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Osteoarthritis (OA) is a degenerative joint disease characterized by obscure etiology and unsatisfactory therapeutic outcomes, making the development of new efficient therapies urgent. Superfluous reactive oxygen species (ROS) have historically been considered one of the crucial factors inducing the pathological progression of OA. Ultrasmall Prussian blue nanoparticles (USPBNPs), approximately sub-5 nm in size, are developed by regulating the configuration of polyvinylpyrrolidone chains. USPBNPs display an excellent ROS eliminating capacity and catalase-like activity, capable of decomposing hydrogen peroxide (H2O2) into O2. The anti-inflammatory mechanism of USPBNPs can be attributed to repolarizing macrophages from pro-inflammatory M1 to anti-inflammatory M2 phenotype by decreasing the ROS levels accompanied by O2 improvement. Additionally, USPBNPs exhibit an exciting therapeutic efficiency against OA, comparable to that of hydrocortisone in vivo. This study not only develops a new therapeutic agent for OA but also offers an estimable insight into the application of the nanozyme.

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Thallium, a highly toxic pollutant, shows greater toxicity to human than other common heavy metals such as mercury, lead, cadmium and its effective removal from wastewater gains great attention. The main restriction for the Tl+ removal is the interference of a high concentration of co-existing ions in wastewater. Therefore, the goal of the current work was to synthesis adsorbent with high selectivity for the Tl+ removal. Herein, the pore size sieving strategy was proposed and Prussian blue-impregnated biochar (BC@PB) particles was synthesized. More than 95% Tl+ can be removed even the concentrations of the coexistence ions (Na+, Cd2+, and Zn2+) 1,000 higher than the initial concentration of Tl+ (500 µg/L). BC@PB also showed large adsorption capacity (9365 µg/g) and more than 99% Tl+ (initial concentration, 500 µg/L) were removed in just 1 min. The BC@PB had excellent and stable Tl+ removal ability (> 99%) over a range of pH from 3 to 9, which covered the pH range of common thallium-containing wastewater. The density functional theory (DFT) calculation confirmed that not only hydrated volume but also the hydration free energy of ions, which governed the energy barrier for ions entering into narrow channels of BC@PB, played essential roles on the selectivity removal of Tl+. Overall, due to its high selectivity, high adsorption capacity and easy preparation process, the synthesized BC@PB particles based on the pore sizing sieving strategy, can be a promising candidate for the removal of thallium from wastewater.

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In recent years, core-shell structured Prussian Blue Analogues (PBAs) have been considered as highly promising cathode materials for sodium-ion batteries. Reducing production costs and simplifying the preparation method for core-shell PBAs have also become crucial considerations. This paper presents a novel approach for the first time: by acid-treating the as-synthesized solution from a simple coprecipitation reaction, a high-crystallinity, sodium-rich Mn2+-doped iron hexacyanoferrate (Fe/MnHCF) shell material is self-grown on the surface of manganese hexacyanoferrate (MnHCF). This method significantly improves the electrochemical properties of the MnHCF material. The core-shell structured PBA exhibits excellent cycling performance (with a capacity retention of 95.5 % for 400 cycles at 1 A/g) and high rate performance (134.2mAh/g@10 mA/g, 95.2mAh/g@1 A/g). In this article, we explore the growth mechanism of the high-sodium content, high-crystallinity shell structure and introduce a green chelating agent that is better suited for the crystallization of Mn and Fe-type PBA systems. Our study demonstrates that Mn2+ doping enhances the conductivity of the shell material. Meanwhile, the heterojunction structure of MnHCF@Fe/MnHCF conducive to charge separation and migration. This straightforward synthesis strategy offers a novel approach for fabricating high-performance core-shell structured Prussian Blue Analogue materials.

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Prussian blue (PB) is regarded as a promising cathode for sodium-ion batteries because of its sustainable precursor elements (e.g., Mn, Fe), easy preparation, and unique framework structure. However, the unstable structure and inherent crystal H2O restrain its practical application. For this purpose, a self-constructed trace Mg2+/K+ co-doped PB prepared via a sea-water-mediated method is proposed to address this problem. The Mg2+/K+ co-doping in the Na sites of PB is permitted by both thermodynamics and kinetics factors when synthesized in sea water. The results reveal that the introduced Mg2+ and K+ are immovable in the PB lattices and can form stronger K‒N and Mg‒N Coulombic attraction to relieve phase transition and element dissolution. Besides, the Mg2+/K+ co-doping can reduce defect and H2O contents. As a result, the PB prepared in sea water exhibits an extremely long cycle life (80.1% retention after 2400 cycles) and superior rate capability (90.4% capacity retention at 20 C relative to that at 0.1 C). To address its practical applications, a sodium salts recycling strategy is proposed to greatly reduce the PB production cost. This work provides a self-constructed Mg2+/K+ co-doped high-performance PB at a low preparation cost for sustainable, large-scale energy storage.

