Apatinib and gamabufotalin co-loaded lipid/Prussian blue nanoparticles for synergistic therapy to gastric cancer with metastasis

Due to the non-targeted release and low solubility of anti-gastric cancer agent,apatinib(Apa),a first-line drug with long-term usage in a high dosage often induces multi-drug resistance and causes serious side effects.In order to avoid these drawbacks,lipid-film-coated Prussian blue nanoparticles(PB NPs)with hyaluronan(HA)modification was used for Apa loading to improve its solubility and targeting ability.Furthermore,anti-tumor compound of gamabufotalin(CS-6)was selected as a partner of Apawith reducing dosage for combinational gastric therapy.Thus,HA-Apa-Lip@PB-CS-6 NPs were constructed to synchronously transport the two drugs into tumor tissue.In vitro assay indicated that HA-Apa-Lip@PB-CS-6 NPs can synergistically inhibit proliferation and invasion/metastasis of BGC-823 cells via downregulating vascular endothelial growth factor receptor(VEGFR)and matrix metalloproteinase-9(MMP-9).In vivo assay demonstrated strongest anti-tumor growth and liver metastasis of HA-Apa-Lip@PB-CS-6 NPs administration in BGC-823 cells-bearing mice compared with other groups due to the excellent penetration in tumor tissues and outstanding synergistic effects.In summary,we have successfully developed a new nanocomplexes for synchronous Apa/CS-6 delivery and synergistic gastric cancer(GC)therapy.

Achieving a superior Na storage performance of Fe-based Prussian blue cathode by coating perylene tetracarboxylic dianhydride amine

Fe-based Prussian blue(Fe-PB)cathode material shows great application potential in sodium(Na)-ion batteries due to its high theoretical capacity,long cycle life,low cost,and simple preparation process.However,the crystalline water and vacancies of Fe-PB lattice,the low electrical conductivity,and the dissolution of metal ions lead to limited capacity and poor cycling stability.In this work,a perylene tetracarboxylic dianhydride amine(PTCDA)coating layer is successfully fabricated on the surface of Fe-PB by a liquid-phase method.The aminated PTCDA(PTCA)coating not only increases the specific surface area and electronic conductivity but also effectively reduces the crystalline water and vacancies,which avoids the erosion of Fe-PB by electrolyte.Consequently,the PTCA layer reduces the charge transfer resistance,enhances the Na-ion diffusion coefficient,and improves the structure stability.The PTCA-coated Fe-PB exhibits superior Na storage performance with a first discharge capacity of 145.2 mAh g^(−1) at 100 mA g^(−1).Long cycling tests exhibit minimal capacity decay of 0.027%per cycle over 1000 cycles at 1 A g^(−1).Therefore,this PTCA coating strategy has shown promising competence in enhancing the electrochemical performance of Fe-PB,which can potentially serve as a universal electrode coating strategy for Na-ion batteries.

Progress on Transition Metal Ions Dissolution Suppression Strategies in Prussian Blue Analogs for Aqueous Sodium-/Potassium-Ion Batteries

Aqueous sodium-ion batteries(ASIBs)and aqueous potassium-ion batteries(APIBs)present significant potential for large-scale energy storage due to their cost-effectiveness,safety,and environmental compatibility.Nonetheless,the intricate energy storage mechanisms in aqueous electrolytes place stringent require-ments on the host materials.Prussian blue analogs(PBAs),with their open three-dimensional framework and facile synthesis,stand out as leading candidates for aqueous energy storage.However,PBAs possess a swift capacity fade and limited cycle longevity,for their structural integrity is compromised by the pronounced dis-solution of transition metal(TM)ions in the aqueous milieu.This manuscript provides an exhaustive review of the recent advancements concerning PBAs in ASIBs and APIBs.The dissolution mechanisms of TM ions in PBAs,informed by their structural attributes and redox processes,are thoroughly examined.Moreover,this study delves into innovative design tactics to alleviate the dissolution issue of TM ions.In conclusion,the paper consolidates various strategies for suppressing the dissolution of TM ions in PBAs and posits avenues for prospective exploration of high-safety aqueous sodium-/potassium-ion batteries.

