Synthesis Of Prussian Blue Nanoparticles Research Articles

Synthesis of Prussian Blue nanoparticles in water/alcohol mixtures

Prussian Blue, a blue coordination polymer has a very promising future in the realm of biomedicine. Its nanoparticles, known as catalytic labels or nanozymes. They exhibit remarkable peroxidase-like properties and serve as effective antioxidants. Demand for synthesizing Prussian Blue nanoparticles with customizable sizes is on the rise. This article unveil a novel approach to synthesizing Prussian Blue nanoparticles. A synthesis of Prussian Blue nanoparticles by reducing an equimolar mixture of FeCl3 and K3[Fe(CN)6] with hydrogen peroxide in different water-alcohol mixtures is demonstrated for the first time. Alcohols with a lower dielectric constant (propanol-1, isopropyl alcohol, and tert-butanol) contribute to an increase in nanoparticle size, particularly at mole fractions of 0.02–0.05 and beyond. Conversely, alcohols with a higher dielectric constant (ethanol, methanol, ethylene glycol, and propylene glycol, excluding glycerol) demonstrate the ability to decrease nanoparticle size at mole fractions of 0.2–0.26 and higher. A scalable and reproducible method for preparing 30–40 nm Prussian Blue nanoparticles using 79.2% ethylene glycol as a solvent is presented. The proposed mechanism behind the effect of ethylene glycol involves the limitation of both growth and secondary aggregation of Prussian Blue nanoparticles. These synthesized nanoparticles prove their efficiency as catalytic labels in a model vertical flow immunoassay designed to detect antibodies against SARS-CoV-2.

Iron-based hybrid polyionic complexes as chemical reservoirs for the pH-triggered synthesis of Prussian blue nanoparticles

HypothesisHybrid polyion complexes (HPICs) obtained from the complexation in aqueous solution of a double hydrophilic block copolymer and metal ions can act as efficient precursors for the controlled synthesis of nanoparticles. In particular, the possibility to control the availability of metal ions by playing on the pH conditions is of special interest to obtain nanoparticles with controlled size and composition. ExperimentsHPICs based on Fe3+ ions were used to initiate the formation of Prussian blue (PB) nanoparticles in presence of potassium ferrocyanide in reaction media with varying pH values. FindingsComplexed Fe3+ ions within HPICs can be easily released by adjusting the pH value either through the addition of a base/acid or by using a merocyanine photoacid. This allows to modulate the reactivity of Fe3+ ions with potassium ferrocyanide present in solution. As a result, PB nanoparticles with different structures (core, core–shell), composition and controlled size are obtained.

Пруська блакить і її аналоги як штучні ензими й перспективи їхнього використання

In recent years, Prussian blue nanoparticles (PB-NPs) and theire analogues, that exhibit an increased catalytic activity, have attracted considerable attention in nanotechnology. Such nanoparticles are regarded as an alternative to natural enzymes and are intensively used in biosensorics, diagnostics and experimental biomedicine. Recently, it has been shown that Prussian blue nanoparticles and their analogs, also referred to as “nanozymes”, can be used as active oxygen scavengers and antibacterial or anti-inflammatory drugs due to their polyenzymatic activities, namely oxidase, peroxidase, superoxide dismutase. Their excellent biocompatibility and biodegradability mean that they are ideal for in vivo use. Prussian blue nanoparticles are highly efficient electron transporters that engage in oxidation and reduction activity, which makes them promising mediators and catalysts of reactions. They also show great promise as nanodrug carriers and biological detection sensors due to their large specific surface area, unique chemical characteristics, and variable qualities, which, more importantly, can significantly increase their therapeutic effect. Prussian blue nanoparticles, as therapeutic and diagnostic tools, have achieved significant success in biological nanomedicine. This review is devoted to the methods of synthesis of Prussian blue nanoparticles, the study of their structure, properties and role in the creation of analytical sensors and their promising significance for biomedicine.

Synthesis of Prussian Blue Nanoparticles and Their Antibacterial, Antiinflammation and Antitumor Applications.

