Search Results (487)

Molten salt chlorination is a key industrial route for producing titanium tetrachloride (TiCl₄), yet the atomistic catalytic role of iron (Fe) in the carbothermic chlorination of titanium oxides remains unclear. Here, the chlorination behavior of the NaCl–C–Cl₂–FeTiO₃ system was investigated by combining thermodynamic calculations with Ab Initio Molecular Dynamics (AIMD) and Deep Potential Molecular Dynamics (DPMD) simulations. AIMD results show that carbon adjacent to Fe exhibits enhanced reactivity, and that Fe-C synergistic electron transfer promotes both titanium oxide reduction and subsequent titanium chlorination. DPMD results further reveal that Fe not only accelerates these transformations, but also improves interfacial contact among carbon, titanium oxides, and molten salt, thereby enhancing mass transfer and shortening the formation time of TiCl₄. Temperature-dependent analysis indicates that Fe-C and C-O coordination numbers remain high near 1073 K, where TiCl₄ formation is efficient and relatively stable. Although increasing temperature can further enhance diffusion, its effect on reaction acceleration is limited, while excessively high temperatures weaken Fe-C interactions and reduce catalytic efficiency. These findings clarify the catalytic mechanism of Fe in molten salt chlorination at the atomic scale and provide theoretical support for process optimization. Full article

Laryngeal squamous cell carcinoma (LSCC) remains a major clinical challenge within head and neck oncology, with five-year survival rates showing minimal improvement over recent decades despite advances in surgical and multimodal therapeutic strategies. Increasing evidence identifies metabolic reprogramming as a central driver of tumor progression, therapeutic resistance, and immune evasion in LSCC. Beyond the classical Warburg effect, LSCC exhibits profound metabolic reprogramming, involving coordinated alterations in carbohydrate, amino acid, lipid, and iron metabolism that support adaptation to hypoxic and nutrient-deprived microenvironments. Hypoxia-inducible factors, particularly HIF-1α, coordinate these key biochemical pathways and enzymatic steps by integrating glycolysis, glutaminolysis, folate-dependent one-carbon pathways, lipid synthesis, and mitochondrial remodeling, while also influencing stromal and immune components of the tumor microenvironment. Metabolic crosstalk between tumor cells, cancer-associated fibroblasts, and immune populations promotes immunosuppression through nutrient competition and accumulation of metabolites such as lactate and lipid-derived mediators. In parallel, dysregulated iron handling and altered ferroptosis susceptibility emerge as key determinants of tumor aggressiveness and treatment response. This review synthesizes current evidence on metabolic rewiring in laryngeal squamous cell carcinoma, highlighting how alterations in metabolic pathways create targetable vulnerabilities that drive tumor biology, immune modulation, and resistance to conventional and emerging therapies. Elucidating these metabolic dependencies may support the development of metabolism-based biomarkers and therapeutic strategies in laryngeal squamous cell carcinoma, providing an integrated and translational perspective that links tumor metabolism with microenvironmental interactions and immune modulation, while highlights emerging therapeutic vulnerabilities. Full article