Experimental and computational optimization of Prussian blue analogues as high-performance cathodes for sodium-ion batteries:A review

In this review,we discuss the electrochemical properties of Prussian blue(PB)for Na^(+)storage by combining structural engineering and electrolyte modifications.We integrated experimental data and density functional theory(DFT)in sodium-ion battery(SIB)research to refine the atomic arrangements and crystal lattices and introduce substitutions and dopants.These changes affect the lattice stability,intercalation,electronic and ionic conductivities,and electrochemical performance.We unraveled the intricate structure-electrochemical behavior relationship by combining experimental data with computational models,including first-principles calculations.This holistic approach identified techniques for optimizing PB and Prussian blue analog(PBA)structu ral properties for SIBs.We also discuss the tuning of electrolytes by systematically adjusting their composition,concentration,and additives using a combination of molecular dynamics(MD)simulations and DFT computations.Our review offers a comprehensive assessment of strategies for enhancing the electrochemical properties of PB and PBAs through structural engineering and electrolyte modifications,combining experimental insights with advanced computational simulations,and paving the way for next-generation energy storage systems.

Effect of cation(Li^+, Na^+, K^+, Rb^+, Cs^+) in aqueous electrolyte on the electrochemical redox of Prussian blue analogue(PBA) cathodes

Prussian blue analogue(PBA)material is a promising cathode for applications in Na-ion and K-ion batteries which can support high c-rates for charge and discharge.In this study,the material of composition[K2 CuIIFeII(CN)6]was synthesized and its structural and electrochemical redox behavior was investigated with 5 different alkali insertion cations(Li^+,Na^+,K^+,Rb^+,Cs^+).Galvanostatic measurements indicate that the redox potential strongly depends on the ionic radius of the inserted cation.The redox potential varies by 400 m V between using Li^+(0.79A)or Cs^+(1.73A)in the electrolyte.The underlying modification of the Fe2^+/Fe3^+redox potential in PBA is proposed to be due to the weakening of the Fe–C bond in the material.This hypothesis is supported by XRD measurements which reveal that the lattice parameter of the de-intercalated host structure follows the same trend of monotonic increase with the cation size.The relatively minor volume changes accompanying the redox(1.2%–2.4%)allow the PBA to accommodate differently sized cations,although the structural hindrances are quite pronounced at high c-rates for the larger ones(Rb^+and Cs^+).Cycle aging studies indicate that the minimum capacity fade rate is observed in case of K^+ and Rb^+ containing electrolyte.The peak intensity corresponding to the[220]crystallographic plane varies depending on the state of charge of PBA,since this plane contains the insertion cations.Owing to the sensitivity of the redox potential to the insertion cation coupled with the observed fast ion-exchange ability,the PBA material may find additional analytical applications such as ion sensing or filtration devices.

Moderate heat treatment of CoFe Prussian blue analogues for enhanced oxygen evolution reaction performance

Prussian blue analogues(PBAs) with inherent ordered structures and abundant metal ion sites are widely explored as precursors for various electrochemical applications,including oxygen evolution reaction(OER).Using a range of characterization techniques including Fourier-transform infrared spectroscopy(FT-IR),X-ray photoelectron spectroscopy(XPS),X-ray diffraction(XRD) and energy dispersive spectroscopy(EDS),this work discloses the process of replacement of K^(+)by NH4^(+)in the interstitial spaces of the CoFe PBA by a hot aqueous urea solution,which influences the transformation of PBAs under further heat treatment and the OER performance of the deriva tives.After heat treatment at 400℃ under Ar flow,high-resolution transmission electron microscopy(HRTEM) images reveal that CoFe alloy nanoparticles grew on the crystalline cubes of CoFe PBA with K^(+),while CoFe PBA cubes with NH4^(+)become amorphous.Besides,the derivative of CoFe PBA with NH4^(+)(Ar-U-CoFe PBA) performs better than the derivative of CoFe PBA with K^(+)(Ar-CoFe PBA) in OER,registering a lower overpotential of 305 mV at 10 mA cm^(-2),a smaller Tafel slope of 36.1 mV dec^(-1),and better stability over a testing course of 20 h in 1.0 M KOH.A single-cell alkaline electrolyzer,using Ar-U-CoFe PBA and Pt/C for the anodic and cathodic catalyst,respectively,requires an initial cell voltage of 1.66 V to achieve 100 mA cm^(-2)at 80℃,with negligible degradation after100 h.

