Search Results (87)

Glioblastoma (GB) is one of the most aggressive and invasive cancers. Current treatment protocols for GB include surgical resection, radiotherapy, and chemotherapy with temozolomide. However, despite these treatments, physicians still struggle to effectively image, diagnose, and treat GB. As such, patients frequently experience recurrence of GB, demanding innovative strategies for early detection and effective therapy. Bioconjugated quantum dots (QDs) have emerged as powerful nanoplatforms for precision imaging and targeted drug delivery due to their unique optical properties, tunable size, and surface versatility. Due to their extremely small size, QDs can cross the blood–brain barrier and be used for precision imaging of GB. This review explores the integration of QDs with click chemistry for robust bioconjugation, focusing on artificial intelligence (AI) to advance GB therapy, mechanistic insights into cellular uptake and signaling, and strategies for mitigating toxicity. Click chemistry enables site-specific and stable conjugation of targeting ligands, peptides, and therapeutic agents to QDs, enhancing selectivity and functionalization. Algorithms driven by AI may facilitate predictive modeling, image reconstruction, and personalized treatment planning, optimizing QD design and therapeutic outcomes. We discuss molecular mechanisms underlying interactions of QDs with GB, including receptor-mediated endocytosis and intracellular trafficking, which influence biodistribution and therapeutic efficacy. Use of QDs in photodynamic therapy, which uses reactive oxygen species to induce apoptotic cell death in GB cells, is an innovative therapy that is covered in this review. Finally, this review addresses concerns associated with the toxicity of metal-based QDs and highlights how QDs can be coupled with AI to develop new methods for precision imaging for detecting and treating GB for induction of apoptosis. By converging nanotechnology and computational intelligence, bioconjugated QDs represent a transformative platform for paving a safer path to smarter and more effective clinical interventions of GB. Full article

This study investigates the impact of tire wear particles (TWPs) and their dissolved organic matter (DOM) on soil DOM dynamics and heavy metal behavior. Through short-term incubation experiments under simulated natural conditions with TWPs of varying particle sizes, we analyzed ecological changes in soil. Using three-dimensional excitation–emission matrix (3D-EEM) spectroscopy coupled with parallel factor analysis, we monitored the photochemical properties and compositional evolution of soil dissolved organic matter. Results demonstrate that TWP amendment substantially alters soil DOM molecular characteristics, inducing a sharp decrease in protein-, carbohydrate-, and lipid-like components, the degradation of low-aromaticity unstable dissolved organic matter, and an overall increase in aromaticity. Furthermore, TWP input directly modified soil properties, triggering the transformation of soil aggregates: the proportion of large aggregates significantly decreased while that of small aggregates increased, thereby reducing overall aggregate stability. The bioaccessibility of heavy metals (HMs) (Cd, Cu, and Zn) extracted by CaCl₂ increased, primarily due to the release of endogenous metals from TWPs, compounded by the disruption of soil aggregates. In contrast, Pb tended to transform into more stable fractions under TWP stress, reducing its bioaccessibility. Further correlation analysis indicated that TWPs indirectly affected HM (Cd, Cu, and Zn) fractionation by influencing the soil dissolved organic matter properties and soil properties. This study provides a new perspective for elucidating the interplay between dissolved organic matter and HMs in urban soils, as mediated by tire wear particles (TWPs). Full article

A rapid, colorimetric sensor for histamine detection is presented using citrate-stabilized gold nanoparticles enhanced with Cu²⁺ coordination. The sensing mechanism involves dual recognition: protonated histamine first adsorbs electrostatically onto AuNP surfaces at pH 5.5, followed by Cu²⁺-mediated coordination between imidazole rings that induces interparticle coupling, resulting in a characteristic shift of the localized surface plasmon resonance from 520 to 620 nm. The optical response, measured as the absorbance ratio A₆₂₀/A₅₂₀, exhibits excellent linearity over the range of 1.25–10 μM with a detection limit of 0.95 μM and total assay time under 30 min. The dual-recognition mechanism provides high selectivity for histamine over structural analogs, including L-histidine, imidazole, and L-lysine. The metal ion-mediated colorimetric approach described here achieves sub-micromolar sensitivity in simple buffer solutions, which is comparable to the histamine level used in in vitro cell assays and food-related studies. Thus, the present system is best viewed as a mechanistic model that can inform the design of future biosensing and analytical methods, rather than as a fully optimized sensor for direct clinical measurements in complex biofluids. Full article

