PLD grown ZnO-K3[Fe(CN)6] composite thin film for biosensing application

Zinc oxide-potassium ferricyanide (ZnO-KFCN) composite film was prepared on ITO coated corning glass using pulsed laser deposition (PLD). The composite film has proved to be a suitable platform for enzyme immobilization. The composite matrix exhibits the advantages of ZnO along with enhanced redox property due to the presence of a mediator in the matrix. Glucose oxidase (GOx) has been chosen as the model enzyme for studying the application of the present matrix to biosensing. The sensing response of the bio-electrode, GOx/ZnO-KFCN/ITO/glass, towards glucose was studied by electrochemical and photometric techniques. The bio-electrode exhibits good linearity and low value of Michaelis-Menten constant. Due to efficient biosensing in a mediator-less system the present bio-electrode should lead to a hand held integrated lab-on-chip device.     

甲胺-铁氰化钾抛光液中铜钝化成膜的机理研究

用电化学循环伏安测试技术研究了铜在甲胺铁氰化钾抛光液中钝化成膜的机理。通过大幅度改变电位扫描速率,分析了氧化峰电流(IApa)、氧化峰电位(EApa)及阳阴峰电流的比值(IApa/IApc)与相应电位扫描速率的关系。结果表明,氧化峰电流和氧化峰电位均与电位扫描速率的平方根成线性关系,说明成膜复盖度θ与电位扫描速率无关,成膜过程符合M櫣ller模型。成膜过程中,电极反应存在后置化学转化,铜在去极化剂作用下发生失去一个电子的阳极溶解反应,然后再进行化学转化反应生成Cu4[Fe(CN)6]钝化膜。在CMP过程中,具有这种钝化膜的铜的腐蚀电流密度及抛光速率随抛光转速的增加而增大。     

高质量水系钠离子电池正极Fe4[Fe(CN)6]3的合成及其电化学性能

采用水热法合成高质量的Fe₄[Fe(CN)₆]₃(HQ-FeHCF)纳米材料, 并对材料进行X射线衍射(XRD), 扫描电子显微镜(SEM), 透射电子显微镜(TEM)和热重分析测试(TGA)等表征。结果表明：Fe₄[Fe(CN)₆]₃呈规则立方体, 颗粒大小约500 nm, 属面心立方结构。Fe₄[Fe(CN)₆]₃在NaClO₄-H₂O-聚乙二醇电解液中1C、2C、5C、10C、20C、30C和40C的容量分别为124、118、105、94、83、74和64 mAh·g ^-1, 表现出优异的倍率性能; 以5C倍率循环500次, 容量保持率接近100%, 表现出极佳的循环稳定性。以Fe₄[Fe(CN)₆]₃和磷酸钛钠分别为正负极的全电池工作电压高达1.9 V, 能量密度可达126 Wh·kg ^-1; 以5C倍率恒流充放电测试140次后全电池容量保持率为92%, 且库伦效率始终接近100%。     

K3[Fe(CN)6]浓度对PEO法制备硫改性Fe3O4膜层结构和降解性能的影响

为了提高铁基类Fenton催化剂的活性,利用等离子体电解氧化法在钛合金上制备出了硫改性Fe3O4膜层类Fenton催化剂,研究了电解液中铁源K3[Fe(CN)6]的浓度对膜层的结构组成和降解苯酚性能的影响.采用SEM、EDS和XRD对催化剂的表面形貌和相组成进行了表征,以苯酚为目标降解物评价其类Fenton催化活性.结...     

A facile synthesis of PEG-coated magnetite (Fe3O4) nanoparticles and their prevention of the reduction of cytochrome c

We report here a facile and green synthetic approach to prepare magnetite (Fe(3)O(4)) nanoparticles (NPs) with magnetic core and polyethylene glycol (PEG) surface coating. The interaction of the bare and PEG-coated Fe(3)O(4) NPs with cytochrome c (cyt c, an important protein with direct role in the electron transfer chain) is also reported in this study. With ultrasonication as the only peptization method and water as the synthesis medium, this method is easy, fast, and environmentally benign. The PEG coated NPs are highly water dispersible and stable. The bare NPs have considerable magnetism at room temperature; surface modification by PEG has resulted in softening the magnetization. This approach can very well be applicable to prepare biocompatible, surface-modified soft magnetic materials, which may offer enormous utility in the field of biomedical research. Detailed characterizations including XRD, FTIR, TG/DTA, TEM, and VSM of the PEG-coated Fe(3)O(4) NPs were carried out in order to ensure the future applicability of this method. Although the interaction of bare NPs with cyt c shows reduction of the protein, efficient surface modification by PEG prevents its reduction.     