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Multivalent ions, especially Al3+ in aqueous electrolyte contributes to higher capacity and color contrast for more sustainable post-lithium electrochromism and energy storages. However, the lack of suitable cathodic and anodic electrochromic materials is a major challenge for Al-ion electrochromic batteries, which limits their optical contrast and lifespan. Herein, we report that Wadsley-Roth phase Nb18W16O93 with open structure achieves Al3+ intercalation/extraction reversibly. The complementary electrochromic energy storage devices based on Nb18W16O93 coupled with Prussian blue using hybrid Al3+/K+ aqueous electrolytes show a fast response, a high capacity and a large coloring efficiency. The superior performances are due to the cations of Al3+ and K+ selectively insert/extract in the electrode of Nb18W16O93 and Prussian blue, respectively. This work provides an effective strategy for high-performance and low-cost electrochromic batteries with higher sustainability.

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The electrochemical splitting of water for hydrogen production faces a major challenge due to its anodic oxygen evolution reaction (OER), necessitating research on the rational design and facile synthesis of OER catalysts to enhance catalytic activity and stability. This study proposes a ligand-induced MOF-on-MOF approach to fabricate various trimetallic MnFeCo-based Prussian blue analog (PBA) nanostructures. The addition of [Fe(CN)6]3- transforms them from cuboids with protruding corners (MnFeCoPBA-I) to core-shell configurations (MnFeCoPBA-II), and finally to hollow structures (MnFeCoPBA-III). After pyrolysis at 800 °C, they are converted into corresponding PBA-derived carbon nanomaterials, featuring uniformly dispersed Mn2Co2C nanoparticles. A comparative analysis demonstrates that the Fe addition enhances catalytic activity, while Mn-doped materials exhibit excellent stability. Specifically, the optimized MnFeCoNC-I-800 demonstrates outstanding OER performance in 1.0 m KOH solution, with an overpotential of 318 mV at 10 mA cm-2, maintaining stability for up to 150 h. Theoretical calculations elucidate synergistic interactions between Fe dopants and the Mn2Co2C matrix, reducing barriers for oxygen intermediates and improving intrinsic OER activity. These findings offer valuable insights into the structure-morphology relationships of MOF precursors, advancing the development of highly active and stable MOF-derived OER catalysts for practical applications.

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Aim: We investigate combining Prussian Blue nanoparticles (PBNPs), as photothermal therapy (PTT) agents, with agonistic CD137 antibodies (αCD137) on a single nanoparticle platform to deliver non-toxic, anti-tumor efficacy in SM1 murine melanoma.Methods: We electrostatically coated PBNPs with αCD137 (αCD137-PBNPs) and quantified their physicochemical characteristics, photothermal and co-stimulatory capabilities. Next, we tested the efficacy and hepatotoxicity of PTT using αCD137-PBNPs (αCD137-PBNP-PTT) in SM1 tumor-bearing mice.Results: The αCD137-PBNPs retained both the photothermal and agonistic properties of the PBNPs and αCD137, respectively. In vivo, SM1 tumor-bearing mice treated with αCD137-PBNP-PTT exhibited a significantly higher survival rate (50%) without hepatotoxicity, compared with control treatments.Conclusion: These data suggest the potential utility of co-localizing PBNP-PTT with αCD137-based agonism as a novel combination nanomedicine.

Photothermal therapy is a strategy to kill cancer cells that uses nanoparticles and lasers to generate heat. Here, we combine photothermal therapy with an immunotherapy that activates the body's T cells, a type of white blood cell, on a single platform, to treat melanoma, a type of skin cancer in a mouse. We find that this novel nanoparticle-based platform significantly improves the survival of mice bearing melanoma, without increasing liver toxicity.