The Yellow River Basin (YRB) is a vital water source and an essential ecological barrier in northern China. Currently, it faces pressing challenges related to water resource security and displays pronounced disparities in regional economic development. In recent years, with the elevation of Ecological Protection and High-Quality Development to a national strategy, examining the interaction between industrial growth and water environmental quality within the basin has become a priority. This study focuses on the mainstem of the YRB. By compiling relevant data from 2000 to 2021 and collecting water samples from 20 mainstem sites, and by integrating spatial distribution information of key industrial sectors with water quality records (including representative heavy metals and anions), we found that the basin’s economic output expanded significantly over the past two decades, approximately 11.7 times. The industrial structure evolved across provinces within the basin, exhibiting an overall upward trend in industrial upgrading; nevertheless, substantial differences in industrial composition and transformation persist between the upper and lower reaches. Spatial variations in different industries are closely associated with pollutant concentrations. In particular, major industries in the middle–lower reaches, notably concentrated in regions such as Shandong, possess high total asset values. Output from certain sectors (e.g., petroleum extraction, coal mining and processing, non-metallic mineral mining and processing) is strongly correlated with pollution changes, with marked spatial linkages between their geographic distribution and concentrations of critical heavy metals (Cu, Se, Mo, Mn, Ni). Moreover, spatial analysis of the industry–pollution nexus reveals an apparent paradox in the middle–lower YRB: high industrial output coupled with relatively low levels of heavy metal contamination. This finding highlights the pivotal role of an advanced industrial structure and elevated regional development quality in mediating the balance between economic expansion and environmental pressure. In conclusion, as a globally significant large river basin, the YRB demonstrates a tight coupling between water quality and industrial structure. The results provide spatially explicit scientific evidence and policy guidance for the coordinated advancement of industrial green transformation and water quality improvement in the YRB, offering broader insights into industrial structure patterns and pollution control strategies applicable to major river basins worldwide. Full article

Photoactivatable nitric oxide donors (photoNORMs) are promising agents for controlled NO release and real-time optical tracking in biomedical theranostics. Here, we report a comprehensive density functional theory (DFT) and time-dependent DFT (TDDFT) study on a series of hybrid ruthenium–gold nanocluster systems of the general formula [(L)Ru(NO)(SH)@Au₂₀], where L = salen, bpb, porphyrin, or phthalocyanine. Structural and bonding analyses reveal that the Ru–NO bond maintains a formal {RuNO}⁶ configuration with pronounced Ru → π*(NO) backbonding, leading to partial reduction of the NO ligand and an elongated N–O bond. Natural Bond Orbital (NBO), Natural Energy Decomposition Analysis (NEDA), and Extended Transition State–Natural Orbitals for Chemical Valence (ETS–NOCV) analyses confirm that Ru–NO bonding is dominated by charge-transfer and polarization components, while Ru–S and Au–S linkages exhibit a delocalized, donor–acceptor character coupling the molecular chromophore with the metallic cluster. TDDFT results reproduce visible–near-infrared (NIR) absorption features arising from mixed metal-to-ligand and cluster-mediated charge-transfer transitions. The calculated zero–zero transition and reorganization energies predict NIR-II emission (1.8–3.8 μm), a region of high biomedical transparency, making these systems ideal candidates for luminescence-based NO sensing and therapy. This study establishes fundamental design principles for next-generation Ru-based photoNORMs integrated with plasmonic gold nanoclusters, highlighting their potential as multifunctional, optically trackable theranostic platforms. Full article

Porcelain-fused-to-metal (PFM) crowns continue to serve as a cornerstone of restorative dentistry owing to their strength, affordability, and esthetics. However, late-onset complications such as oral burning and lichenoid reactions have been observed in long-serving PFMs, suggesting complex host–material interactions that extend beyond simple mechanical wear. This Perspective introduces the Nallan–Nickel Effect, a theoretical model proposing that a host- and environment-dependent threshold of bioavailable nickel ions (Ni²⁺), once exceeded, may trigger a neuro-immune cascade culminating in a burning phenotype. Within this framework, slow corrosion at exposed PFM interfaces releases Ni²⁺ into saliva and crevicular fluid, facilitating epithelial uptake and activation of innate immune sensors such as TLR4 and NLRP3. The resulting cytokine milieu (IL-1β, IL-6, TNF-α) drives NF-κB, mediated inflammation and T-cell activation, while neurogenic mediators—including nerve growth factor (NGF), substance P, and CGRP—sensitize TRPV1/TRPA1 nociceptors, establishing feedback loops of persistent burning and neurogenic inflammation. Modifying factors such as low salivary flow, acidic oral pH, mixed-metal galvanic coupling, and parafunctional stress can lower this threshold, whereas replacement with high-noble or all-ceramic materials may restore tolerance. The model generates testable predictions: elevated local free Ni²⁺ levels and increased expression of TLR4 and TRPV1 in symptomatic mucosa, along with clinical improvement following substitution of nickel-containing restorations. Conceptually, the Nallan–Nickel Effect reframes PFM-associated burning and lichenoid lesions as threshold-governed, neuro-immune phenomena rather than nonspecific irritations. By integrating corrosion chemistry, mucosal immunology, and sensory neurobiology, this hypothesis offers a coherent, testable framework for future translational research and patient-centered management of PFM-related complications. Full article