In recent years, Prussian blue nanoparticles (PBNPs), also named Prussian blue nano-enzymes, have been shown to demonstrate excellent multi-enzyme simulation activity and anti-inflammatory properties, and can be used as reactive oxygen scavengers. Their good biocompatibility and biodegradability mean that they are ideal candidates for in vivo use. PBNPs are highly efficient electron transporters with oxidation and reduction activities. PBNPs also show considerable promise as nano-drug carriers and biological detection sensors owing to their huge specific surface area, good chemical characteristics, and changeable qualities, which might considerably increase the therapeutic impact. More crucially, PBNPs, as therapeutic and diagnostic agents, have made significant advances in biological nanomedicine. This review begins with a brief description of the synthesis methods of PBNPs, then focuses on the applications of PBNPs in tissue regeneration and inflammation according to the different properties of PBNPs. This article will provide a timely reference for further study of PBNPs as therapeutic agents.

Polyethylenimine-mediated controlled synthesis of Prussian blue-gold nanohybrids for biomedical applications.

We report on polyethylenimine (PEI)-mediated synthesis of Prussian blue nanoparticles (PBNPs) and gold nanoparticles (AuNPs); the formation of PBNP-AuNP nanohybrids with a remarkable change in Prussian blue character as a function of gold cation concentration was also considered. It was shown that PEI-protected polycrystalline PBNPs can be synthesized in an acidic medium from the precursor potassium ferricyanide [K3Fe(CN)6] at 60 °C. Since PEI also enables the controlled formation of gold nanoparticles (AuNPs) in the presence of formaldehyde under ambient conditions, nanohybrids of PBNPs and AuNPs were prepared. The formation of AuNPs was recorded over a wide range of PEI concentrations, which allowed control over polymeric cation capping of the AuNPs. PEI concentration-dependent enhancement/quenching of fluorescence/resonance Rayleigh scattering was useful for non-enzymatic detection of serum glucose levels. The resonance Rayleigh scattering intensity of PBNPs was several-fold higher than that of AuNPs and acted as a potent quencher of fluorescence. At an optimal concentration of PEI, AuNPs allowed an increase in the fluorescence signal as function of glucose concentration; the quenching ability of PB was demonstrated to be a function of the glucose concentration. This method is efficient for fast glucose sensing and offers a wider linear dynamic range, 0-10 mM, which is useful for non-enzymatic detection of serum glucose levels.

Synthesis of uniform Prussian blue nanoparticles by a polyol process using a polyethylene glycol aqueous solution.

A polyol process was applied to the synthesis of Prussian blue nanoparticles that have a narrow size distribution. Potassium hexacyanidoferrate(iii) and iron(iii) nitrate aqueous solutions were introduced into a 50% polyethylene glycol (PEG) aqueous solution under magnetic stirring at 50 °C and reacted for 48 h. The shape of the so-obtained particles was cubic with somewhat rounded edges and the mean size was 70 nm. In the formation process, nanoparticles of Prussian green, which is a partially oxidized state of Prussian blue, were firstly generated via reduction of the precursors by PEG molecules. The Prussian green nanoparticles were then reduced subsequently to Prussian blue nanoparticles. Rate constants for both the reduction steps have been estimated using the time evolution of absorbance.

Large-scale synthesis of monodisperse Prussian blue nanoparticles for cancer theranostics via an "in situ modification" strategy.

BackgroundThe intrinsic properties of Prussian blue (PB) nanoparticles make them an attractive tool in nanomedicine, including magnetic resonance imaging (MRI), photoacoustic imaging (PAI), and photothermal therapy (PTT) properties. However, there still remains the challenge of their poor dispersible stability in the physiological environment. In this study, we developed an efficient hydrothermal method to address the poor dispersible stability of PB nanoparticles in the physiological environment.Materials and methodsThe concentration of H+, the mass of polyvinylpyrrolidone (PVP), and iron sources (K3[Fe(CN)6]) are very vital in the preparation of PB nanoparticles. Through exploring the preparation process, optimized PB nanoparticles (OPBs) with excellent physiological stability were prepared. Hydrodynamic diameter and UV-vis absorption properties were measured to verify the stability of the prepared OPBs. Properties of dual-mode imaging, including MRI/PAI, and PTT of OPBs were investigated both in vitro and in vivo. In addition, the in vivo biosafety of OPBs was systematically assessed.ResultsOPBs were stable in different environments including various media, pH, and temperatures for at least 90 days, indicating that they are suitable for biomedical application via intravenous administration and easily stored in a robust environment. Compared with other research into the synthesis of PB nanoparticles, the “in situ modification” synthesis of PB nanoparticles had advantages, including a simple process, low cost, and easy mass preparation. OPBs showed no significant signs of toxicity for 90 days. As a proof of concept, the OPBs served as dual-mode image contrast agents and photothermal conversion agents for cancer diagnosis and therapy both in vitro and in vivo.ConclusionOur findings suggest a facile but efficient strategy with low cost to address the poor dispersible stability of PB nanoparticles in physiological environments. This will promote the development of further clinical transformations of PB nanoparticles, especially in cancer theranostics.