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Aqueous sodium-ion batteries (ASIBs) are promising for large-scale electrical energy storage (LSEES) applications due to their cost and safety advantages. However, the low voltage stabilization window of water (∼1.23 V) and the lack of cathode with high specific capacity and long cycle life have limited their development. Cobalt-based Prussian blue analogues (NaCoPBAs) have the advantage of high theoretical specific capacity but short cycle life. Recently, the molecular crowding electrolyte (MCE) strategy has been proposed to improve the electrolyte voltage stability window (ESW) of electrolytes, in this work, we report an improved xMC (x: ratio, MC: molecular crowding agent) electrolyte that uses N-N dimethylacetamide (DMAC) as the molecular crowding agent and NaOTf as the advanced salt with an ESW of 2.65 V and excellent nonflammability. The side reactions of the NaCoPBA//Hard Carbon (HC) full-cell active material are improved with the aid of the electrolyte. Capacity retention of 75 % after 600 cycles with excellent cycling stability. These results demonstrate that this advanced MCE strategy can be utilized for practical applications designed for safety, high specific capacity and long cycle (ASIB).

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Prussian blue analogs (PBAs) have attracted extensive attention in the field of aqueous organic degradation due to the tremendous potential for peroxydisulfate (PDS) activation. However, the relationship between the d-band center of the catalyst and the activation behavior of PDS remained largely unexplored. Herein, a series of Fe-Co PBAs-based catalysts with different Fe/Co ratios (Fe-Co PBAs-1 = 1: 0.52; Fe-Co PBAs-2 = 1: 1.21, and Fe-Co PBAs-3 = 1: 1.48) have been prepared by a facile hydrothermal procedure and subsequent acid treatment (Fe-Co PBAs-xH). The as-prepared Fe-Co PBAs-xH exhibited superior PDS activation performance and excellent recyclability in the degradation of methylene blue (MB). Density functional theory calculations revealed that the electron-occupied state of the Fe-Co PBAs was shifted to the Fermi level, indicating a strong interaction and easier electron transfer. Moreover, the d-band center of Fe-Co PBAs was upshifted relative to that of Fe PBAs, suggesting easier adsorption of MB and PDS, which was beneficial to enhancing catalytic activation and subsequent dissociation. Radicals such as •OH, 1O2, O2•-, and SO4•- were determined by the radical quenching experiment and electron paramagnetic resonance (EPR) testing in the Fe-Co PBAs-3H/PDS system, and the order of MB degradation by the free active radical is •OH > 1O2 > O2•- > SO4•-. The degradation pathway and potential ecotoxicity of MB and its intermediates were also studied. This work can provide new insights to construct the efficient catalysts for the activation of PDS and the degradation of organic pollutants.

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Prussian blue analogues (PBAs) have attracted increasing attention in aqueous zinc-based batteries (AZBs) with the advantages of an open framework, adjustable redox potential, and easy synthesis. However, they exhibited a low specific capacity and a poor cycle performance. In this work, crystalline potassium iron hexacyanoferrate (FeHCF) with dislocation was designed and prepared by a poly(vinylpyrrolidone) (PVP) additive. The metastable state provided by PVP would cause an electrostatic interaction between cyanogen and water molecules. The reduced force increases the steric resistance of the water molecules entering the crystal. The low content of crystal water in FeHCF is associated with the formation of dislocation. The dislocation effect effectively improves the electrochemical reactivity and reaction kinetics of FeHCF. Thus, it presents a high reversible capacity of 131 mAh g-1 with a superior capacity retention of 85% after 550 cycles at 0.5 A g-1. When used as a cathode, the AZBs display a high voltage of 2.6 V, a fast charging capability (<5 min), and a satisfactory cycle stability with a capacity retention of 82% after 400 cycles at 0.2 A g-1 in decoupling electrolytes. This work provides an effective strategy for the design of high-performance PBA-based cathodes for 2.6 V AZBs.

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Therapeutic vaccine becomes a promising strategy to fight cancer by enhancing and sustaining specific anti-tumor immune responses. However, its efficacy is often impeded by low immunogenicity, the immunosuppressive tumor microenvironment (TME), and immune-related adverse events. Herein, we introduce 1-tetradecanol (TD)-wrapped, CpG-loaded porous Prussian blue nanoparticles (pPBNPs-CpG@TD) as a nanoimmunomodulator to initiate photothermal-induced immunogenic cell death (ICD) and photothermal-responsive release of CpG for augmenting the ICD effect. It was revealed that the dual-photothermal action significantly potentiated the in situ anti-tumor vaccine-like immunotherapy in terms of enhanced immunogenicity, promoted dendritic cell maturation, and increased T lymphocyte infiltration, consequently eliciting a robust immune response for inhibiting both primary and rechallenge tumors on a subcutaneous 4T1 tumor-bearing mouse model. The development and use of photoactive nanoimmunomodulators represents a novel and effective strategy to boost immunogenicity and counteract immunosuppressive TME, marking a significant advancement in the realm of ICD-driven in situ anti-tumor vaccine-like immunotherapy.

