普鲁士蓝纳米粒子在生物医学诊断和治疗中的应用及进展

随着生物医学诊断和治疗的持续深入研究,出现了多种医学诊断和治疗新方法,为人类的健康提供了更大的保证,其中纳米生物技术在生物医学诊断和治疗中的应用日益增多,基于纳米技术,开发传统材料的生物医学新应用成为了人们的研究热点。普鲁士蓝是一种历史悠久的蓝色染料,其制备过程简单、绿色、成本低,化学结构稳定,具有优良的物理、化学、光学以及磁性等性能,已经在许多领域得到了广泛的应用。近年来,普鲁士蓝开始在生物医学诊断和治疗领域中崭露头角,它已经成功的被开发为新型的核磁共振造影剂和光声成像造影剂,并且在药物输送系统和光热治疗等领域也开始占有一席之地,开发基于纳米技术的普鲁士蓝的生物医学应用已经成为极具吸引力的研究方向。本文对普鲁士蓝在生物医学诊断和治疗中的应用及进展进行综述。     

Boosting Photoelectrochemical Water Oxidation of Hematite in Acidic Electrolytes by Surface State Modification

State‐of‐the‐art water‐oxidation catalysts (WOCs) in acidic electrolytes usually contain expensive noble metals such as ruthenium and iridium. However, they too expensive to be implemented broadly in semiconductor photoanodes for photoelectrochemical (PEC) water splitting devices. Here, an Earth‐abundant CoFe Prussian blue analogue (CoFe‐PBA) is incorporated with core–shell Fe₂O₃/Fe₂TiO₅ type II heterojunction nanowires as composite photoanodes for PEC water splitting. Those deliver a high photocurrent of 1.25 mA cm^?2 at 1.23 V versus reversible reference electrode in acidic electrolytes (pH = 1). The enhancement arises from the synergic behavior between the successive decoration of the hematite surface with nanolayers of Fe₂TiO₅ and then, CoFe‐PBA. The underlying physical mechanism of performance enhancement through formation of the Fe₂O₃/Fe₂TiO₅/CoFe‐PBA heterostructure reveals that the surface states’ electronic levels of hematite are modified such that an interfacial charge transfer becomes kinetically favorable. These findings open new pathways for the future design of cheap and efficient hematite‐based photoanodes in acidic electrolytes.     

Reduction of Prussian Blue by the two iron-reducing microorganisms Geobacter metallireducens and Shewanella alga

Cyanide or cyanide-metal complexes are frequent contaminants of soil or aquifers at industrial sites, which can be released from such sites by outgassing or transport with the groundwater. They form very stable complexes with iron, which may occur in the subsurface as an insoluble blue mineral, the so-called Prussian Blue (Fe(4)[Fe(CN)(6)](3)). In this study, we show that the insoluble and colloidal Fe(III)-cyanide complex Prussian Blue can be reduced and utilized as electron acceptor by the dissimilatory iron-reducing bacteria Geobacter metallireducens and Shewanella alga strain BrY. The microbial reduction of the dark blue pigment Prussian Blue leads to the formation of a completely colourless solid mineral, presumably Prussian White (Fe(2)[Fe(CN)(6)]), which could be reoxidized through exposure to air, regaining the dark blue colour. In addition, the microorganisms were able to grow with Prussian Blue, using it as the sole electron acceptor. Geobacter metallireducens could also reduce Prussian Blue coatings on sand, which was sampled from a contaminated site.     

Interfacial Scaffolding Preparation of Hierarchical PBA‐Based Derivative Electrocatalysts for Efficient Water Splitting

The development of highly efficient and durable electrocatalysts is crucial for overall water splitting. Herein, the in situ scaffolding formation of 3D Prussian blue analogues (PBAs) on a variety of 2D or 1D metal hydroxides/oxides to fabricate hierarchical nanostructures is first demonstrated. Typically, cobalt hydroxide or oxide nanoarrays are used as the precursor and structural oriented template for the subsequent growth of 3D PBA nanocubes. The mechanism study reveals that the interfacial scaffolding process can be reversibly controlled via the in situ ion exchange process with adjusting coordination ions. Thus, the facile, versatile strategy can extend to successfully fabricate a variety of hierarchical PBA‐based nanostructures including on cobalt fluoride hydroxide, copper hydroxide, monometal or bimetal nickel–cobalt hydroxides, cobalt oxide, and manganese oxide nanosheets with structural tailor‐ability and chemical diversity. More interestingly, the metal nitride derivatives obtained via controlled calcination process exhibit good electrocatalytic activity for water splitting with low overpotentials, and remarkable durability for 1200 h, thanks to the superior intrinsic activity of bimetal nature and the scrupulous hierarchical structure. This versatile strategy provides a paradigm for rational design of PBA‐based functional nanomaterials, which is highly promising in energy conversion, storage, and electrocatalytic fields.     