Arsenic contamination in polymetallic mining areas is closely linked to surrounding iron-rich manganese minerals. However, conclusive evidence remains limited regarding the retention and migration process of As(V) in naturally manganese-rich manganese ores (especially those with different manganese/iron mass ratios) under dynamic flow conditions. This study investigated As(V) adsorption and transport by four natural manganese minerals (FM1–FM4) through batch/column experiments, characterization, and numerical modeling. Their Mn/Fe mass ratios were 22.7 for FM1, 4.2 for FM2, 3.7 for FM3, and 16.4 for FM4. Batch experiments showed that As(V) adsorption on FM1–FM3 was better described by the Freundlich model, indicating heterogeneous adsorption behavior. Under the tested experimental conditions, the apparent Langmuir qₘ values of these minerals decreased from 0.066 to 0.015 mmol·g⁻¹ with decreasing Mn/Fe ratio. However, As(V) adsorption on FM4, which had the lowest Mn and Fe contents, followed the Langmuir model (qₘ = 0.012 mmol·g⁻¹), suggesting monolayer adsorption. Column experiments demonstrated rapid As(V) retention for all minerals. In the time domain, increasing the flow rate from 0.5 to 2.0 mL·min⁻¹ generally advanced breakthrough and shortened the desorption tail, although the breakthrough behavior expressed in pore-volume coordinates was not strictly monotonic for all minerals. The Two-Site Kinetic Attachment Model (TSKAM) successfully simulated these dynamics (R² > 0.90, RMSE < 0.05), revealing adsorption controlled by fast and slow kinetic sites, with slow-site contributions diminishing at higher flow rates. Characterization results indicated that adsorbed arsenic on FM1 remained mainly as As(V) and was immobilized primarily through surface complexation involving surface hydroxyl and Fe/Mn–O groups. XRD and SEM-EDS suggested the participation of Fe/Mn-bearing phases, while XPS on FM1 showed pronounced changes in Mn surface species during adsorption. Therefore, As(V) removal by these natural manganese minerals is a coupled physicochemical process influenced by both mineral properties, including Mn/Fe ratio, specific surface area, pore structure, pH_PZC, and Mn surface-state changes, and hydrodynamic conditions in the polymetallic mining areas. Full article

Agentic artificial intelligence—systems that reason, plan, and act autonomously within governed workflows—is converging with autonomous electric mobility and urban robotics to reshape how cities govern, move, and manage physical space. We argue that the simultaneous arrival of these three vectors is triggering a transformation comparable in scope to the Industrial Revolution. Cities that deploy across all three domains are becoming the new hubs of innovation: they concentrate talent, accelerate knowledge circulation, enable cross-fertilisation, and generate hybrid proposals that no single vector could produce alone. Just as Manchester, Birmingham, and the Ruhr became the defining centres of industrialisation because steam, textiles, iron, and coal recombined through the proximity of the engineers and entrepreneurs who moved between them, a small number of cities today are pulling ahead because they host the shared talent pool around which agentic governance, autonomous mobility, and urban robotics co-evolve. Conceptually, we extend the mirroring hypothesis in two directions: dynamically, arguing that organisations and urban ecosystems converge toward the configurations new technologies make possible; and ontologically, arguing that agentic AI introduces non-human agents into organisational architectures, requiring hybrid human–AI coordination. We formalise this dynamic as five propositions (P1–P5) of cumulative recursive hybridisation (CRH), operating through four reinforcing feedback loops—data, regulation, infrastructure, and talent. Together, these loops explain why the emerging urban order is path-dependent: early movers accumulate compounding advantages, while latecomers face exponentially rising costs of entry. We demarcate CRH from adjacent frameworks—general-purpose technologies, organisational complementarities, and complex adaptive systems—and test it against counterfactual evidence from failed, stalled, and Global South trajectories (Sidewalk Toronto, the Cruise rollback, Songdo, Bengaluru). We also examine its political-economy, equity, and surveillance limits. Drawing on comparative evidence from public-sector chatbot deployments, autonomous mobility ecosystems in the United States and China, and emerging urban robotics cases, we conclude that what is at stake is not incremental modernisation but the construction of a new urban order. The cities that act as innovation hubs for the agentic AI era will shape global standards, attract global talent, and define the institutional templates that others eventually adopt—much as the industrial cities of the eighteenth and nineteenth centuries did. Full article