Abnormal magnetic behavior of prussian blue analogs modified with multi-walled carbon nanotubes

This work examines the origin of the abnormal magnetism exhibited by Cu Mn Fe-PBAs modified with multi-walled carbon nanotubes(MWCNTs).The system of Cu Mn Fe-PBAs@MWCNTs coexists with both large and small clusters.Cu Mn Fe-PBAs clusters have an average particle size of 28 nm,and some of the smaller particles are adsorbed on the surface of MWCNTs.Surprisingly,the magnitude of magnetization increases linearly with decreasing temperature.When above the Curie temperature,the magnitude of magnetization is significantly greater than that of PBAs without being modified.This phenomenon can be attributed to magnetostatic interactions between ultra-fine magnetic nanoparticles adsorbed on the surface of MWCNTs.Using the Monte Carlo method,we simulated the magnetostatic interaction of cylindrical adsorbed particles,and the simulation results are almost identical to those observed experimentally.The results indicate that 0.089Cu Mn Fe-PBAs clusters per 1 nm^(2)can be adsorbed onto the surface area of MWCNTs.We demonstrate that MWCNTs adsorbing magnetic particles exhibit magnetic behavior,and suggest a method for producing ultrafine materials.It also introduces a new method of calculating the adsorption efficiency of carbon nanotubes,offering theoretical guidance for future research on nanomaterials with enhanced adsorption efficiency.

Ultralow-Energy-Barrier H_(2)O_(2)Dissociation on Coordinatively Unsaturated Metal Centers in Binary Ce-Fe Prussian Blue Analogue for Efficient and Stable Photo-Fenton Catalysis

The low intrinsic activity of Fenton catalytic site and high demand for light-energy input inhibit the organic-pollution control efficiency of photo-Fenton process.Here,through structural design with density functional theory(DFT)calculations,Ce is predicted to enable the construction of coordinatively unsaturated metal centers(CUCs)in Prussian blue analogue(PBA),which can strongly adsorb H_(2)O_(2)and donate sufficient electrons for directly splitting the O-O bond to produceOH.Using a substitution-co-assembly strategy,binary Ce-Fe PBA is then prepared,which rapidly degrades sulfamethoxazole with the pseudo-first-order kinetic rate constant exceeding reported values by 1-2 orders of magnitude.Meanwhile,the photogenerated electrons reduce Fe(Ⅲ)and Ce(Ⅳ)to promote the metal valence cycle in CUCs and make sulfamethoxazole degradation efficiency only lose 6.04%in 5 runs.Overall,by introducing rare earth metals into transition metal-organic frameworks,this work guides the whole process for highly active CUCs from design and construction to mechanism exploration with DFT calculations,enabling ultrafast and stable photo-Fenton catalysis.

Depolarization of Li-rich Mn-based oxide via electrochemically active Prussian blue interface providing superior rate capability

The high-rate cyclability of Li-rich Mn-based oxide(LMO)is highly limited by the electrochemical polarization resulting from the slow kinetic of the Li2MnO3 phase.Herein,the Prussian blue(PB)coating layer with specific redox potential is introduced as a functionalized interface to overcome the side effect and the escaping of O on the surface of LMO,especially its poor rate capability.In detail,the PB layer can restrict the large polarization of LMO by sharing overloaded current at a high rate due to the synchronous redox of PB and LMO.Consequently,an enhanced high rate performance with capacity retention of 87.8%over 300 cycles is obtained,which is superior to 50.5%of the pristine electrode.Such strategies on the high-rate cyclability of Li-rich Mn-based oxide compatible with good low-rate performances may attract great attention for pursuing durable performances.