This study evaluates the impact of mineralogy, elemental composition, and reaction pathways on hydrogen (H₂) generation in seven ultramafic and mafic (basaltic) rocks. Experiments were conducted under typical low-temperature hydrothermal conditions (150 °C) and captured early and evolving stages of fluid–rock interaction. Pre- and post-interactions, the solid phase was analyzed using X-ray Diffraction (XRD) and X-ray Photoelectron Spectroscopy (XPS), while Inductively Coupled Plasma Mass Spectrometry (ICP-MS) was used to determine the composition of the aqueous fluids. Results show that not all geologic H₂-generating reactions involving ultramafic and mafic rocks result in the formation of serpentine, brucite, or magnetite. Our observations suggest that while mineral transformation is significant and may be the predominant mechanism, there is also the contribution of surface-mediated electron transfer and redox cycling processes. The outcome suggests continuous H₂ production beyond mineral phase changes, indicating active reaction pathways. Particularly, in addition to transition metal sites, some ultramafic rock minerals may promote redox reactions, thereby facilitating ongoing H₂ production beyond their direct hydration. Fluid–rock interactions also regenerate reactive surfaces, such as clinochlore, zeolite, and augite, enabling sustained H₂ production, even without serpentine formation. Variation in reaction rates depends on mineralogy and reaction kinetics rather than being solely controlled by Fe oxidation states. These findings suggest that ultramafic and mafic rocks may serve as dynamic, self-sustaining systems for generating H₂. The potential involvement of transition metal sites (e.g., Ni, Mo, Mn, Cr, Cu) within the rock matrix may accelerate H₂ production, requiring further investigation. This perspective shifts the focus from serpentine formation as the primary driver of H₂ production to a more complex mechanism where mineral surfaces play a significant role. Understanding these processes will be valuable for refining experimental approaches, improving kinetic models of H₂ generation, and informing the site selection and design of engineered H₂ generation systems in ultramafic and mafic formations. Full article

Chrysin (5,7-dihydroxyflavone) is a flavonoid widely distributed in propolis, honey, and various plant sources. It exhibits a wide range of pharmacological activities, including anti-inflammatory, antioxidant, anticancer, antimicrobial, and anti-diabetic effects. However, its clinical translation is hampered by poor aqueous solubility, low bioavailability, and rapid metabolic clearance. To address these limitations and expand the chemical space of this natural scaffold, extensive synthetic efforts have focused on generating structurally diverse chrysin derivatives that possess improved drug-like properties. This review systematically categorizes synthetic methodologies—such as etherification, esterification, transition-metal-mediated couplings, sigmatropic rearrangements, and electrophilic substitutions—and integrates them with corresponding biological outcomes. Particular emphasis is placed on recent (2020–present) advances that directly link structural modifications with pharmacological enhancements, thereby offering comparative structure–activity relationship (SAR) insights. In addition, transition-metal-catalyzed C–C bond-forming reactions are highlighted in a dedicated section, underscoring their growing role in accessing bioactive chrysin analogs previously unattainable by conventional chemistry. Unlike prior reviews that mainly summarized biological activities or broadly covered flavonoid scaffolds, this article bridges synthetic diversification with pharmacological evaluation. It provides both critical synthesis and mechanistic interpretation. Overall, this work consolidates current knowledge and suggests future directions that integrate synthetic innovation with pharmacological validation and address pharmacokinetic challenges in chrysin derivatives. Full article