Gram-scale synthesis of Prussian blue nanoparticles as hydrophobic drug carrier for photothermal-chemo combination treatment of cancer

Gram-scale synthesis of Prussian blue nanoparticles as hydrophobic drug carrier for photothermal-chemo combination treatment of cancer

Functional alkoxysilane mediated controlled synthesis of Prussian blue nanoparticles, enabling silica alginate bead development; nanomaterial for selective electrochemical sensing

We report herein the controlled synthetic strategy for Prussian blue nanoparticles (PBNPs) formation justifying the role of functional alkoxysilanes, [2-(3,4-Epoxycyclohexyl)ethyl]trimethoxysilane (EETMSi) in the presence of tetrahydrofuran hydroperoxide (THF-HPO) with following major findings: (i) significant change in nanogeometry from 40 to 8 nm by addition of EETMSi and (ii) allowed fabrication of PBNPs encapsulated silica-alginate beads. As made nanoparticles were characterized by UV–Vis spectroscopy, TEM, FT-IR, and SEM. Size dependent electrochemical behavior of three different PBNPs i.e. PBNPs-1 (26 nm), PBNPs-2 (17 nm) and PBNPs-3 (8 nm) was recorded based on cyclic voltammetry. Apart from unprecedented size-dependent properties, as made PBNPs-3 display excellent peroxidase mimetic activity with Km value to the order of ∼0.9 mM. In addition, EETMSi also allows to cast Prussian blue film and simultaneously enable the formation of silica-alginate beads with controlled pores size perfectly suitable for encapsulating these nanoparticles which allocate selective electrochemical oxidation of Pyrogallol (Py) at 0.3 V vs. Ag/AgCl.

Paper-based synthesis of Prussian Blue Nanoparticles for the development of whole blood glucose electrochemical biosensor

Nowadays, environmentally friendly synthesis pathways for preserving the environment and minimizing waste are strongly required. Herein, we propose filter paper as a convenient scaffold for chemical reactions. To demonstrate this novel approach, Prussian Blue Nanoparticles (PBNPs) were synthesized on filter paper by utilizing few μL of its precursors without external inputs, i.e. pH, voltage, reducing agents, and without producing waste as well. The functional paper, named “Paper Blue”, is successfully applied in the sensing field, exploiting the reduction of hydrogen peroxide at low applied potential. The eco-designed “Paper Blue” was combined with wax- and screen-printing to manufacture a reagentless electrochemical point-of-care device for diabetes self-monitoring, by using glucose oxidase as the biological recognition element. Blood glucose was linearly detected for a wide concentration range up to 25 mM (450 mg/dL), demonstrating its suitability for management of diabetes and glucose-related diseases. The Paper Blue-based biosensor demonstrated a correlation coefficient of 0.987 with commercial glucose strips (Bayer Contour XT). The achieved results demonstrated the effectiveness of this approach, which is also extendible to other (bio)systems to be applied in catalysis, remediation, and diagnostics.

Direct Synthesis of Prussian Blue Nanoparticles in Liposomes Incorporating Natural Ion Channels for Cs+ Adsorption and Particle Size Control.