基于PBNPs-Ag纳米粒子的ROS清除和抗菌协同作用促进伤口愈合行为研究

目的利用普鲁士蓝纳米颗粒(PBNPs)与纳米银粒子(Ag)制备一种兼具ROS清除与抗菌作用的PBNPs-Ag纳米粒子以用于促进伤口愈合。方法通过XRD、IR、Zeta电位、粒径测量对PBNPs-Ag进行表征。在细胞层面上,首先使用MTT法测试PBNPs-Ag的细胞毒性,接下来利用H_(2)O_(2)作为ROS引发剂,建立细胞ROS预防模型。利用DCFH-DA对细胞内ROS直接染色。最后,利用抑菌圈法测试PBNPs-Ag对细菌的抑制效果。结果PBNPs-Ag纳米粒子粒径均匀,结晶度高,无明显细胞毒性,具有良好的ROS清除能力与抗菌能力。结论PBNPs-Ag是一种效果良好,具有前景的治疗皮肤损伤的纳米颗粒药物。

Performance and mechanism of Prussian blue (PB) modified carbon felt electrode

Prussian blue (PB) modified carbon felt electrodes were prepared. The electrochemical behavior was investigated by cyclic voltammetry, electrochemical impedance spectroscopy and charge-discharge experiments. In order to distinguish the mechanism of the PB modified carbon felt electrode, the electrochemical quartz crystal microbalance (EQCM) was employed. The results of cyclic voltammetry show that the modification can improve the reversibility and the suitable PB deposition is the amount of 10 circles deposition. PB modified carbon felt electrode can effectively decrease the charge transfer resistance. The voltage efficiency of VRB employing PB modified carbon felt electrode can be increased by 12%. The mass change of the PB modified Pt crystal electrode in the process of the potential scan is obvious. The reaction of substitution of VO2+ for high-spin Fe ion in PB is probable to happen and the possible reaction equation is given. The preliminary exploration shows that PB modified carbon felt is electrochemically promising for redox flow battery.

Prussian Blue Analogues in Aqueous Batteries and Desalination Batteries

In the applications of large-scale energy storage,aqueous batteries are considered as rivals for organic batteries due to their environmentally friendly and low-cost nature.However,carrier ions always exhibit huge hydrated radius in aqueous electrolyte,which brings difficulty to find suitable host materials that can achieve highly reversible insertion and extraction of cations.Owing to open threedimensional rigid framework and facile synthesis,Prussian blue analogues(PBAs)receive the most extensive attention among various host candidates in aqueous system.Herein,a comprehensive review on recent progresses of PBAs in aqueous batteries is presented.Based on the application in different aqueous systems,the relationship between electrochemical behaviors(redox potential,capacity,cycling stability and rate performance)and structural characteristics(preparation method,structure type,particle size,morphology,crystallinity,defect,metal atom in highspin state and chemical composition)is analyzed and summarized thoroughly.It can be concluded that the required type of PBAs is different for various carrier ions.In particular,the desalination batteries worked with the same mechanism as aqueous batteries are also discussed in detail to introduce the application of PBAs in aqueous systems comprehensively.This report can help the readers to understand the relationship between physical/chemical characteristics and electrochemical properties for PBAs and find a way to fabricate high-performance PBAs in aqueous batteries and desalination batteries.

Indocyanine Green-Conjugated Magnetic Prussian Blue Nanoparticles for Synchronous Photothermal/Photodynamic Tumor Therapy

Indocyanine green(ICG) is capable of inducing a photothermal effect and the production of cytotoxic reactive oxygen species for cancer therapy. However, the major challenge in applying ICG molecules for antitumor therapy is associated with their instability in aqueous conditions and rapid clearance from blood circulation,which causes insufficient bioavailability at the tumor site.Herein, we conjugated ICG molecules with Prussian blue nanoparticles enclosing a Fe_3O_4 nanocore, which was facilitated by cationic polyethyleneimine via electrostatic adsorption. The nanocarrier-loaded ICG formed stable aggregates that enhanced cellular uptake and prevented fluorescence quenching. Moreover, the strong superparamagnetism of the Fe_3O_4 core in the obtained nanocomposites further improved cellular internalization of the drugs guided by a localized magnetic field. The therapeutic efficacy of this nanoplatform was evaluated using tumor models established in nude mice, which demonstrated remarkable tumor ablation in vivo due to strong photothermal/photodynamic effects. This study provides promising evidence that this multifunctional nanoagent might function as an efficient mediator for combining photothermal and photodynamic cancer therapy.