Structure–property relationships in imidazolium-based hybrid Sb(III) chlorides provide critical guidance for designing high-performance materials. Three zero-dimensional metal halides, namely, [C₃mmim]₂SbCl₅ (1, [C₃mmim]⁺ = 1-propyl-2,3-dimethylimidazolium), [C₅mmim]₂SbCl₅ (2, [C₅mmim]⁺ = 1-pentyl-2,3-dimethylimidazolium), and [C₅mim]₂SbCl₅ (3, [C₅mim]⁺ = 1-pentyl-3-methylimidazolium), are synthesized by ionothermal methods. These compounds exhibit markedly distinctly photophysical properties at their optimal excitation wavelengths. Structural analyses reveal that elongated alkyl chains in compounds 2 and 3 increase Sb–Sb distances compared to that in 1, effectively isolating [SbCl₅]²⁻ units, suppressing inter-center energy transfer, and reducing non-radiative transitions, thereby enhancing the photoluminescence quantum yield (PLQY). Furthermore, methyl substitution at the C2-position of the imidazolium ring in compounds 1 and 2 induces asymmetric coordination environments around the [SbCl₅]²⁻ emission centers, leading to pronounced structural distortion. This distortion promotes non-radiative decay pathways and diminishes luminescent efficiency. Furthermore, temperature-dependent spectroscopy analysis and fitting of the Huang–Rhys factor (S) reveal significant electron–phonon coupling in compounds 1–3, which effectively promotes the formation of self-trapped excitons (STEs). However, compound 1 exhibits extremely high S, which significantly enhances phonon-mediated non-radiative decay and ultimately reduces its PLQY. Overall, compound 3 has the highest PLQYs. Full article

The photon spin Hall effect (PSHE) arises from the spin–orbit interaction of light. Metasurfaces enable precise control over the PSHE through their influence. Using electromagnetic simulations as its foundation, this work engineers a metal–insulator–metal (MIM) metasurface for generating vortex beams in the near-infrared band, targeting enhanced modulation of the PSHE. Electromagnetic simulations embed vanadium dioxide (VO₂)—a thermally responsive phase-change material—within the MIM metasurface architecture. Numerical evidence confirms that harnessing VO₂’s insulator–metal-transition-mediated optical switching dynamically tailors spin-dependent splitting in the illuminated MIM-VO₂ hybrid, thereby achieving a significant amplification of the PSHE displacement. Electromagnetic simulations determine the reflection coefficients for both VO₂ phase states in the MIM-VO₂ structure. Computed spin displacements under vortex beam incidence reveal that VO₂’s phase transition couples to the MIM’s top metal and dielectric layers, modifying reflection coefficients and producing phase-dependent PSHE displacements. The simulation results show that the displacement change of the PSHE before and after the phase transition of VO₂ reaches 954.7 µm, achieving a significant improvement compared with the traditional layered structure. The dynamic modulation mechanism of the PSHE based on the thermal–optical effect has been successfully verified. Full article

Seamounts are distributed globally across the oceans and are generally considered oases of biomass abundance as well as hotspots of species richness. Diverse microbial communities are essential for biogeochemical cycling, yet their functional partitioning among seamounts with geographic features remains poorly investigated. Through metagenomic sequencing and genome-resolved analysis, we revealed that Proteobacteria (33.18–40.35%) dominated the bacterial communities, while Thaumarchaeota (5.98–10.86%) were the predominant archaea. Metagenome-assembled genomes uncovered 117 medium-quality genomes, 81.91% of which lacked species-level annotation, highlighting uncultured diversity. In the Nazuna seamount, which is located in the Marcus-Wake seamount region, microbiomes exhibited heightened autotrophic potential via the 3-hydroxypropionate cycle and dissimilatory nitrate reduction, whereas in the Magellan seamounts regions, nitrification and organic nitrogen metabolism were prioritized. Sulfur oxidation genes dominated Nazuna seamount microbes, with 33 MAGs coupling denitrification to sulfur redox pathways. Metal resistance genes for tellurium, mercury, and copper were prevalent, alongside habitat-specific iron transport systems. Cross-feeding interactions mediated by manganese, reduced ferredoxin, and sulfur–metal integration suggested adaptive detoxification strategies. This study elucidates how deep-sea microbes partition metabolic roles and evolve metal resilience mechanisms across geographical niches. It also supports the view that microbial community structure and metabolic function across seamount regions are likely influenced by the geomorphological features of the seamounts. Full article

Acetone carboxylase (AC) from Xanthobacter autotrophicus is a 360 KDa α₂β₂γ₂ heterohexamer that catalyzes the ATP-dependent formation of phosphorylated acetone and bicarbonate intermediates that react at Mn(II) metal active sites to form acetoacetate. Structural models of X. autotrophicus AC (XaAC) with and without nucleotides reveal that the binding and phosphorylation of the two substrates occurs ~40 Å from the Mn(II) active sites where acetoacetate is formed. Based on the crystal structures, a significant conformational change was proposed to open and close a tunnel that facilitates the passage of reaction intermediates between the sites for nucleotide binding and phosphorylation of substrates and Mn(II) sites of acetoacetate formation. We have employed electron paramagnetic resonance (EPR), kinetic assays, and hydrogen/deuterium exchange mass spectrometry (HDX-MS) of poised ligand-bound states and site-specific amino acid variants to complete an in-depth analysis of Mn(II) coordination and allosteric communication throughout the catalytic cycle. In contrast with the established paradigms for carboxylation, our analyses of XaAC suggested a carboxylate shift that couples both local and long-range structural transitions. Shifts in the coordination mode of a single carboxylic acid residue (αE89) mediate both catalysis proximal to a Mn(II) center and communication with an ATP active site in a separate subunit of a 180 kDa α₂β₂γ₂ complex at a distance of 40 Å. This work demonstrates the power of combining structural models from X-ray crystallography with solution-phase spectroscopy and biophysical techniques to elucidate functional aspects of a multi-subunit enzyme. Full article