In this study, a hydrogel was developed based on a chondroitin sulfate–iron complex (CSFe) incorporated into a sodium alginate matrix. The CSFe complex was first prepared through the interaction of chondroitin sulfate (CS) with Fe³⁺ ions, achieving an iron content of 2.06%. Structural characterization confirmed that Fe³⁺ coordinated with the carboxyl, sulfate, and N-acetyl groups of CS, resulting in increased molecular weight and altered physicochemical properties. The CSFe complex exhibited significant antibacterial activity against Escherichia coli and Staphylococcus aureus (S. aureus), and was further incorporated into a sodium alginate matrix to form an injectable hydrogel with favorable physicochemical properties such as spreadability, shear-thinning behavior, and a compact porous microstructure. In a mouse model of S. aureus-infected wounds, the CSFe hydrogel significantly accelerated wound closure, reduced the levels of pro-inflammatory cytokines (TNF-α and IL-6), and increased the anti-inflammatory cytokine IL-10, indicating potent anti-infective and immunomodulatory functions. Overall, this work presents a multifunctional CSFe-incorporated hydrogel system that integrates antibacterial, anti-inflammatory, and tissue-regenerative properties, offering a promising strategy for infected wound healing and highlighting the potential of trivalent iron–polysaccharide coordination complexes in the development of advanced biomedical materials. Full article

The zinc–iron redox battery (ZIRB) has become one of the hot technologies of electrochemical energy storage due to its safety, stability and low cost of the electrolyte. In this paper, a collaborative control strategy for an MW-level zinc–iron flow battery energy storage system is studied, and the operation control and management of the MW-level zinc–iron flow battery energy storage system are coordinated and optimized to improve the operation efficiency of the whole system. The model of the megawatt zinc–iron flow battery energy storage system is established in this paper. A ZIRB state of charge (SOC) estimation method based on least squares (LS) and an extended Kalman filter (EKF) is proposed. Experiments under constant-current discharge show that the proposed LS-EKF method can achieve accurate SOC estimation for the tested ZIRB system, with a maximum estimation error of approximately 2.3%. Experiments show that the proposed algorithm has good accuracy, rapidity and robustness at different SOC initial values. According to SOC differences between battery cells, the coordination strategy of each cell is designed to meet the requirements of frequency modulation while taking into account the safety of battery operation. On this basis, the optimization problem is designed and solved with the goal of optimal frequency modulation effect and battery energy loss, and the collaborative control of the MW-level ZIRB energy storage system is realized. Full article

Ferroptosis is an iron-dependent form of regulated cell death driven by lipid peroxidation and oxidative stress, increasingly implicated in cancer biology. However, its molecular regulation across breast cancer subtypes and its potential systemic manifestations remain incompletely understood. The aim of this study was to identify ferroptosis-associated molecular alterations that are largely shared across subtypes and to evaluate their systemic reflection following localized tissue injury. Tumor and matched normal breast tissues representing major molecular subtypes were analyzed. Global mRNA and miRNA expression profiling was performed using microarrays, followed by validation of selected genes using quantitative reverse transcription polymerase chain reaction (qRT-PCR) and enzyme-linked immunosorbent assay (ELISA). Functional enrichment and protein–protein interaction analyses were conducted to characterize associated pathways. In addition, systemic responses were assessed in patients undergoing fibroadenoma cryoablation through longitudinal blood sampling. Six ferroptosis-related genes (SLC7A11, GPX4, FTH1, NQO1, NFE2L2, SQSTM1) demonstrated consistent upregulation across all breast cancer subtypes, with higher expression observed in more aggressive tumors. These genes are functionally linked to antioxidant defense, iron metabolism, and oxidative stress regulation, and their coordinated expression pattern is consistent with activation of NRF2-dependent cytoprotective pathways. Downregulation of selected miRNAs may contribute to this expression profile but likely represents a secondary regulatory mechanism. Survival analysis revealed heterogeneous and subtype-dependent associations, with limited and gene-specific prognostic relevance. Cryoablation induced transient increases in circulating levels of the analyzed proteins, reflecting systemic responses to localized tissue injury. In conclusion, breast cancer is characterized by a largely shared ferroptosis-associated molecular signature across subtypes; however, its clinical impact appears to be variable and context-dependent. Systemic detection of related molecular signals suggests potential utility as indicators of tissue stress responses, although their role as specific biomarkers of ferroptosis requires further validation. Full article