Achieving High‐Voltage and High‐Capacity Aqueous Rechargeable Zinc Ion Battery by Incorporating Two‐Species Redox Reaction

Herein, a two‐species redox reaction of Co(II)/Co(III) and Fe(II)/Fe(III) incorporated in cobalt hexacyanoferrate (CoFe(CN)6) is proposed as a breakthrough to achieve jointly high‐capacity and high‐voltage aqueous Zn‐ion battery. The Zn/CoFe(CN)₆ battery provides a highly operational voltage plateau of 1.75 V (vs metallic Zn) and a high capacity of 173.4 mAh g^?1 at current density of 0.3 A g^?1, taking advantage of the two‐species redox reaction of Co(II)/Co(III) and Fe(II)/Fe(III) couples. Even under extremely fast charge/discharge rate of 6 A g^?1, the battery delivers a sufficiently high discharge capacity of 109.5 mAh g^?1 with its 3D opened structure framework. This is the highest capacity delivered among all the batteries using Prussian blue analogs (PBAs) cathode up to now. Furthermore, Zn/CoFe(CN)₆ battery achieves an excellent cycling performance of 2200 cycles without any capacity decay at coulombic efficiency of nearly 100%. One further step, a sol–gel transition strategy for hydrogel electrolyte is developed to construct high‐performance flexible cable‐type battery. With the strategy, the active materials can adequately contact with electrolyte, resulting in improved electrochemical performance (≈18.73% capacity increase) and mechanical robustness of the solid‐state device. It is believed that this study optimizes electrodes by incorporating multi redox reaction species for high‐voltage and high‐capacity batteries.     

Contrasty Staining And Quantitative Determination Of Mucopolysaccharides On Filter Paper By Means Of Colloidal Iron

The contrast between the Prussian blue color of the mucopolysaccharide spots and paper background was increased by differentiation of the paper strips (dyed in acid colloidal iron solution made up in 60% ethanol) with thioglycolic acid. Thus the trivalent iron bound to the paper background was reduced but that adsorbed by the mucopolysaccharides was precipitated as ferric ammonium thioglycolate. This procedure was found to stain equally well acid (including sulfated) and neutral mucopolysaccharides, even though these varieties exhibited different staining properties by the periodic acid-Schiff and toluidine blue dyeing procedures. Staining of different depolymerization products of hyaluronate was little influenced by their chain lengths. Quantitative determination of the mucopolysaccharide content of the spots was performed by elution of ferrocyanide with hot sodium hydroxide and measuring of the Prussian blue color of the extracts, developed on acidification and addition of FeCl₃.     

An Application of the Prussian Blue Technique to a Light Microscope Study of Water Movement in Transpiring Leaves of Cotton (Gossypium hirsutum L.)

Prussian blue deposition in transpiring leaves of Gossypiumhirsutum L. indicated that water moved rapidly from the trachearyelements by a path along the bundle sheath parenchyma to thebundle sheath extension parenchyma and then laterally throughthe epidermis to the sub-stomatal cavities or to the tnchomes.A slower pathway of water movement to the substomatal cavitiesoccurred through the mesophyll. The path of Prussian blue depositionindicated that waterleft the leaf through the stomata and toa lesser extent through the trichomes. In the outer periclinalwall of epidermalcells Prussian blue was deposited below butnot within the cuticle.     

Screen-printed electrodes modified with glucose oxidase immobilized in hybrid organosilicon sol-gel matrix

A new polymer composition was developed based on hybrid sol-gel material for the immobilization of enzymes on the surface of screen-printed carbon electrodes modified with Prussian blue. The existing and developed methods for the glucose oxidase (GO) immobilization are compared. Highly stable bioelectrodes were shown to be obtained by enzyme immobilization on a hybrid composition consisting of solgel/poly vinyl alcohol (PVA) (up to 60 sequential chains) and agar gel (up to 45 sequential chains). The range of glucose concentrations detected during enzyme immobilization in a hybrid sol-gel/PVA composition or agar gel without dilution of a sample was 1.0–5.9 μM and 3.6–6.3 μM, respectively. An analysis of wine products was conducted. The results obtained using the proposed biosensors were shown to differ insignificantly from those obtained by high-performance liquid chromatography (the correlation coefficient was 0.9998).     

