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.

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.

普鲁士改革研究的意义、方法和问题

19世纪初的普鲁士改革开启了普鲁士—德国通向现代的大门。改革的成果既是德国的遗产,也是欧洲的共同遗产。改革激发了一代代历史学家强烈的研究兴趣,成为德国历史研究的经典话题。普鲁士改革史研究的范式经历了种种转变,但其关注的核心问题一直是改革与德国历史连续性的关系、改革的思想基础,以及如何评价改革的成功与失败。对普鲁士改革的历史学考察,不仅是为未来的改革研究提供新的思路和方向,更是为了使人们对改革所引发的一系列重要问题做出更加深入的学术思考。

普鲁士蓝纳米颗粒促进糖尿病皮肤创面愈合

背景:炎症、氧化应激及细菌感染是糖尿病创面难愈合的主要原因,近年来各种无机纳米材料以其抗菌活性被广泛应用于皮肤创面愈合的治疗,但抗氧化和抗炎方面的作用有限。目的:考察普鲁士蓝纳米颗粒在抗氧化、抗炎和光热抗菌多方面的糖尿病创伤修复的效果。方法:制备普鲁士蓝纳米颗粒并进行表征。(1)体外实验:采用MTT法检测不同浓度普鲁士蓝纳米颗粒的生物相容性;在过氧化氢条件下,检测普鲁士蓝纳米颗粒的细胞保护作用及活性氧荧光表达;检测普鲁士蓝纳米颗粒分解过氧化氢和超氧阴离子自由基的能力;考察普鲁士蓝纳米颗粒抑制脂多糖诱导巨噬细胞炎症的作用;采用平板菌落计数法检测普鲁士蓝纳米颗粒的光热抗菌能力。(2)体内实验:腹腔注射链脲佐菌素建立糖尿病ICR小鼠模型,使用打孔器在背部建立直径6 mm全厚皮肤创面,分对照组(未给予治疗)、普鲁士蓝组及普鲁士蓝光照组干预,观察创面愈合与组织形态学变化。结果与结论:(1)体外实验:普鲁士蓝纳米颗粒在25-200μg/mL质量浓度下对细胞无毒性;普鲁士蓝纳米颗粒具有极强的抗氧化能力,能够抑制氧化应激条件下过度活性氧的产生及对细胞的杀伤,对过氧化氢有降解活性且具有很强的清除超氧阴离子自由基的能力;普鲁士蓝纳米颗粒还显示出显著的抗炎活性,并且在光照后显示出极强的抗菌能力。(2)体内实验:造模14 d后,普鲁士蓝组、普鲁士蓝光照组创面明显缩小,其中普鲁士蓝光照组创面愈合速度最快。苏木精-伊红和Masson染色显示,普鲁士蓝组、普鲁士蓝光照组创面可见大量的肉芽组织形成及胶原沉积,其中以普鲁士蓝光照组最多;免疫荧光染色显示,与对照组比较,普鲁士蓝组和普鲁士蓝光照组α-SMA和CD31表达明显增多(P<0.05),F4/80表达明显减少(P<0.05),其中以普鲁士蓝光照组改善更明显。(3)结果表明,普鲁士蓝纳米颗粒通过发挥抗炎、抗氧化及抗菌作用促进糖尿病小鼠模型皮肤创面的愈合。

基于普鲁士蓝纳米粒子的免疫层析法检测小麦中的呕吐毒素

该研究采用普鲁士蓝纳米粒子(Prussian blue nanoparticles,PBNPs)作为信号标签,通过制备PBNPs和聚多巴胺包裹普鲁士蓝纳米粒子(polydopamine coated Prussian blue nanoparticles,PB@PDA),优化测试参数、测试试纸条灵敏度和特异性等,研究PBNPs和PB@PDA对呕吐毒素(deoxynivalenol,DON)的检测性能。结果表明,在最优实验条件下,所构建的基于PBNPs和PB@PDA的免疫层析试纸条对DON标准溶液视觉检出限分别为1.0 ng/mL和0.2 ng/mL,在0.1~0.5 ng/mL保持良好的线性关系,PB@PDA比PBNPs-LFIA检测灵敏度提高5倍,2种试纸条均显示良好的特异性。将PBNPs和PB@PDA两种试纸条应用于小麦样品检测,显示试纸条能排除小麦基质干扰,其检测限分别为20 ng/g和5 ng/g,且PB@PDA检测灵敏度高于商品化胶体金试纸条(10 ng/g)。可见,PB@PDA试纸条表现高灵敏性和抗干扰性,可满足呕吐毒素国家安全标准的限量检测要求,为现场快速筛查小麦中呕吐毒素污染提供一种新方法。

