Prussian Blue Research Articles

A Highly Efficient and Energy Saving Electrochromic Platform for Adaptive Visible and Near-Infrared Light Modulation

Dual-band electrochromic devices (DBEDs) with reversible optical properties in visible (VIS) and near-infrared (NIR) spectral ranges are highly desirable for intelligent technologies (e.g. electrochromic smart windows, adaptive and military camouflages). However, most available DBEDs only have two optical states - namely the bleached and colored states, and efforts are committed to increasing the optical modulation between them, while durability of cycling is rarely reported. Herein, we report a novel multicolored rocking-chair DBED based on Prussian blue (PB) thin films as electrochromic layers and a conductive carbon cloth (CC) frame as the counter electrode. During the electrochromic process, cations from the electrolyte migrate back and forth between PB and CC, and electrolysis of aqueous electrolyte can be effectively avoided to extend device longevity. The PB-CC DBED exhibits superior dual-band electrochromic performance with a wide range of switchable colors, including transparent, blue, green and yellow, large optical modulation in VIS-NIR ranges, fast response speed, high coloration efficiency and long-term durability. Based on the diverse color change in the VIS range and thermal control in the NIR range, the camouflage ability of the device is also described. Finally, an adaptive optical modulation platform is demonstrated, obtained by connecting the PB-CC device to a voltage-controlled circuit module to realize intelligent and autonomous color switching of the device.

Probing the Electronic Structure of Prussian Blue and Analog Films by Photoemission and Electron Energy Loss Spectroscopies.

X-ray photoelectron spectroscopy (XPS) and reflection electron energy loss spectroscopy (REELS) were employed to characterize the electronic properties of Prussian blue (PB) and its analogs when electrodeposited over metal-decorated carbon nanotubes (CNTs). Through an investigation of the influence of carbon nanotubes (CNTs) and preparation conditions on the electronic structure, valuable insights were obtained regarding their effects on electrochemical properties. XPS analysis enabled the probing of the chemical composition and oxidation states of the film materials, unveiling synthesis-driven variations in their electronic properties. REELS provided information on energy loss and electronic transitions, enabling further characterization of the changes in the electronic structure induced by different preparation methods. Such findings emphasize the importance of surface characterization to understand how the unique electronic properties of such materials can be harnessed to enhance their performance and functionality.

Targeted delivery of rosuvastatin enhances treatment of hyperhomocysteinemia-induced atherosclerosis using macrophage membrane-coated nanoparticles

Rosuvastatin (RVS) is an excellent drug with anti-inflammatory and lipid-lowering properties in the academic and medical fields. However, this drug faces a series of challenges when used to treat atherosclerosis caused by hyperhomocysteinemia (HHcy), including high oral dosage, poor targeting, and long-term toxic side effects. In this study, we applied nanotechnology to construct a biomimetic nano-delivery system, macrophage membrane (Møm)-coated RVS-loaded Prussian blue (PB) nanoparticles (MPR NPs), for improving the bioavailability and targeting capacity of RVS, specifically to the plaque lesions associated with HHcy-induced atherosclerosis. In vitro assays demonstrated that MPR NPs effectively inhibited the Toll-like receptor 4 (TLR4)/hypoxia-inducible factor-1α (HIF-1α)/nucleotide-binding and oligomerization domain (NOD)-like receptor thermal protein domain associated protein 3 (NLRP3) signaling pathways, reducing pyroptosis and inflammatory response in macrophages. Additionally, MPR NPs reversed the abnormal distribution of adenosine triphosphate (ATP)-binding cassette transporter A1 (ABCA1)/ATP binding cassette transporter G1 (ABCA1)/ATP binding cassette transporter G1 (ABCG1) caused by HIF-1α, promoting cholesterol efflux and reducing lipid deposition. In vivo studies using apolipoprotein E knockout (ApoE−/−) mice confirmed the strong efficacy of MPR NPs in treating atherosclerosis with favorable biosecurity, and the mechanism behind this efficacy is believed to involve the regulation of serum metabolism and the remodeling of gut microbes. These findings suggest that the synthesis of MPR NPs provides a promising nanosystem for the targeted therapy of HHcy-induced atherosclerosis.