An Electron Microscope Study of the Path of Water Movement in Transpiring Leaves of Cotton (Gossypium hirsulum L.)

Precipitation of ferrocyanide by ferric ions in cotton leavesproduced electron-opaque crystals visible with othe electronmicroscope and identifiable as Prussian blue by X-ray and electrondiffraction. These crystals were formed within the lumina andexposed primary walls of the tracheary elements but not withintheir secondary walls. The precipitation pattern indicated thatwater moved from the tracheary elements into the parenchymaof the bundle sheath and bundle sheath extensions. From thesecells water moved into the epidermis or through the mesophyllto the transpirational exits. Prussian blue accumulated in thewalls of cells lining the substomatal cavities and to a lesserextent between adjacent covering hairs. Ferrocyanide anionsdid not follow the water stream through the cuticle. In parenchymaand epidermal cells Prussian blue crystals were found withinthe primary wall, in the region between the plasma-lemma andthe cell wall, and within the protoplast.     

The blood circulation inside the spleen. I. The arterial blood vessels general distribution in the rat spleen

As an attempt to investigate the different pathways followed by the blood into the spleen and to analyse their functional significance, a technique was used mainly based on the intraarterial perfusion of a Prussian blue "solution" added of some chemical mediators and vasoactive substances. Such technique provides results which may be analysed taking into account the effect of the anaesthetic used, that may influence the findings. From the anaesthetic used, the sulfuric ether and the barbital sodium produce vasoconstriction of the white pulp blood vessels, whereas the chlorpromazine-promethazine doesn't have this effect, and so the Prussian blue appears inside these vessels. The vasodilator drugs, such as succinonitrile and papaverine hydrochloride, show a general vasodilator effect on the splenic arterial system. Teh arterial vessels of the white and the red pulp, including those placed at the subcapsular areas, become enlarged; into the white pulp, either the central or the peripheral blood vessel plexus of the lymphatic follicle becomes evident. The latter readily constitutes the perifollicular and the pericolumnar plexus. The blood vessels of this plexus become permeable to the Prussian blue "solution" by the heparin sodium effect, and so the dye particles enter the marginal zone and the splenic sinuses. In addition, from the white pulp arteries arise 2 types of anastomotic arterioles which appear enlarged after succinonitrile treatment: The short anastomotic arterioles that crosses the marginal zone entering the red pulp near the white pulp; the long anastomotic arterioles which enter the red pulp and after a long course end up into or around a collector sinus. The addition of histamine dihydrochloride to the perfusion solutions shows a slight vasodilator effect mainly on the subcapsular penicillar arterioles, including the helicine arterioles. The adrenergic stimulation of the splenic blood vessels induces a generalized arterial constriction, except of the anastomotic arterioles, that becomes open; in such way, the blood pathway follows the course of the anastomotic arterioles and the collector arterioles also become constricted. The adrenergic vasoconstrictor effect is inhibited by the phenoxy-benzamine hydrochloride. The addition of acetylcholine chloride, in the dosage, used, induces a generalized arterial vessel constriction, mainly of the perifollicular plexus. This effect is inhibited by atropine sulfate which, on the other hand, produces evident enlargement of the perifollicular and pericolumnar arterial plexus.     

链霉菌-ZLT产生的蓝色素性质研究

报道了一株链霉菌产生的蓝色素的性质。研究表明,该色素水溶性好,具有较高的热稳定性;低pH条件下,抗氧化还原能力较强。大多数所测试的金属离子基本不影响色素的性质。中性条件下色素耐日光,碱性条件下耐紫外光。     

Combined in situ zymography, immunofluorescence, and staining of iron oxide particles in paraffin-embedded, zinc-fixed tissue sections