Ternary Ni-based Prussian blue analogue with superior sodium storage performance induced by synergistic effect of Co and Fe

Prussian blue analogue Na2Ni[Fe(CN)6](Ni-PB)has been widely studied as a cathode material for sodium-ion battery due to its excellent cycling performance.However,Ni-PB has a low theoretical capacity of 85 mAh g^(−1) because of the electrochemical inertness of Ni.Herein,ternary Ni-PB is successfully synthesized by double doping with Co and Fe at Ni-site,and the effect of doping with Co and Fe on the electrochemical performance of Ni-PB is systematically investigated through theoretical calculations and electrochemical tests.The first principles calculations confirm that double doping with Co and Fe can significantly reduce the energy barrier and bandgap of Ni-PB.X-ray diffraction and composition analysis results indicate that ternary NiCoFe-PB composite not only has good crystallinity and high Na content but also has low defects and crystal water.Electrochemical tests reveal that,besides the capacity contribution of high-spin Co/Fe and low-spin Fe,Co-doping enhances the electrochemical activity of low-spin Fe and Fe-doping improves the activity of high-spin Co;moreover,double doping can decrease the diffusion resistance of Na+ions through solid electrolyte interface film,accelerate the kinetics for both ion diffusion process and Faradic reaction,and increase active sites.Under the synergistic effect of Co and Fe,this ternary NiCoFe-PB exhibits outstanding electrochemical performance with a high initial discharge capacity of 120.4 mAh g^(−1) at 20mA g^(−1) and an extremely low capacity fading rate of 0.0044%per cycle at a high current density of 2 A g^(−1) even after 10,000 cycles,showing great application potential of ternary NiCoFe-PB in the field of large-scale energy storage.

Flow-injection Spectrophotometric Determination of Uric Acid in Urine via Prussian Blue Reaction

A simple and sensitive flow injection（FI） spectrophotometric method was reported for the determination of uric acid based on the reduction of Fe（III）/ferricyanide in the presence of uric acid. The in situ reduced ions reacted with unreduced portion of ferricyanide/Fe（III） to form soluble Prussian blue, which was monitored at an absorption wavelength of 735 nm. The optimized conditions allow a linear calibration graph in a concentration range of 1―100 μmol/L. The relative standard deviation was in a range of 0.5%―2.5%, with a detection limit（3σ blank） of 0.3 μmol/L and a sampling frequency of 60 injection/h was obtained. The effect of common substances present in human physiological fluids on the determination of uric acid was examined. The method was applied to determining uric acid in human urine samples with the recoveries in a range of 96%―105%. The results agree well with those by spectrophotometric reference method at a confidence level of 95%. Spectrophotometric procedures for uric acid determination in clinical samples were reviewed briefly.

Application of Prussian blue staining in the diagnosis of ocular siderosis

AIM:To explore the value of Prussian blue staining in the diagnosis of ocular siderosis.METHODS:Between January 2012 and January 2013,the Prussian blue stain used in anterior lens capsule and vitreous liquid after centrifugation from patients with definitive diagnosis and suspicious diagnosed of ocular siderosis. At the same time, give a negative control.RESULTS:Anterior lens capsule membrane and liquid of vitreous cavity from patients with definitive diagnosis and suspicious diagnosed of ocular siderosis revealed ferric ions that stained positively with Prussian blue. In the control group, there is no positive reaction.CONCLUSION:Prussian blue staining in the diagnosis of ocular siderosis has a very significant worth,suspected cases can be definitive diagnosed.

Construction of hierarchical photocatalysts by growing ZnIn_(2)S_(4) nanosheets on Prussian blue analogue-derived bimetallic sulfides for solar co-production of H_(2) and organic chemicals