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Regulating the complex microenvironment after tooth extraction to promote alveolar bone regeneration is a pressing challenge for restorative dentistry. In this study, through modulating the mechanical properties of the cellular matrix, we guided various types of cells by self-organizing to form multicellular spheroids (MCSs) and hybridized MCSs with Prussian Blue nanoparticles (PBNPs) in the process. The constructed Prussian Blue nanohybridized multicellular spheroids (PBNPs@MCSs) with empowered antioxidant functions effectively reduced cell apoptosis under peroxidative conditions and exhibited enhanced ability to regulate the microenvironment and promote bone repair both in vitro and in vivo. In addition, the PBNPs@MCSs exhibited enhanced photoacoustic imaging ability to trace low doses of PBNPs. Therefore, the constructed PBNPs@MCSs based on the biomimetic hydrogel can be used as a form of an engraftment building block, with a greater potential for pro-bone repair application in the complex microenvironment of the oral cavity.

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Zeolitic Imidazolate (metal organic) Frameworks (ZIFs) and Prussian Blue Analogues (PBAs) are promising materials in electrochemical sensing due to their unique properties. In this study, a composite material comprising NiFe-PBA and ZIF-67 was synthesized and made to form a uniform layer onto a glassy carbon electrode (GCE) to enhance electrochemical performance for furazolidone (FZD) detection. The synthesized NiFe-PBA/ZIF-67 composite exhibited excellent sensitivity, selectivity, and stability towards FZD detection, with a low limit of detection (LOD). The electrochemical behaviour of FZD on the NiFe-PBA/ZIF-67/GCE electrode was investigated, revealing a diffusion-controlled process. Differential pulse voltammetry (DPV) analysis demonstrated the synergetic effect of the PBA/MOF core-shell structure in enhancing FZD electro-reduction. The sensor exhibited exceptional LOD of 0.007 µM. Selectivity studies confirmed the sensor's ability to distinguish FZD from potential interferents. Extensive evaluations demonstrated the sensor's reproducibility, repeatability, and long-term stability, affirming its practical utility. Real sample analysis further validated the sensor's excellent analytical capabilities in diverse matrices.

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Long-term inflammation and impaired angiogenesis are the main reasons for the difficulty of diabetic wound healing. What to do to effectively promote vascular endothelial cell response and immune cell reprogramming is the key to diabetic skin healing. However, contemporary therapies cannot simultaneously coordinate the promotion of vascular endothelial cells and macrophage polarization, which leads to an increased rate of disability in patients with chronic diabetes. Therefore, we developed a method of repair composed of self-assembling Prussian blue nanoenzymes, which achieved synergistic support for the immune microenvironment, and also contributed to macrophage polarization in the tissue regeneration cycle, and enhanced vascular endothelial cell activity. The template hydrothermal synthesis PB-Zr nanoplatform was prepared and locally applied to wounds to accelerate wound healing through the synergistic effect of reactive oxygen species (ROS). PB-Zr significantly normalized the wound microenvironment, thereby inhibiting ROS production and inflammatory response, which may be because it inhibited the M1 polarization of macrophages in a rat model of wound. PB-Zr treatment significantly promoted the activity of vascular endothelial cells, which better promoted the growth and regeneration of other tissues in the body. The results confirmed the disease microenvironment of PB-Zr-mediated wound therapy and indicated its application in other inflammation-related diseases.

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High entropy material (HEM) has emerged as an appealing material platform for various applications, and specifically, the electrochemical performances of HEM could be further improved through self-assembled structure design. However, it remains a big challenge to construct such high-entropy self-assemblies primarily due to the compositional complexity. Herein, we propose a bottom-up directional freezing route to self-assemble high-entropy hydrosols into porous nanosheets. Taking Prussian blue analogue (PBA) as an example, the simultaneous coordination-substitution reactions yield stable high-entropy PBA hydrosols. During subsequent directional freezing process, the anisotropic growth of ice crystals could guide the two-dimensional confined assembly of colloidal nanoparticles, resulting in high-entropy PBA nanosheets (HE-PBA NSs). Thanks to the high-entropy and self-assembled structure design, the HE-PBA NSs manifests markedly enhanced sodium storage kinetics and performances in comparison with medium/low entropy nanosheets and high entropy nanoparticles.