Superparamagnetic iron oxide particles are used as potent contrast agents in magnetic resonance imaging. In histology, these particles are frequently visualized by Prussian blue iron staining of aldehyde-fixed, paraffin-embedded tissues. Recently, zinc salt-based fixative was shown to preserve enzyme activity in paraffin-embedded tissues. In this study, we demonstrate that zinc fixation allows combining in situ zymography with fluorescence immunohistochemistry (IHC) and iron staining for advanced biologic investigation of iron oxide particle accumulation. Very small iron oxide particles, developed for magnetic resonance angiography, were applied intravenously to BALB/c nude mice. After 3 hours, spleens were explanted and subjected to zinc fixation and paraffin embedding. Cut tissue sections were further processed to in situ zymography, IHC, and Prussian blue staining procedures. The combination of in situ zymography as well as IHC with subsequent Prussian blue iron staining on zinc-fixed paraffin-embedded tissues resulted in excellent histologic images of enzyme activity, protease distribution, and iron oxide particle accumulation. The combination of all three stains on a single section allowed direct comparison with only moderate degradation of fluorescein isothiocyanate-labeled substrate. This protocol is useful for investigating the biologic environment of accumulating iron oxide particles, with excellent preservation of morphology.     

Amperometric glucose biosensors based on layer-by-layer assembly of chitosan and glucose oxidase on the Prussian blue-modified gold electrode

A glucose biosensor based on layer-by-layer (LBL) self-assembling of chitosan and glucose oxidase (GOD) on a Prussian blue film was developed. First, Prussian blue was deposited on a cleaned gold electrode then chitosan and GOD were assembled alternately to construct a multilayer film. The resulting amperometric glucose biosensor exhibited a fast response time (within 10 s) and a linear calibration range from 6 μM to 1.6 mM with a detection limit of 3.1 μM glucose (s/n = 3). With the low operating potential, the biosensor showed little interference to the possible interferents, including ascorbic acid, acetaminophen and uric acid, indicating an excellent selectivity.     

Combined In Situ Zymography, Immunofluorescence, And Staining Of Iron Oxide Particles In Paraffin-embedded, Zinc-fixed Tissue Sections

AbstractSuperparamagnetic iron oxide particles are used as potent contrast agents in magnetic resonance imaging. In histology, these particles are frequently visualized by Prussian blue iron staining of aldehyde-fixed, paraffin-embedded tissues. Recently, zinc salt-based fixative was shown to preserve enzyme activity in paraffin-embedded tissues. In this study, we demonstrate that zinc fixation allows combining in situ zymography with fluorescence immunohistochemistry (IHC) and iron staining for advanced biologic investigation of iron oxide particle accumulation. Very small iron oxide particles, developed for magnetic resonance angiography, were applied intravenously to BALB/c nude mice. After 3 hours, spleens were explanted and subjected to zinc fixation and paraffin embedding. Cut tissue sections were further processed to in situ zymography, IHC, and Prussian blue staining procedures. The combination of in situ zymography as well as IHC with subsequent Prussian blue iron staining on zinc-fixed paraffin-embedded tissues resulted in excellent histologic images of enzyme activity, protease distribution, and iron oxide particle accumulation. The combination of all three stains on a single section allowed direct comparison with only moderate degradation of fluorescein isothiocyanate-labeled substrate. This protocol is useful for investigating the biologic environment of accumulating iron oxide particles, with excellent preservation of morphology.     

PATHWAY OF WATER MOVEMENT IN HYDROIDS OF POLYTRICHUM COMMUNE HEDW. (BRYOPSIDA)

The pathway of water movement in hydroids of Polytrichum was determined by the precipitation of an electron-dense crystal (Prussian blue) in the transpirational stream. Hydrolysed end walls appear highly water permeable since Prussian blue granules were localized within the loose fibrillar network. Electron-dense granules were found free in the lumen but not in the lateral wall or in the middle lamella. These results are compared with data from vascular plant tracheary elements.     

Molecule-based magnets with TC above room temperature: Improved synthesis of vanadium–chromium Prussian blue analogues with inserted alkali cations

We report the synthesis of several new vanadium–chromium Prussian blue analogues with a Curie temperature above room temperature. A catalytic amount of vanadium(III) during the synthesis allows to get improved magnetic properties, stable Curie temperatures (T_C) and a magnetisation at saturation in satisfying agreement with the stoichiometry. The insertion of alkali cations (potassium, rubidium, caesium) allows to reach a V:Cr stoichiometry close to 6:5, hence to enhance the number of magnetic neighbours compared to the usual V:Cr 3:2 stoichiometry and to increase accordingly the Curie temperature. For the same stoichiometry, the ferrimagnetic ordering temperature varies slightly with the nature of the inserted alkali cation (T_C/K = 360, 346 and 340 K for the potassium, rubidium and caesium derivatives, respectively). X-ray absorption spectroscopy allows to characterise the local surroundings of the chromium and vanadium ions and to propose an explanation of the magnetic properties.     