Elaborating the Crystal Water of Prussian Blue for Outstanding Performance of Sodium Ion Batteries.

Prussian blue (PB) is one of the main cathode materials with industrial prospects for the sodium ion battery. The structural stability of PB materials is directly associated with the presence of crystal water within the open 3D framework. However, there remains a lack of consensus regarding whether all forms of crystal water have detrimental effects on the structural stability of the PB materials. Currently, it is widely accepted that interstitial water is the stability troublemaker, whereas the role of coordination water remains elusive. In this work, the dynamic evolution of PB structures is investigated during the crystal water (in all forms) removal process through a variety of online monitoring techniques. It can be inferred that the PB-130 °C retains trace coordination water (1.3%) and original structural integrity, whereas PB-180 °C eliminates almost all of crystal water (∼12.1%, including both interstitial and coordinated water), but inevitably suffers from structural collapse. This is mainly because the coordinated water within the PB material plays a crucial role in maintaining structural stability via forming the -N≡C-FeLS-C≡N- conjugate bridge. Consequently, PB-130 °C with trace coordination water delivers superior reversible capacity (113.6 mAh g-1), high rate capability (charge to >80% capacity in 3 min), and long cycling stability (only 0.012% fading per cycle), demonstrating its promising prospect in practical applications.

Highly-Efficient Gallium-Interference Tumor Therapy Mediated by Gallium-Enriched Prussian Blue Nanomedicine.

Prussian blue (PB)-based nanomedicines constructed from metal ion coordination remain restricted due to their limited therapeutic properties, and their manifold evaluation complexity still needs to be unraveled. Owing to the high similarities of its ionic form to iron (Fe) and the resulting cellular homeostasis disruption performance, physiologically unstable and low-toxicity gallium (Ga) has garnered considerable attention clinically as an anti-carcinogen. Herein, Ga-based nanoparticles (NPs) with diverse Ga contents are fabricated in one step using PB with abundant Fe sites as a substrate for Ga substitution, which aims to overcome the deficiencies of both and develop an effective nanomedicine. A systematic comparison of their physicochemical properties effectively reveals the saturated Ga introduction state during the synthesis process, further identifying the most Ga-enriched PB NPs with a substitution content of >50% as a nanomedicine for subsequent exploration. It is verified that the Ga interference mechanisms mediated by the most Ga-enriched PB NPs are implicated in metabolic disorders, ionic homeostasis disruption, cellular structure dysfunction, apoptosis, autophagy, and target activation of the mammalian target of the rapamycin (mTOR) and mitogen-activated protein kinase (MAPK) pathways. This study provides significant guidance on exploiting clinically approved agents for Ga interference and lays the foundation for the next generation of PB-based theranostic agents.

Developing Prussian blue/wood-derived biochar catalyst for persistent organic pollutant degradation: Preparation, characterization, and mechanism

Biomass-derived biochar shows broad promise for persistent organic pollutants (POPs) degradation and thus establishes a more sustainable homestead. However, effective catalytic performance is still challenging. Herein, an efficient catalyst (Prussian blue decorated wood-derived biochar, PBB) was constructed by introducing Prussian blue (PB) into wood-based biochar to activate peroxymonosulfate (PMS) for removing POPs. After anchoring of PB, the degradation performance of biochar was enhanced (degradation efficiency of methylene blue (MB, 20 mg/L) increased from 52% of biochar to 95% of PBB within 60 min). The PBB presents effective MB degradation performance with a wide pH value (3.0 < pH < 11.0) or co-existing diverse anions (Cl−, NO3−, H2PO4−, and HCO3−). Electron paramagnetic resonance (EPR) analysis as well as electrochemical tests confirmed that the non-radical pathway (1O2) is the key to biochar activation of PMS, but by restricting PB into the biochar, the radical pathway (SO4•- and •OH), the non-radical pathway (1O2), and direct electron transfer can work together to activate PMS. In addition, the degradation efficiency could remain about 80% after five-time cyclic tests. This work elucidates the role of PB nanoparticles in enhancing biochar catalysts, which can inspire the development of a carbon-neutralized, cost-effective, and effective strategy for POPs removal.