强钴—氧键合作用提升缺陷型Co_(2)MnO_(4)酸性析氧反应稳定性

通过实验和理论已经验证钴基氧化物是一种很有前景的析氧反应(OER)催化剂。然而,普通的钴基催化剂在酸性环境中非常不稳定,在酸性电解质中容易被腐蚀。因此,在目前的研究中,设计出能在强酸性条件下同时保持活性和稳定性的析氧催化剂是实现大规模工业制氢应用的一项重要挑战。因此,我们报道了通过在四氧化三钴的尖晶石晶格中引入锰(Mn)从而产生富含缺陷的催化剂(CoMn_(1)O),它在酸性电解质中具有较长的使用寿命。我们利用X射线衍射(XRD)、X射线光电子能谱(XPS)、高分辨率透射电子显微镜(HRTEM)和能量色散光谱(EDS)元素图研究了晶相结构和化学价态。在引入锰后,由于局部晶体结构的改变,产生了大量的缺陷。此外,随着锰含量的增加,可以观察到Co 2p光谱的红移,这表明Co的总价逐渐增加,形成了更稳定的Co-O键。此外,当Mn与Co的比例达到1(CoMn_(1)O)时,目标催化剂表现出良好的OER活性,在10和50mA·cm^(-2)时,过电位分别为415和552 mV。详细的物理表征和电化学测试表明,CoMn_(1)O比不含锰的Co_(3)O_(4)(CoMn_(0)O)能稳定4倍以上的时间。这可以归因于锰的引入调节了Co的电子密度偏向O,从而形成更稳定的Co-O键。Mn可以通过延缓Co活性位点的氧化速率来促进酸性氧的进化,并进一步提升稳定性。密度泛函理论(DFT)计算进一步分析了CoMn_(1)O和CoMn_(0)O的电子结构。与CoMn_(0)O相比,CoMn_(1)O中Co 3d的d带中心(εd)向费米能级(EF)移动。这表明CoMn_(1)O通过加强与OER中间物的键合作用从而降低了反应能垒。本研究为设计非贵金属电催化剂实现高效稳定的酸性析氧提供有前景的策略。

学科前沿案例融合下的物理化学实验教学设计——以“高熵普鲁士蓝的合成及应用”为例

培养更多拔尖创新人才是现阶段大学教育的重要任务。化学专业学生的培养不仅需要重视扎实的专业知识学习,还要重视科研创新思维的培养。系统熵变是热力学部分的重要教学内容,在课程原来包含的实验中,有的实验开了十几年甚至几十年,更新速度缓慢,跟不上科研发展的步伐,缺乏新颖性、趣味性及时代性。因此,设计开展高熵材料的合成及应用的创新型实验,不仅可以让学生掌握合成高熵材料的方法,了解高熵材料的研究进展,而且能够让学生探究熵值对材料性质的影响,为后续科学研究打下良好的基础。

表面硫化普鲁士蓝比色法测定GSH的综合实验设计

设计了以硫化法制备表面硫化的普鲁士蓝催化剂,用于比色法检测谷胱甘肽(GSH)。该催化剂可以有效消除本身蓝色的干扰,显著提升类过氧化物酶活性。在H_(2)O_(2)存在下,该催化剂催化3,3′,5,5′-四甲基联苯胺(TMB)氧化形成蓝色的氧化型TMB(oxTMB)。动力学分析表明,催化剂与底物的亲和力强,呈现优异的类过氧化物酶活性。硫化的普鲁士蓝用于比色法检测GSH时表现出较高的灵敏度和选择性。实验包含材料制备、仪器表征和检测,可分割成多个模块在无机化学、仪器分析和生物化学中开展,有利于增强学生创新实践能力,提高学生整合所学知识的能力。

普鲁士蓝类钠离子电池正极材料导电性研究进展

发展具有快充性能(即超高倍率性能)的钠离子电池是目前储能领域研究的重点和热点。普鲁士蓝及其类似物(PBAs)具有有利于钠离子储存和扩散的开放式三维骨架结构,已经被证明作为钠离子电池正极材料具有巨大的潜力。然而,目前所制备的PBAs大多数存在结构缺陷和结晶水,以及其本身较差的电子电导率,导致其倍率性能不理想。本文针对PBAs导电性差的问题,从离子导电和电子导电两个方面进行讨论,首先分析了PBAs中结构缺陷以及结晶水的存在对离子导电的影响以及其本身价键结构对电子电导的影响。综述了近期对于提高PBAs导电性的相关研究:①改变晶体结构,通过减少PBAs晶体内部缺陷及结晶水,从而降低钠离子迁移距离及减少阻碍;②设计特殊的PBAs晶体结构,能有效减少钠离子传输路径;③采用复合导电材料,能构建新的电子运输途径。最后对提高PBAs导电性的三种策略进行了总结和展望,指出应该在优化PBAs结构的基础上,复合导电材料,同时增强离子电导和电子电导,以期达到最佳的倍率性能。