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Prussian blue analogs (PBAs) show promise as cathodes for sodium-ion batteries due to their notable cycle stability, cost-effectiveness, and eco-friendly nature, yet the presence of interstitial water limits the specific capacity and obstructs Na+ mobility within the material. Although considerable experimental efforts are focused on dehydrating water for capacity enhancement, there is still a deficiency of a comprehensive understanding of the low capacity of low-spin Fe resulting from interstitial water, which holds significance in Na+ storage. This study introduces a novel gas-assisted heat treatment method to efficiently remove interstitial water from Fe-based PBA (NaFeHCF) electrodes and combines experiments and theoretical calculations to reveal the iron spin state regulation that is related to the capacity enhancement mechanism. This dehydration strategy significantly enhances battery capacity, especially the portion at higher voltages (3.4-4.0 V). The increase in capacity is attributed to the following factors: an enhanced proportion of Fe2+, reduced water content which facilitates faster charge transfer, and the activation of low spin Fe2+. The optimized NaFeHCF demonstrated impressive half-cell performance of retaining 87.3% capacity after 2000 cycles at a 5 C rate and achieving 100 mAh g-1 capacity over 200 cycles when being paired with hard carbon, exhibiting its practical potential.

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This study addresses the urgent need to focus on the nitrite reduction reaction (NO2-RR) to ammonia (NH3). A ternary-metal Prussian blue analogue (CoCuFe-PBA) was utilized as the template material, leveraging its tunable electronic properties to synthesize CoCuFe oxide (CoCuFe-O) through controlled calcination. Subsequently, a CoCuFe alloy (CoCuFe-A) was obtained via pulsed laser irradiation in liquids. The electrochemical properties of CoCuFe-O, derived from the PBA crystal structure, demonstrated a high yield of NH4+ at a rate of 555.84 µmol h-1 cm-2, with the highest Faradaic efficiency of 91.8% and a selectivity of 97.3% during a 1-h NO2-RR under an optimized potential of -1.0 V vs. Ag/AgCl. In situ Raman spectroscopy revealed the collaborative role of redox pairs (Co3+/Co2+ and Fe3+/Fe2+) as proton (H+) suppliers, with Cu centers serving as NO2- binders, thereby enhancing the reaction rate. Additionally, theoretical studies confirmed that Fe and Co atoms are more reactive than Cu toward intermediates playing crucial roles in hydrogenation, while Cu primarily activates NO owing to hydrogenation by the Fe and Co atoms and a high kinetic barrier in H2O* adsorption. This comprehensive investigation provides valuable insights into the electrochemical NO2-RR, establishing a foundation for efficient and sustainable NH3 synthesis strategies.

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Prussian blue analogues (PBA) are a large family of functional materials with diverse applications such as in electrochemical fields. However, their use in the emerging two-electron oxygen reduction reaction for clean production of hydrogen peroxide (H2O2) is lagging. Herein, a general solvent exchange induced reconstruction strategy is demonstrated, through which an abnormal NiNi-PBA superstructure is synthesized as a high-performance electrocatalyst for H2O2 generation. The resultant NiNi-PBA superstructure has a stoichiometric composition with saturated lattice water, and a leaf-like morphology composed of interconnected small-size nanosheets with identical orientation and predominate {210} side surface exposure. Our studies show that the Ni-N centers on {210} facets are the active sites, and the saturated lattice H2O favors a six-coordinated environment that results in high selectivity. The "perfect" structure including stoichiometric composition and ideal facet exposure leads to a high selectivity of ~100% and H2O2 yield of 5.7 mol g-1 h-1, superior to the reported MOF-based electrocatalysts and most other electrocatalysts.

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Understanding the interfacial composition in heterostructures is crucial for tailoring heterogenous electrochemical and photoelectrochemical processes. This work aims to elucidate the structure of a series of Co-Fe Prussian blue analogue modified ZnO (PBA/ZnO) electrodes with interface-sensitive vibrational sum frequency generation (VSFG) spectroscopy. Our measurements revealed, for the first time, a cyanide linkage isomerism at the PBA/ZnO interface, when the composite is fabricated at elevated temperatures. In situ VSFG spectro-electrochemistry measurements correlate the CoII➝CoIII oxidation with the flip of the bridging CN ligand from Co-NC-Fe coordination mode to a Co-CN-Fe one.  Photoluminescence measurements and X-ray photoelectron spectroscopy reveal that this unprecedented linkage isomerism originates from surface defects, which act as oxidation sites for the PBA. The presence of such surface defects is correlated with the fabrication temperature for PBA/ZnO. Thus, this contribution identifies the interplay between the surface states of the ZnO substrates and the chemical composition of PBA at the ZnO surface, suggesting an easily accessible approach to control the chemical composition of the interface.