowest bandgap (2.59 eV) among the three materials, which enhanced its visible-light absorption efficiency. Photoelectrochemical tests demonstrated that BCND exhibited the smallest charge transfer resistance and the highest transient photocurrent density (eight times that of CN), indicating efficient separation of photogenerated electron–hole pairs. Photocatalytic water splitting experiments showed that BCND achieved the highest Hydrogen production rate of 792.34 μmol·g⁻¹·h⁻¹, which was about 4 times that of CN (158.41 μmol·g⁻¹·h⁻¹) and 1.36 times that of 2.5% BCN (584.30 μmol·g⁻¹·h⁻¹). Free-radical trapping experiments indicated that hydroxyl radicals (·OH) played a crucial promotional role in Hydrogen production, while superoxide anions (·O₂⁻) exerted an inhibitory effect. The enhanced performance of BCND was attributed to the synergistic effects of boron doping (narrowing bandgap) and acid exfoliation (increasing specific surface area). A possible photocatalytic Hydrogen production mechanism was proposed based on the experimental results. This study provides a feasible strategy for the structural modification and performance optimization of g-C₃N₄-based photocatalysts for water splitting. Full article