Repairing maxillofacial bone defects remains a major clinical challenge due to inadequate vascularisation and poor integration with host tissue. While bioactive scaffolds have shown promise in supporting osteogenesis and angiogenesis, achieving robust and synchronised dual regenerative outcomes is still elusive. This study presents a multifunctional, cell-free magnetic hydrogel platform designed to biomimetically coordinate osteogenic and angiogenic processes for effective maxillofacial bone regeneration. The composite poly(vinyl alcohol)-vaterite (PVA-Vat) hydrogel scaffold incorporates tuneable magnetic nanoparticles (MNPs) composed of single-domain superparamagnetic iron oxide (Fe₃O₄). By harnessing magneto-mechanical cues to orchestrate bilateral communication between human bone mesenchymal stem cells and endothelial cells, this platform provides a deeper mechanistic understanding of coupled tissue regeneration and delivers superior dual-regenerative performance for maxillofacial bone repair. Under magnetic stimulation, a coculture system demonstrated strong osteogenesis-angiogenesis coupling mediated by reciprocal VEGFA-BMP2 signalling. This reciprocal crosstalk was evidenced by a synergistic amplification of VEGFA and BMP2 expression in coculture compared to monocultures, where MNP-stimulated osteoprogenitors secreted VEGFA to drive endothelial capillary-like network formation, while endothelial cells reciprocally enhanced endogenous BMP2 levels to accelerate osteoblastic mineralisation. These findings establish MNP-integrated hydrogels as a cell-free, multifunctional platform capable of synchronising dual regenerative pathways, offering a biomimetic strategy to overcome vascularisation and integration barriers in maxillofacial bone repair. Full article

Background: Post-Traumatic Stress Disorder (PTSD) is among the most prevalent and disabling mental health conditions affecting military veterans in Western countries. In recent decades, PTSD has increasingly been conceptualized as a systemic neuropsychological injury shaped not only by individual psychopathology, but also by institutional, cultural, and political contexts, particularly in settings of prolonged conflict and political violence. This shift has given rise to diverse national rehabilitation models that extend beyond symptom-focused care. This narrative comparative review aims to examine national models of PTSD rehabilitation among military veterans and to derive policy-relevant insights for Israel. Methods: We conducted a narrative comparative review of peer-reviewed literature and national policy documents published between 2014 and 2023, examining military and veteran PTSD rehabilitation frameworks in six Western countries: the United States, Canada, the United Kingdom, Germany, Australia, and the Netherlands. Sources were identified through PubMed, PsycINFO, Google Scholar, and governmental repositories. The review focused on system-level rehabilitation structures, including clinical services, peer-based programs, occupational integration, community and cultural components, and national monitoring practices. Results: Across countries, recurring challenges included persistent stigma limiting help-seeking, fragmented service delivery, inconsistent access to evidence-based care and a lack of standardized outcome indicators capturing functional and social recovery. Innovative approaches included biopsychosocial-spiritual rehabilitation models, peer-led interventions, intra-systemic employment pathways, and symbolic forms of social recognition. In this context, the biopsychosocial-spiritual approach refers to integrative rehabilitation models that extend beyond traditional frameworks by incorporating meaning-making, identity reconstruction, and value-based recovery processes. Conclusions: The findings highlight the need to reconceptualize PTSD rehabilitation as a multidimensional, system-level process. In light of the 2023 “Iron Swords” war and the scale of trauma exposure in Israel, the review informs actionable recommendations for developing a coordinated national rehabilitation strategy that integrates clinical care with occupational, community and cultural recovery. Full article