Biodegradation of alkali lignin by a newly isolated Rhodococcus pyridinivorans CCZU-B16

Bioprocess and Biosystems Engineering - Based on the Prussian blue spectrophotometric method, one high-throughput screening strategy for screening lignin-degrading microorganisms was built on...     

A Stable Graphitic,Nanocarbon‐Encapsulated,Cobalt‐Rich Core–Shell Electrocatalyst as an Oxygen Electrode in a Water Electrolyzer

The oxygen electrode plays a vital role in the successful commercialization of renewable energy technologies, such as fuel cells and water electrolyzers. In this study, the Prussian blue analogue‐derived nitrogen‐doped nanocarbon (NC) layer‐trapped, cobalt‐rich, core–shell nanostructured electrocatalysts (core–shell Co@NC) are reported. The electrode exhibits an improved oxygen evolution activity and stability compared to that of the commercial noble electrodes. The core–shell Co@NC‐loaded nickel foam exhibits a lower overpotential of 330 mV than that of IrO₂ on nickel foam at 10 mA cm^?2 and has a durability of over 400 h. The commercial Pt/C cathode‐assisted, core–shell Co@NC–anode water electrolyzer delivers 10 mA cm^?2 at a cell voltage of 1.59 V, which is 70 mV lower than that of the IrO₂–anode water electrolyzer. Over the long‐term chronopotentiometry durability testing, the IrO₂–anode water electrolyzer shows a cell voltage loss of 230 mV (14%) at 95 h, but the loss of the core–shell Co@NC–anode electrolyzer is only 60 mV (4%) even after 350 h cell‐operation. The findings indicate that the Prussian blue analogue is a class of inorganic nanoporous materials that can be used to derive metal‐rich, core–shell electrocatalysts with enriched active centers.     

Effect of zinc on translocation of iron in soybean plants

Zinc interfered with translocation of iron from roots to above ground parts of Glycine max. (L.) Merrill var. Hawkeye. During periods in which zinc impeded iron translocation, it also suppressed the production of reductant by roots. Addition of iron, as a ferric metal chelate (iron ethylenediaminedihydroxyphenylacetic acid), to the growth medium overcame the interference of zinc. In the root epidermis, potassium ferricyanide formed a precipitate (Prussian blue) with ferrous iron derived from the previously supplied iron ethylenediaminedihydroxyphenylacetic acid. The reduction of ferric iron was suppressed by zinc.     

Metal‐Organic Framework Cathodes Based on a Vanadium Hexacyanoferrate Prussian Blue Analogue for High‐Performance Aqueous Rechargeable Batteries

Despite the unique advantages of the metal‐organic framework of Prussian blue analogues (PBAs), including a favorable crystallographic structure and facile diffusion kinetics, the capacity of PBAs delivered in aqueous systems has been limited to ≈60 mA h g^?1 because only single species of transition metal ions incorporated into the PBAs are electrochemically activated. Herein, vanadium hexacyanoferrate (V/Fe PBA) is proposed as a breakthrough to this limitation, and its electrochemical performance as a cathode for aqueous rechargeable batteries (ARBs) is investigated for the first time. V/Fe PBAs are synthesized by a simple co‐precipitation method with optimization of the acidity and molar ratios of precursor solutions. The V/Fe PBAs provide an improved capacity of 91 mA h^?1 under a current density of 110 mA g^?1 (C‐rate of ≈1.2 C), taking advantage of the multiple‐electron redox reactions of V and Fe ions. Under an extremely fast charge/discharge rate of 3520 mA g^?1, the V/Fe PBA exhibits a sufficiently high discharge capacity of 54 mA h g^?1 due to its opened structure and 3D hydrogen bonding networks. V/Fe PBA‐based ARBs are the most promising candidates for large‐scale stationary energy storage systems due to their high electrochemical performance, reasonable cost, and high efficiency.