Exploring highly efficient bifunctional photocatalysts for simultaneous H2 evolution and organic chemical production in pure water represents a green route for sustainable solar energy storage and conversion.Herein,a facile strategy was explored for preparing a hierarchical porous heterostructure of Fe_(4)Ni_(5)S_(8)@ZnIn_(2)S_(4)(FNS@ZIS)by the in situ growth of ZIS nanosheets on Prussian blue analogue(PBA)-derived bimetallic FNS sulfides.A series of FNS@ZIS hierarchical structures were facilely prepared by adjusting the loading amount(n%)of FNS(n=19,26,and 32 for FNS@ZIS-1-3).These structures can efficiently drive the solar co-production of H_(2) and organic chemicals.The optimal co-production was achieved with FNS@ZIS-2,affording a H_(2) evolution rate of 10465μmol·g^(-1)·h^(-1),along with high selectivity for the oxidation of benzyl alcohol to benzaldehyde(>99.9%).The performance was 22 and 31 times higher than that of FNS and ZIS,respectively,and even superior to the state-of-the-art results achieved using various sacrificial agents.Further mechanistic study indicated that the unique hierarchical core/shell architecture can facilitate interfacial charge separation,afford bimetallic synergy,abundant active sites and excellent photostability.This work highlights a simple and efficient method for preparing porous multimetallic hierarchical structures for the solar co-production of organic chemicals and H_(2) fuel.

3D Prussian blue/Pt decorated carbon nanofibers based screen-printed microchips for the ultrasensitive hydroquinone biosensing

Nowadays,water pollution has become more serious,greatly affecting human life and healthy.Electrochemical biosensor,a novel and rapid detection technique,plays an important role in the realtime and trace detection of water pollutants.However,the stability and sensitivity of electrochemical biosensors remain a great challenge for practical detections in real samples to the strong interferences derived from complex components and coagulation effects.In this work,we reported a novel threedimensional architecture of Prussian blue nanoparticles(PBNPs)/Pt nanoparticles(PtNPs)composite film,using 3 D interweaved carbon nanofibers as a supporting matrix,for the construction of screenprinted microchips-based biosensor.PtNPs with diameters of-2.5 nm was highly dispersed on the carbon nanofibers(CNFs)to build a 3 D skeleton nanostructure through a solvothermal reduction.Subsequently,uniform PBNPs were in-situ self-assembled on this skeleton to construct a 3 D architecture of PB/Pt-CNF composite film.Due to the synergistic effects derived from this special feature,the as-prepared hydroquinone(HQ)biosensor chips can synchronously promote both surface area and conductivity to greatly enhance the electrocatalysis from enzymatic reaction.This biosensor has exhibited a high sensitivity of 220.28μA·L·mmol^(-1)·cm^(-2) with an ultrawide linear range from 2.5μmol·L^(-1) to 1.45 mmol·L^(-1) at a low potential of 0.15 V,as well as the satisfactory reproducibility and usage stability.Besides,its accuracy was also verified in the assays of real water samples.It is highly expected that the 3 D PB/Pt-CNF based screen-printed microchips will have wide applications in dynamic monitoring and early warning of analytes in the various practical fields.

Insights into the Structure Stability of Prussian Blue for Aqueous Zinc Ion Batteries

The reversible storage of Zn^(2+)ions in Prussian blue analogues with typical aqueous solution was challenged by fast degradation and poor coulombic efficiency,while the mechanism is yet to be uncovered.This study correlates the performance of the nickel hexacyanoferrate to the dynamics of H_(2)O in the electrolyte and the associated phase stability of the electrode.It demonstrates severe Ni dissolution in conventional diluted aqueous electrolyte(1 M ZnSO^(4)or 1 M Zn(TFSI)^(2)),leading to structure collapse with the formation of an electrochemical inert phase.This is regarded as the descriptor for the fast decay of nickel hexacyanoferrate in diluted aqueous electrolyte.However,a well-preserved open framework for zinc storage was obtained in concentrated aqueous electrolyte(1 M Zn(TFSI)_(2)+21 M LiTFSI)—the H_(2)O activity is highly suppressed by extensive coordination—thus,reversible capacity of 60.2 m Ah g^(-1)over 1600 cycles could be delivered.

Magnetization of mixed ferri-ferrimagnets composed of Prussian blue analogs A1_xA2_(1-x)B

The magnetization of ternary metal Prussian blue analogues AlxA21-xB, formed by three different sublattices A1, A2 and B, is studied by using the effective-field theory with self-spin correlations. Effects of the mole fraction x, the anisotropy and the transverse magnetic field on the magnetization are discussed.