Flexible Composite Electrochromic Device with Long-Term Bistability Based on a Viologen Derivative and Prussian Blue.

Viologen and Prussian blue (PB) exhibit good electrochromic properties, but certain limitations still exist. To improve the electrochromic properties of viologen, a viologen derivative 1,1'-bis(4-(bromomethyl)benzyl)-[4,4'-bipyridine]-1,1'-diium hexafluorophosphate (BBDV) was synthesized, and its electrochromic properties were investigated. Additionally, a flexible composite electrochromic device (FC-ECD) was prepared by using BBDV and PB as active materials. The structure of the FC-ECD was PET-ITO/gel electrolyte-BBDV/PB/PET-ITO. The applied voltage required for the FC-ECD was found to be lower than that of the ECD based on BBDV(FBBDV-ECD). Compared to FBBDV-ECD, FC-ECD exhibited a higher optical contrast (71.42%) and cyclic stability (89.51%). The FC-ECD exhibited multicolor changes under different applied voltages (ranging from -2.0 to +1.6 V). Especially, the color of the FC-ECD remained stable for 14 h after the removal of the applied voltage.

Enhancing tumor photodynamic synergistic therapy efficacy through generation of carbon radicals by Prussian blue nanomedicine.

Significant progress has been achieved in tumor therapies utilizing nano-enzymes which could convert hydrogen peroxide into reactive oxygen species (ROS). However, the ROS generated by these enzymes possess a short half-life and exhibit limited diffusion within cells, making it challenging to inflict substantial damage on major organelles for effective tumor therapy. Therefore, it becomes crucial to develop a novel nanoplatform that could extend radicals half-life. Artesunate (ATS) is a Fe (II)-dependent drug, while the limited availability of iron (II), coupled with the poor aqueous solubility of ATS, limits its application. Here, Prussian blue (PB) was selected as a nano-carrier to release Fe (II), thus constructing a hollow Prussian blue/artesunate/methylene blue (HPB/ATS/MB) nanoplatform. HPB degraded and released iron(III), ATS and MB, under the combined effects of NIR irradiation and the unique tumor microenvironment. Moreover, Fe (III) exploited GSH to formation of Fe (II), disturbing the redox homeostasis of tumor cells and Fe (II) reacted with H2O2 and ATS to generate carbon radicals with a long half-life in situ. Furthermore, MB generates 1O2 under laser irradiation conditions. In vitro and in vivo experiments have demonstrated that the HPB/ATS/MB NPs exhibit a synergistic therapeutic effect through photothermal therapy, photodynamic therapy and radical therapy.

Physicochemical and pharmacotechnical characterization of Prussian blue for future Prussian blue oral dosage forms formulation

Ferric hexacyanoferrate, Fe4 [Fe(CN)6]3 · xH2O, known as Prussian blue (PB), has proven its effectiveness as an antidote in cases of accidental poisoning or poisoning caused by radioactive materials such as cesium (Cs) and thallium (Tl); which due to their solubility in water, when absorbed by the human body, cause serious damage to vital organs. The local development of a drug with PB as an active ingredient arises as a response to the civil and military needs established within the Ministry's pharmacy request for national defense. This fact contemplates the circumstances related to public health protection in the nuclear, radiological, biological and chemical (NRBQ) of the emergency institutions in health and national security. In this paper and by using various analytical techniques, the characterization of the locally synthesized PB with pharmaceutical quality has been described, as a first step to predict its behavior in the preparation of a drug that contains it as an active ingredient.The research findings demonstrate that locally synthesized PB is suitable for use in oral dosage forms, enabling the local development of drug formulations incorporating PB, thus being able to potentially become a main resource in the treatment of Cs and Tl poisoning in any accidental or intended of the population. This development opens up the possibility of creating drug formulations that incorporate PB at a local level, making it a potentially significant resource in the treatment of Cs and Tl poisoning. The ability to locally produce and utilize PB in oral dosage forms could be crucial in addressing cases of accidental or intentional exposure within the population. This advancement not only contributes to the scientific understanding of PB but also holds promising implications for practical applications in public health and emergency situations.

Enhanced dispersion of prussian blue via intercalation into layered double hydroxides for efficient solar seawater evaporation.