Two-dimensional transition metal carbides/nitrides (MXenes) have shown potential in biosensors, cancer theranostics, microbiology, electromagnetic interference shielding, photothermal conversion, and thermal energy storage due to their unique electronic structure, ability to absorb a wide range of light, and tunable surface chemistry. In spite of the growing interest in MXenes, there are relatively few studies on their applications in phase-change materials for enhancing thermal conductivity and weak photo-responsiveness between 0 °C and 150 °C. Thus, this study aims to provide a current overview of recent developments, to examine how MXenes are made, and to outline the combined effects of different processes that can convert light into heat. This study illustrates the mechanisms that include enhanced broadband photon harvesting through localized surface plasmon resonance, electron–phonon coupling-mediated nonradiative relaxation, and interlayer phonon transport that optimizes thermal diffusion pathways. This study emphasizes that MXene-engineered 3D thermal networks can greatly improve energy storage and heat conversion, solving important problems with phase-change materials (PCMs), like poor heat conductivity and low responsiveness to light. This study also highlights the real-world issues of making MXene-based materials on a large scale, and suggests future research directions for using them in smart thermal management systems and solar thermal grid technologies. Full article

This review systematically examines the critical mechanisms and process optimization strategies of algal–bacterial granular sludge (ABGS) technology in wastewater treatment. The key findings highlight the following: (1) enhanced pollutant removal—ABGS achieves >90% COD removal, >80% total nitrogen elimination via nitrification–denitrification coupling, and 70–95% phosphorus uptake through polyphosphate-accumulating organisms (PAOs), with simultaneous adsorption of heavy metals (e.g., Cu²⁺, Pb²⁺) via EPS binding; (2) energy-saving advantages—microalgal oxygen production reduces aeration energy consumption by 30–50% compared to conventional activated sludge, while the granular stability maintains >85% biomass retention under hydraulic shocks; (3) AI-driven optimization—machine learning models enable real-time prediction of nutrient removal efficiency (±5% error) by correlating microbial composition (e.g., Nitrosomonas abundance) with operational parameters (DO: 2–4 mg/L, pH: 7.5–8.5). This review further identifies EPS-mediated microbial co-aggregation and Chlorella–Pseudomonas cross-feeding as pivotal for system resilience. These advances position ABGS as a sustainable solution for low-carbon wastewater treatment, although challenges persist in scaling photobioreactors and maintaining symbiosis under fluctuating industrial loads. Full article

This study pioneers the development of a synergistic Ag-doped molecularly imprinted TiO₂ photocatalyst (MIP-Ag-TiO₂) through a multi-strategy engineering approach, integrating molecular imprinting technology with plasmonic metal modification via a precisely optimized sol–gel protocol. Breaking from conventional non-selective photocatalysts, our material features an engineered surface architecture that combines selective molecular recognition sites with enhanced charge separation capabilities, specifically tailored for the targeted degradation of recalcitrant salicylic acid (SA) contaminants. Advanced characterization (XRD, EPR, FT-IR, TEM-EDS) reveals unprecedented structure–activity relationships, demonstrating how template molecule ratios (Ti:SA = 5:1) and calcination parameters (550 °C) collaboratively optimize both adsorption selectivity and quantum efficiency. The optimized MIP-Ag-TiO₂ achieves breakthrough performance metrics: 98.6% SA degradation efficiency at 1% Ag doping, coupled with a record selectivity coefficient R = 7.128. Mechanistic studies employing radical trapping experiments identify a dual •OH/O_2⁻-mediated degradation pathway enabled by the Ag-TiO₂ Schottky junction. This work establishes a paradigm-shifting “capture-and-destroy” photocatalytic system that simultaneously addresses the critical challenges of selectivity and quantum yield limitations in advanced oxidation processes, positioning molecularly imprinted plasmonic photocatalysts as next-generation smart materials for precision water purification. Full article