Coordination polymer (CP) nanoparticles (NPs) formed by a self-assembly of organic ligands and metal ions are one of the attractive materials for molecular capture and deliver/release in aqueous media. Control of particle size and prevention of aggregation among CP NPs are important factors for improving their adsorption capability in water. We demonstrate here the potential of a liposome incorporating an antibiotic ion channel as a vessel for synthesizing Prussian blue (PB) NPs, being a typical CP. In the formation of PB NPs within liposomes, the influx rate of Fe2+ ions into liposome encapsulated [Fe(CN)6]3- through channels was fundamental for the change of NPs' sizes. The optimized PB NP-liposome composite showed higher adsorption capacity of Cs+ ions than that of aggregated PB NPs that are prepared without liposome in aqueous media.

In situ synthesis of a Prussian blue nanoparticles/graphdiyne oxide nanocomposite with high stability and electrocatalytic activity

Herein we report an in situ synthesis of Prussian blue nanoparticles (PB) on graphdiyne oxide (GDYO) which acts as an excellent substrate. The hybrid was then used as an electrode with high electrochemical catalytic activity towards hydrogen peroxide. The PB/GDYO hybrid was prepared by simply adding FeCl3 to GDYO solution, and then mixing with Fe(CN)63− at room temperature. The GDYO was able to anchor PB in nanoparticle form and stabilize it in neutral and weakly basic solutions. The hybrid was investigated by transmission electron microscopy, X-ray diffraction, X-ray photoelectron spectroscopy and electrochemical measurements. The PB/GDYO hybrid showed high electrochemical catalytic activity and stability for the detection of hydrogen peroxide.

Radiation-assisted synthesis of Prussian blue nanoparticles using sugar as stabilizer

Prussian blue (PB) nanoparticles were successfully synthesized via a γ radiation route in aqueous solutions using sugar as stabilizer at room temperature and ambient pressure. The particle size and shape can be affected by stabilizer and radiation conditions. When the stabilizer was sucrose and the radiation dose was 30 kGy, well-dispersed and uniform PB nanoparticles were obtained, which are 100–200 nm in diameter. They exhibit good ions exchange properties and have maximal Cs+ adsorption capacity of 125.8 mg g−1, which may be applied in radioactive wastewater treatments, ion battery etc.

Facile synthesis of Prussian blue nanoparticles as pH-responsive drug carriers for combined photothermal-chemo treatment of cancer

Multifunctional PEGylated PB-DOX NPs with a lipid-PEG shell were developed as a gram-scale manner and used as novel pH-responsive drug delivery vehicles for combined photothermal-chemo treatment of cancer cells with high efficacy.

Synthesis and properties of Prussian blue nanoparticles prepared by using Cetyl Pyridinium Chloride as protecting agent

A new approach for the synthesis of Prussian blue nanoparticles using the cationic surfactant Cetyl Pyridinium Chloride (CPC) as capping agent has been developed in the present work. Powder X-ray diffraction, transmission electron microscopy, UV–vis absorption spectra, and IR spectroscopy were employed to characterize the product. The TEM image showed that the Prussian blue nanoparticles with diameters of 8-22 nm were obtained. A particle size effect on optical and conductivity properties of the Prussian blue particles was observed. The higher value of activation energy for the nano compound compared to bulk Prussian blue indicates that the ionic conductions are predominant in the nano compound.

One-step synthesis of gradient gadolinium ironhexacyanoferrate nanoparticles: a new particle design easily combining MRI contrast and photothermal therapy.

A one-step synthesis of Prussian blue nanoparticles possessing a concentration gradient of Gd3+ counterions, g-Gd-PB, has been developed, and the potential for the particles to perform as both MRI positive contrast agents and photothermal therapy agents is demonstrated. The synthesis of potassium/gadolinium ironhexacyanoferrate is performed under increasing concentration of Gd3+ ions forming particles with a higher concentration of gadolinium toward the outer layers. The proton relaxivity (r1) measured for the particles is 12.3 mM(-1) s(-1), and T1 weighted images of phantoms containing the particles show their potential as MRI contrast agents. In addition, the Prussian blue host can rapidly and efficiently convert energy from near-IR light into thermal energy, allowing g-Gd-PB to be used as a photothermal therapy agent. The photothermal properties are demonstrated by measuring temperature changes of particle suspensions under irradiation and by photothermal ablation of CCRF-CEM cancer cells.