水热法制备NaFeHCF@CC电极材料及性能研究

为提高铁铁基普鲁士蓝(NaFeHCF)电极材料中电荷迁移速率以及离子扩散速率,采用水热合成法在碳布(CC)表面原位生长NaFeHCF晶体,制备了无粘结剂的NaFeHCF@CC电极材料,采用扫描电子显微镜和粉末X射线衍射仪对晶体结构和形貌进行表征,探究了碳布的活化处理和不同水热反应时间对NaFeHCF晶粒结构及电化学性能的影响。结果表明,碳布活化处理后,碳纤维表面有较多的生长位点,提高了碳布对NaFeHCF晶体的负载量;在活化处理的碳布基底上水热反应12h生长的NaFeHCF晶体结构较为完整,结晶度高,制备的电极材料循环300圈后面容量达0.10mAh/cm^(2),容量保持率达到74.5%。

不同Fe/Ni比值普鲁士蓝类正极材料的制备及储锂性能的研究

采用络合剂辅助共沉淀法合成了不同Fe/Ni比值的铁镍普鲁士蓝化合物(FeNiHCF)粉末,并将制得的FeNiHCF粉末进行了储锂性能探究,利用X射线衍射(XRD)、X光电子能谱(XPS)和扫描电镜(SEM)对于材料的微观结构和形貌进行表征,使用蓝电系统进行恒流充放电测试表征材料的储锂性能。结果表明:不同Fe/Ni比值的掺杂会影响材料的储锂性能及循环稳定性,总体而言,随着镍离子掺杂量的增加,材料的循环稳定性不断上升,但容量有一定的下降。在m(FeCl_(3)·6H_(2)O)∶m(NiCl_(2)·6H_(2)O)=1∶4,1C的电流密度下,首次放电比容量为46.2mAh/g,经500圈循环后放电比容量仍达47.6mAh/g。同时,经过20C的高循环倍率测试后,电流密度回到1C时,比容量仍能恢复到倍率性能测试前,表现出了优异的倍率性能。

H_(2)O_(2)催化氧化缓释螯合铁离子处理碱性含氰废水的研究

黄金氰化过程中产生的废水多为碱性且含有大量亚铁氰络离子、铜氰络离子和游离氰根,为消除废水中氰化物对环境的污染并实现处置后废水回用,本文采用在弱碱性环境下引入EDDHA-Fe有机螯合铁离子并加入H_(2)O_(2)催化氧化方法分解氰根,同时氧化螯合剂释放铁离子形成普鲁士蓝沉降,实现对碱性废水中络合氰根进行了有效脱除。结果表明,在最佳实验条件下,滤液中氰化物沉淀去除效果显著,去除率达99.77%,滤液中总氰化物浓度由221.59mg/L下降至0.51mg/L,在不影响水体碱度的前提下有效实现了废水脱氰,处置后的废水可直接回用。

普鲁士蓝及其类似物的研究进程及应用

普鲁士蓝(PB)材料及其类似物(PBAs)具有理论容量高、离子交换能力优越、电化学稳定性好等优势,被广泛应用于环境等诸多领域,具有重要研究意义。结合近年来的研究热点,综述了普鲁士蓝及其类似物在电池、环境、医疗、催化剂、检测等领域的研究进展及具体应用,详细介绍了普鲁士蓝的特点与性能优化方法,为重金属吸附剂、比面积优化的电极材料等设计与开发提供了新思路,且为深入了解类普鲁士蓝吸附机理、电催化析氧性能增添了新见解,并结合目前尚存在的不足,对普鲁士蓝材料的未来应用空间和发展前景进行了展望。

阶梯形貌铁基普鲁士蓝制备及性能

采用柠檬酸辅助单一源法水热制备了具有表面从边缘向中心依次凹陷降低形貌的铁基普鲁士蓝(SFePBA)。与典型立方形貌FePBA(C-FePBA)相比,BET测试证明阶梯型特殊形貌使其具有增大一倍的比表面积,EIS测试证明其具有更低的阻抗。不同扫描速率下的循环伏安分析证明其具有赝电容效应,从而具有优异的倍率性能。电流密度由0.1 A/g增大到5 A/g,容量几乎不变,保持率为94%。此外不同电压下的非原位XRD测试证明其具有良好的结构可逆性,循环稳定性优良,在0.6 A/g电流密度下循环1500次后容量保持率为89%。