Prussian blue (PB) is favored for its photothermal absorption capability in solar vapor generation applications. However, the photothermal conversion efficiency of current PB-based devices is limited by the material's poor dispersion. Herein, we report a method of incorporating PB in the interlayers of layered double hydroxides (LDHs) to prevent its aggregation. The dispersion is further enhanced and stabilized by the addition of sodium dodecyl sulfate (SDS). The thermal and water stability of PB is improved due to the rigid structure of LDHs and interactions between layers and anions. Elemental analysis confirms that with the increase of molar ratio of Mg/Al and the introduction of SDS, concentrations of PB are decreased accordingly. As a result, the rate of solar vapor generation is increased by 35.9% for powders containing 50 mg of equivalent PB. Of note, converting this material into a three-dimensional structure of high rebound foam further enhances solar water evaporation rate, from 0.79 kg m-2 h-1 to 0.98 kg m-2 h-1, with only 20 mg of equivalent PB, increasing the corresponding photothermal conversion efficiency from 53.8% to 66.3%.

A hydrophobic alloy-coated Zn anode for durable electrochromic devices.

To mitigate Zn corrosion, dendrite growth and hydrogen evolution reactions (HER) in Zn-anode based electrochromic devices, hydrophobic CuZn5 alloy was coated on Zn@CuZn with lower nucleation potential, high coulombic efficiency, inhibited HER, and prolonged reversibility, enabling improved switching kinetics and cycling stability in an electrochromic Zn@CuZn||Prussian Blue (PB) device.

Thallium - poisoner’s poison: An overview and review of current knowledge on the toxicological effects and mechanisms

Thallium (Tl) is one of the most toxic metals and its historic use in homicides has led it to be known as “the poisoner’s poison.” This review summarizes the methods for identifying Tl and determining its concentrations in biological samples in recently reported poisoning cases, as well as the toxicokinetics, toxicological effects, toxicity mechanisms, and detoxication methods of Tl. Recent findings regarding Tl neurotoxicological pathways and toxicological effects of Tl during pregnancy are also presented. Confirmation of elevated Tl concentrations in blood, urine, or hair is indispensable for diagnosing Tl poisoning. The kidneys show the highest Tl concentration within 24 h after ingestion, while the brain shows the highest concentration thereafter. Tl has a very slow excretion rate due to its large distribution volume. Following acute exposure, gastrointestinal symptoms are observed at an early stage, and neurological dysfunction is observed later: Tl causes the most severe damage in the central nervous system. Alopecia and Mees’ lines in the nails are observed within 1 month after Tl poisoning. The toxicological mechanism of Tl is considered to be interference of vital potassium-dependent processes with Tl+ because its ionic radius is similar to that of K+, as well as inhibition of enzyme reactions by the binding of Tl to -SH groups, which disturbs vital metabolic processes. Tl toxicity is also related to reactive oxygen species generation and mitochondrial dysfunction. Prussian blue is the most effective antidote, and metallothionein alone or in combination with Prussian blue was recently reported to have cytoprotective effects after Tl exposure. Because Tl poisoning cases are still reported, early determination of Tl in biological samples and treatment with an antidote are essential.

Bufotalin-loaded biomimetic Prussian blue nanoparticles for colorectal cancer chemo-photothermal ferroptosis therapy.

Purpose: We constructed biomimetic nanoparticles with biocompatible, tumor-targeting, laser-responsive properties for ferroptosis-induced colorectal cancer chemo-photothermal therapy, with the aim to realize double-hit ferroptosis treatment for colorectal cancer. Methods: The nanoparticles were prepared by first loading the chemotherapy drug bufotalin (CS-5) with Prussian blue (PB), then combining a hybridized erythrocyte-tumor membrane (M) with PB@CS-5 to produce PB@CS-5@M. The chemo-photothermal therapy efficiency of PB@CS-5@M was tested by in vitro and in vivo experiments. Results and conclusion: The combined PB and CS-5 act as promising ferroptosis inducers to enhance ferroptosis efficacy. The hyperthermia induced by laser stimulation can trigger PB to release CS-5 and iron and ferrous ions, which further promotes ferroptosis.