Complexation in Binary Systems Uranyl(VI)-8-Quinolinethiol in Gelatin-immobilized (UO2)2[Fe(CN)6] Matrices

Complexation processes occurring in gelatin-immobilized uranyl(VI) hexacyanoferrate(II) matrixsystems on contact with aqueous alkaline (pH 12.0) solutions of 8-quinolinethiol, its 5-chloro, 5-bromo' and 5-methylthio derivatives were studied. Incorporation of the ligand into the inner coordination sphere ofUO₂ ^{2 +} is preceded by alkali transformation of gelatin-immobilized (UO₂)₂[Fe(CN)₆] to uranic acid (H₂UO₄). In the course of complexation in each of the uranyl(VI)-ligand systems studied, only coordination compounds UO₂L₂ (L^- is the deprotonated form of the ligand) are formed.     

Fe2O3 core-NaCo[Fe(CN)6] shell nanoparticles—Synthesis and characterization

A facile precipitation route was developed for the synthesis of cobalt hexacyanoferrate (CoHCF) as a thin shell around cores of nanoparticles of iron(III) oxide, forming nanoparticles of iron(III) oxide@CoHCF (n-Fe₂O₃@NaCo[Fe(CN)₆]). The morphology and structure of the as-prepared n-Fe₂O₃@NaCo[Fe(CN)₆] were characterized by the techniques of electron microscopies, X-ray diffraction measurements, X-ray photoelectron spectroscopy, infrared spectroscopy and thermogravimetry. Carbon composite electrodes of n-Fe₂O₃@NaCo[Fe(CN)₆] were prepared and the electrochemical behavior of the nanoparticles was evaluated using cyclic voltammetry. The redox couples of n-Fe₂O₃@NaCo[Fe(CN)₆] were investigated and the diffusion coefficients of counter cation in the shell of CoHCF were obtained. The effect of size of particles and the structure of CoHCF was also evaluated. n-Fe₂O₃@NaCo[Fe(CN)₆] represented prominent electrocatalytic activity toward the oxidation of some biologically active compounds.     

铜在甲胺-铁氰化钾化学机械抛光液中的腐蚀与钝化

用电化学测试技术研究了腐蚀介质和成膜剂浓度对铜表面的腐蚀与钝化成膜的影响,分析了钝化膜的成分,探讨了钝化膜在抛光压力和转速作用下的磨损与表面再钝化的行为,测量了铜在化学机械抛光过程中的极化曲线。结果表明铜在甲胺溶液介质铁氰化钾抛光液中易钝化,钝化膜的主要成分为Cu4[Fe(CN)6],有少量Cu20存在。钝化膜的磨损特性随成分浓度不同而不同。钝化膜的磨损难易程度与钝化膜的本身特性、抛光压力及转速有关。抛光过程中因钝化膜被磨损,腐蚀加快,腐蚀电流密度大幅增加。配方0．1％甲胺溶液 0．5％K3Fe(CN)6 5％Al2O3可行。     

Synthesis of Fe3N by mechano-chemical reactions between iron and organic H x (CN)6 ring compounds

Novel mechanically activated solid state synthesis reactions between elemental Fe powder and amine compounds-piperazine (Hi₁₀C₄N₂) and pyrazine (H₄C₄N₂) — have been studied. Powder samples prepared after 144 and 228 h of ball milling in vacuum were examined by X-ray diffraction, scanning electron microscopy and thermal analysis methods. After ball milling for a time brief compared to that required for most solid state-gas reactions formation of a crystalline iron nitride (Fe₃N) a predominant phase with nitrogen concentration up to ca. 9.0 wt% was observed. Thermal analysis experiments showed structural stability of the Fe₃N phase up to ca. 720 K. In the final product a small residual fraction was formed from Fe and carbon dispersed during mechanical processing. The concentration of carbon in this fraction, estimated from thermogravimetric analysis was up to 2.5 wt%, dependent on milling conditions and the organic compound used. Mechanochemical synthesis, reaction effectiveness, product composition and particle morphology depends on the milling time and chemical characteristics of the organic compound used. Fine Fe₃N particles at a submicrometre size range were obtained only by milling with pyrazine. Further, the higher chemical reactivity of pyrazine than piperazine was confirmed through the higher level of nitridation achieved in the same preparation time.     