Siderophores are high-affinity iron-chelating metabolites that underpin microbial survival in iron-limited environments and play central roles in metal homeostasis, ecological competition, and pathogenesis. Traditionally viewed as dedicated Fe(III) scavengers, siderophores are now recognized as structurally and functionally versatile coordination agents whose donor-set architectures—particularly catecholate and α-hydroxycarboxylate motifs—permit conditional interactions beyond iron. In iron- and boron-rich niches, especially marine and mildly alkaline systems where borate availability increases, certain siderophores are chemically capable of forming reversible borate complexes through cis-diol coordination. Although Fe(III) exhibits substantially higher thermodynamic affinity and remains the primary biological target, boron binding represents a predictable secondary property arising from shared oxygen-donor chemistry. This dynamic interplay allows siderophores to cycle between iron-bound, boron-bound, and apo states depending on local redox conditions, pH, and metal availability. Here, we synthesize current knowledge on the structural classes of microbial siderophores, their transport and regulatory mechanisms, and emerging evidence for boron coordination within catecholate and carboxylate systems. By integrating coordination chemistry with microbial ecology, we propose an expanded model in which siderophores function not only as iron acquisition molecules but also as modulators of boron speciation and environmental sensing. This functional plasticity positions siderophores at the intersection of iron and boron biogeochemical cycles and highlights new directions for understanding microbial adaptation in complex metal-rich environments. Full article

The widespread use of plastics has inevitably led to the accumulation of persistent plastic debris in aquatic systems, where gradual fragmentation generates microplastics (MPs) that threaten ecological and biological health. Their small size, chemical stability, and resistance to degradation make effective removal particularly challenging. In this work, a composite adsorbent was fabricated through the in situ solvothermal growth of Materials of Institute Lavoisier 100 (Iron) (MIL-100(Fe)) onto coconut shell-derived activated carbon (CSAC), yielding a monolithic material denoted as CSAC@MIL-100(Fe). The integration of porous C with a metal–organic framework created a hierarchically structured adsorbent rich in accessible binding sites. The composite achieved a maximum polystyrene (PS) removal efficiency of 97.4% and maintained 91.44% efficiency after seven regeneration cycles. Stable adsorption performance was observed across a broad pH range. Structural and chemical analyses (scanning electron microscopy (SEM), Brunauer–Emmett–Teller (BET), X-ray diffraction (XRD), Fourier transform infrared spectroscopy (FTIR), X-ray photoelectron spectroscopy (XPS)) combined with adsorption modeling revealed heterogeneous multilayer adsorption behavior consistent with the Freundlich isotherm and pseudo-second-order kinetics. π–π interactions, electrostatic attraction, and coordination effects jointly governed PS capture. The Langmuir maximum adsorption capacity reached 746.27 mg/g. These findings demonstrate a practical and recyclable strategy for efficient MP remediation in aquatic environments. Full article

To address the low efficiency of finite element modeling and the reliance on manual measurements in electric/magnetic field analysis of complex overhead transmission line structures, this paper develops an IronPython-based automated computational platform within ANSYS Maxwell for 3-D modeling and electric/magnetic field analysis. First, by parsing transmission line data from the Grid Information Model (GIM), a unified coordinate transformation method is proposed to convert geographical coordinates into three-dimensional (3-D) Cartesian coordinates for finite element analysis. Based on the extracted line parameters, conductor sag is calculated and catenary modeling is implemented. An equivalent radius method is also introduced to simplify multi-bundle conductor modeling, enabling fast parametric construction of complex 3-D transmission line models. Second, by combining the IronPython scripting language with the .NET Windows Forms control library, a visualized finite element modeling and computation platform is developed. Finally, a typical double-circuit transmission line on the same tower is taken as a case study to calculate the spatial distribution of electric/magnetic fields. The influence of solution domain size on electric/magnetic field computation results is investigated, and optimal solution domain parameters are determined. The finite element results generated by the developed platform are further validated through comparison with measured data. The results demonstrate good agreement between calculated and measured values, confirming the accuracy and engineering applicability of the developed platform for electric/magnetic environment analysis of overhead transmission lines. Full article