Towards a large-scale and high-performance smart window based on Prussian blue: a revolutionary two-dimensional-material assisted in situ growth preparation method utilizing MXene

Electrochromic smart windows (ESWs) hold great promise in improving energy efficiency in buildings.

Mechanisms of inclusion of thallium-201 into Prussian blue nanoparticles for nuclear medicine applications.

Prussian blue is known for its high affinity for thallium and other univalent metal cations and has been used as a treatment for radiocaesium and thallium/radiothallium poisoning. While Prussian blue nanoparticles (PBNPs) show potential for binding radioactive thallium for further use in nuclear medicine applications, the inclusion mechanism remains elusive. Understanding the interaction between PBNPs and 201Tl is essential for identifying the physicochemical and radiochemical properties required for optimal in vivo performance. In this work, we evaluated the binding mechanism between Tl and PBNPs with different coatings and core shapes. Combining PBNPs with [201Tl] thallium(I) chloride provided high radiolabelling yields and radiochemical stabilities under physiological conditions. Comprehensive characterisation by different X-ray techniques confirmed that Tl ions are located in the interstitial sites within the crystal structure, maintaining the integrity of the iron (Fe) 4p electronic distribution and inducing local modifications in the nearby C-N ligands. Additionally, this inclusion does not impact the core or the shell of the nanoparticles but does alter their ionic composition. The PB ionic network undergoes significant changes, with a substantial drop in K+ content, confirming that Tl+ ions replace K+ and occupy additional spaces within the crystal structure. These results open new opportunities in nuclear medicine applications with 201Tl-PBNPs where the size, shape and composition of the particles can be specifically tuned depending on the desired biological properties without affecting the radiochemical performance as a vehicle for 201Tl.

Technological Features of the Group of Nev’yansk Icons from Nev’yansk Icon Museum

The article is devoted to the technological examination of eight icons from the largest collection of Ural icon painting in Russia. For the first time the subject of study is the material component of Nev’yansk icons of the first half of the 18th century. The authors determined the painting techniques and artistic materials used by the first icon painters of the mining and metallurgical Ural. The phenomenon of the Old Believers’ Ural Region icon school of this period is doubted and questioned by some modern experts, but in fact this phenomenon is confirmed by the coincidence of technological features of the Nev’yansk icon “Our Lady of Egypt” (1734) and other icons of that period (identical processing of wooden panels, composition of prime and paints, style of so-called lichnόe (painting of exposed body parts) and dolíchnoe (painting of clothing), as well as the painting stratigraphy). The icons were obviously painted in a very small workshop. One technological factor speaks in favor of their Ural Region origin: the use of anhydrite as a filler for the prime. The technique of lichnόe is also very special — alternating layers of white paint and ocher when painting a carnation; in some cases applying the first modeling layer (white) directly over the sankir (proplasmos). The second point indicates the early Nev’yansk icon painters’ familiarity with the techniques of the court icon painters in the Armory in Moscow. The latter in turn agrees with the historical facts that from the 20–30s of the 18th century masters from the Volga Region who had previously been employed by the Armoury then moved to the Ural Region. In addition, the blue pigments are the most important chronological indicator for the icons of this period. The synthetic azurite predominates among the author’s paints; also, indigo and smalt are found, while Prussian blue is completely absent.

Energy Density in Ionic Thermoelectric Generators by Prussian Blue Electrodes

Solid-state ionic thermoelectric generators have emerged as promising solutions for efficient harvesting of low-grade waste heat. However, the main challenge in achieving continuous power supply is the low efficiency of thermoelectric conversion. In this work, substantial achievements have been made in improving the thermoelectric conversion characteristics by introducing redox pairs on the electrode surfaces. This approach takes advantage of the synergistic effect of thermal diffusion and thermoelectric effects to maximize the conversion efficiency. To improve the thermoelectric storage and output power performance, Prussian blue was attached to a carbon woven fabric and used as an electrode. The incorporation of Prussian blue/carbon woven fabric electrodes results in an increase in current density output and an instantaneous power density of 3.7 mW/m 2 ·K 2 . Furthermore, under a temperature gradient of 10 K, the output energy density for 2 h is 194 J/m 2 , and the Carnot relative efficiency is as high as 0.12% at a hot side temperature ( T H ) of 30 °C and a cold side temperature ( T C ) of 20 °C. Our findings validate the efficacy of integrating thermal diffusion and redox reactions in ionic thermoelectric generators, paving the way for the progress of thermocharged devices and their potential commercial applications.