Tetrahydrofuran hydroperoxide mediated synthesis of Prussian blue nanoparticles: a study of their electrocatalytic activity and intrinsic peroxidase-like behavior

We report herein, tetrahydrofuran hydroperoxide (THF-HP) mediated conversion of potassium ferricyanide into Prussian blue nanoparticles (PBNPs). The new process allows controlled conversion of single precursor (i.e., potassium ferricyanide) into water dispersible PBNPs that demonstrates potential viability for use in both homogeneous and heterogeneous catalysis. The typical process involves the mixing of optimum concentrations of potassium ferricyanide and tetrahydrofuran hydroperoxide resulting into the formation of PBNPs under ambient conditions as characterized by UV-Vis spectroscopy, atomic force microscopy, transmission electron microscopy, XRD and cyclic voltammetry. The as synthesized PBNPs shows wide practical applications i.e. (1) homogeneous electrocatalysis of glutathione (GSH), (2) peroxidase-like catalytic activity for H2O2 detection, (3) colorimetric determination of GSH based on competitive reaction of o-dianisidine and GSH with H2O2, (4) electrocatalytic reduction of lipid hydroperoxides with better selectivity and sensitivity. The electrocatalytic and peroxidase mimetic abilities of these PBNPs promise a strong impact on practical biomedical devices.

Novel synthesis of Prussian blue nanoparticles and nanocomposite sol: Electro-analytical application in hydrogen peroxide sensing

This paper reports a new method for the synthesis of Prussian blue nanoparticles (PBNPs) sol of homogeneous dispersion with average particle size to the order of 15.8nm. The new method of PBNPs sol synthesis is based on the interaction of active concentrations of 3-aminopropylalkoxysilane, cyclohexanone and single precursor potassium ferricyanide under ambient conditions. The PBNPs sol shows excellent electrochemistry with electron transfer rate constant to the order of 32.1s−1. The resulting PBNPs sol has been found highly stable for practical applications and shows functional activity for making nanocomposite sol with tris(2,2′-bipyridyl) ruthenium (Rubpy). The PB-Rubpy nanocomposite shows high sensitivity for H2O2 electrochemical sensing to the order of 1102.0μAmM−1cm−2 and storage stability of the materials for more than 3 months. In addition, these nanocomposite exhibits excellent electrocatalytic property for hydrogen peroxide (H2O2) sensing with catalytic rate constant to the order of 3.14×103M−1s−1. The PB-Rubpy nanocomposite sol, apart from electrocatalytic application, shows photoluminiscent ability for many opto-electroanalytical applications. In addition to that functional property of PBNPs sol for making nanodispersion with several known nanoparticles of gold, silver, palladium along with in situ synthesis of mixed metal hexacyanoferrate have also been observed.

Size- and shape-controlled synthesis of Prussian Blue nanoparticles by a polyvinylpyrrolidone-assisted crystallization process

The preparation of coordination polymer nanoparticles is currently the focus of research attention because of the advantage of increasing the specific surface area. In this paper, we report a facile method to prepare Prussian Blue (PB) nanoparticles with different particle sizes. Their particle sizes have a wide range from a few dozen nanometres to a submicrometre, depending on the synthetic conditions. The obtained particles can be divided into three categories: small (around 20 nm), medium-sized (around 100 nm), and large (in excess of 200 nm). The medium-sized and large particles are formed by oriented aggregation of fine nanoparticles, showing a mesocrystal conformation (i.e., pseudo-single crystal nature). Our results strongly suggested that non-classical crystallization dominates the present system, which can help to further control and understand the crystallization process of other coordination polymers. By means of N2 gas adsorption–desorption measurements, the nanoporosity and specific surface areas for typical samples with three different particle sizes are characterized. Among these samples, medium-sized PB particles show the highest surface area of 260 m2 g−1, while large PB particles exhibit very poor porosity. The results show that the gas uptakes of coordination polymers can be adjusted by the particle size and shape.

Synthesis of Prussian Blue Nanoparticles with a Hollow Interior by Controlled Chemical Etching

A facile route has been found to prepare Prussian blue (PB) hollow particles with a cubic shape (see picture). With PB mesocrystals used as a starting material, hollow interiors were created through controlled chemical etching in the presence of poly(vinylpyrrolidone). The hollow cavities and particle sizes could be tuned by changing the synthetic conditions, and the original PB crystallinity was preserved even after formation of interior hollows.