In this work, the electrochemical behavior of potassium jarosite-type solid solutions synthesized via a controlled hydrothermal method was evaluated. Structural characterization by X-ray diffraction (XRD) confirmed the formation of potassium jarosite. FTIR spectra complemented these findings, revealing bands characteristic of Fe–O metal coordination (625 and 505 cm⁻¹). Voltammetric tests evidenced redox processes attributable to the Fe³⁺/Fe²⁺ couple, suggesting that iron within the jarosite framework contributes electrochemically to the observed conductivity. The assembled galvanic cells demonstrated the capability for electrical energy microgeneration, and the presence of jarosite was found to enhance ionic transport within the system. Overall, these results suggest an intergranular ionic-conduction mechanism, possibly facilitated by the mineral matrix, which would act as a structural medium enabling the mobility of charged species. Full article

Carnosine (or β-alanyl-L-histidine) is an endogenous compound playing very important roles in human organisms as antiglycation and antioxidant agents, and, in addition, helping to mitigate illnesses such as cancer and neurodegenerative diseases. Aiming to explore the chelating ability of carnosine, based on its coordinating possibilities, we started to investigate the metal complexes of essential copper(II), zinc(II), and iron(II) ions coordinated to this dipeptide. Different compounds were isolated in the solid state by adding stoichiometric amounts of metal salts to carnosine at controlled pH or under a controlled atmosphere, with the formation of mono-, bi- and polynuclear species. These complexes were subsequently characterized mainly by spectroscopic techniques (UV–Vis, IR, EPR), in addition to elemental analysis. A binuclear species was isolated with copper(II) and had its structure determined by X-ray diffraction, improving previously reported data in the literature. Two insoluble correlated trinuclear species were isolated with zinc(II) ions, using perchlorate or chloride as counter-ions. In the case of iron, a mononuclear species was verified with Fe(II) ions, obtained under an inert atmosphere. Further, the antioxidant properties of free carnosine and the copper–carnosine complex were verified by their scavenging activity toward the ABTS^•+ radical, using Trolox as a reference, showing significant activity. The carnosine–metal complexes were also tested as potential antineoplastic agents, in comparison to the free ligand, after 24 h of incubation at 37 °C, using malignant HeLa, SKMEL 28 and SKMEL 147, and non-tumor fibroblast cells. Results indicated neglected or poor anti-proliferative properties of these metal complexes, when compared to other similar compounds described in the literature. Full article

Background/Objectives: Transfusion-dependent β-thalassaemia (TDT) is a lifelong condition requiring coordinated multidisciplinary care. In France, where the disease is rare, transition from pediatric to adult care remains poorly structured, potentially compromising adherence and long-term outcomes. Methods: This national retrospective study evaluated current transition practices and their clinical impact among young adults with TDT. Patients aged 20–25 years in December 2022 were identified from the national NaThalY registry. Those diagnosed and managed in France before age 15 were included. Clinical data were collected for the two years preceding and following transition. Transition practices were assessed using a standardized questionnaire sent to pediatric centers. Results: Thirty-four patients were included (mean transition age: 19 years). The rate of response to the questionnaire was 90.5%, with feedback from 19 centers. Only one-third of centers offered joint pediatric–adult consultations, and one-quarter provided transition-focused education. No written transition protocols were reported. Mean pre-transfusion hemoglobin levels were significantly lower after the transition (8.5 vs. 8.0 g/dL; p = 0.01). Ferritin levels showed a non-significant increase, with no statistically significant changes observed in hepatic or cardiac iron concentrations. Conclusions: This study demonstrates marked heterogeneity and limited formalization of transition practices in France. Development of structured, standardized transition pathways is urgently needed to ensure continuity of care and optimal disease management in adults with TDT. Full article