Electrofluorochromism based on the valence change of europium complexes in electrochemical devices with Prussian blue as the counter electrode.

The electrofluorochromism of Eu complexes based on the valence change between Eu3+ and Eu2+ is demonstrated in a two-electrode electrochemical device consisting of Prussian blue (PB) as the counter electrode. This study aims to improve the electrofluorochromic (EFC) performance of luminescence switching between Eu3+ and Eu2+ by enhancing the electrochemical reactivity of the EFC device. By introducing a PB film as a counter electrode in a two-electrode device, the redox reaction of Eu3+/2+ is promoted because of charge compensation by the counter PB film. The increase in the reaction charge enables faster changes in the photoluminescence from Eu3+ to Eu2+ and an increase in the blue luminescence intensity from the Eu2+ state. This approach achieves a lowered driving voltage, accelerates the electrochemical redox reaction of the Eu complex, and enhances the reversibility of the valence change of the Eu ion.

A self-calibrating flexible SERS substrate incorporating PB@Au assemblies for reliable and reproducible detection.

The precise quantitative analysis using surface-enhanced Raman spectroscopy (SERS) in an uncontrollable environment still faces a significant obstacle due to the poor reproducibility of Raman signals. Herein, we propose a facile method to fabricate a self-calibrating substrate based on a flexible polyvinyl alcohol (PVA) film comprising assemblies of Prussian blue (PB) and Au NPs (PB@Au) for reliable detection. PB cores were coated with an Au shell through simple electrostatic interaction, forming core-shell nanostructure PB@Au assemblies within the PVA film. The outer Au layer provided identical trends in enhancement for both the PB core and neighboring targets while PB cores served as an internal standard (IS) to correct signal fluctuations. The prevention of competitive adsorption on the metal surface between targets and ISs was achieved. The proposed PVA/PB@Au film exhibited enhanced stability of Raman signals after IS correction, resulting in improved spot-to-spot and batch-to-batch reproducibility with significantly reduced standard deviation (RSD) values from 11.42% and 25.02% to 4.43% and 9.39%, respectively. Simultaneously, a higher accuracy in the quantitative analysis of 4-mercaptobenzoic acid (4-MBA) and malachite green (MG) was achieved with fitting coefficient (R2) values improving from 0.9675 and 0.9418 to 0.9974 and 0.9832, respectively. Moreover, the PVA/PB@Au film was successfully applied to detect residual MG in real fish samples. This work opens up an avenue to improve the reproducibility of Raman signals for flexible SERS substrates in the detection of residues under various complex conditions.

A reagentless molecularly imprinted polymer-based electrochemical biosensor for single-step detection of troponin I in biofluids.

Reagentless molecular-imprinted polymer (MIP) electrochemical biosensors can offer the next generation of biosensing platforms for the detection of biomarkers owing to their simplicity, cost-efficacy, tunability, robustness, and accuracy. In this work, a novel combination of Prussian blue (PB), coated as an embedded redox probe on a gold working electrode (GWE), and a signal-off MIP assay has been proposed in an electrochemical format for the detection of troponin I (TnI) in biofluids. TnI is a variant exclusive to heart muscles, and its elevated level in the bloodstream is indicative of acute myocardial infarction (AMI). The proposed lab-manufactured PB/MIP electrochemical biosensor, consisting of a simple signal-off MIP assay and a PB redox probe embedded on the GWE surface, is the first of its kind that allows for reagentless, label-free, and single-step electrochemical biosensing of proteins. The preparation steps of the biosensor were fully characterized by cyclic voltammetry (CV), atomic force microscopy (AFM), and Raman spectroscopy. Finally, the performance of the optimized biosensor was investigated through the determination of various concentrations of TnI, ranging from 10 to 100 pg mL-1 within 5 min, in serum and plasma with limits of detection less than 3.6 pg mL-1, and evaluation of selectivity towards TnI using some relevant proteins that exist in biofluids with higher concentrations.