Direct electrochemistry and electrocatalytic behavior of hemoglobin entrapped in chitosan/gold colloid/3-aminopropyl triethylene silane/Prussian blue composite film

Direct electrochemistry of hemoglobin (Hb) is achieved by immobilizing Hb-chitosan on a gold colloid/3-aminopropyl triethylene silane/Prussian blue composite film-modified glassy carbon electrode. The modified electrode exhibits a pair of well defined and quasi-reversible peaks with a formal potential of 0.205 V. The immobilized Hb retains its biological activity and shows high catalytic activity to the reduction of hydrogen peroxide. Experimental conditions influencing the biosensor performances such as pH and potential are optimized and assessed. Under the optimized conditions, the catalytic currents are linear to the concentrations of H₂O₂ in the ranges of 2-480 μM. The detection limit is 0.1 μM (S/N = 3). The electrochemical sensor has high stability and good reproducibility. Ultraviolet visible absorption spectra and Fourier transform infrared spectroscopy show that Hb keeps almost natural structure in the composite film. Therefore, the composite film is an alternative matrix for protein immobilization and biosensor preparation.     

Hybrid Molecular Metals Based on BEDO-TTF Salts with Paramagnetic [CrNO(CN)5]3− and [M(CN)6]3− Anions, M=Fe, Cr

Two different β″-type crystals have been obtained in the syntheses of the title salts. The crystals show metallic behavior of conductivity and paramagnetic response from the metal complex anions.     

Thermal,structural and textural studies on the double complex salt [Co(NH3)6][Fe(CN)6] and on its silica-supported catalysts

Thermal analyses were carried out for the simple complexes [Co(NH₃)₆]Cl₃ and K₃[Fe(CN)₆] together with the double complex [Co(NH₃)₆][Fe(CN)₆] using thermogravimetric analysis, differential thermal analysis (DTA) and derived DTA (DDTA). Two series of silica-supported catalyst samples were prepared with soaking periods ranging from 5 h to 7 days, and likewise investigated. Structural changes of the original samples and their thermally treated products obtained at temperatures < 500 °C were monitored using X-ray diffraction and infrared spectroscopy. Textural variations were also studied using the N₂ adsorption technique. The decomposition of the simple complex [Co(NH₃)₆]Cl₃ occurs in two main steps that give rise to two asymmetric endothermic peaks centred at 225 and 350 °C. The first step involves two decomposition processes in which primarily two chloride ions migrate to the inner coordination sphere, thereby releasing two coordinated NH₃ that are evolved, followed by simultaneous decomposition and reduction to CoCl₂ · 2NH₃. The second step involves the decomposition of this latter compound to CoCl₂ with some reduction to Co. K₃[Fe(CN)₆] decomposes in a more complex manner, yet two strong exotherms are observed at 345 and 400 °C — the former being accompanied by a loss in weight due to its decomposition, whereas the latter is accompanied by a small increase in weight where an oxidation process seems to take place with its further decomposition. The double complex [Co(NH₃)₆][Fe(CN)₆] exhibits five consecutive decomposition steps in the temperature range 210–305 °C. The first is reproduced as an endotherm at 180 °C, whereas the remaining four steps cannot be distinguished separately by DTA due to the strong exothermic effects and only two exotherms are observed at 255 and 280 °C. The steps are identified according to the simultaneous reaction of six molecules together, leaving a final solid product with empirical formula Fe(CN)₂Co. X-ray diffraction of the double complex retains the characteristics of the constituent simple complexes with the appearance of two new very strong bands with a d- spacing of 0.5483 and 0.3005 nm. The specific surface areas of the catalyst samples are found to depend on the ion moiety supported first during preparation as well as on the soaking period. The catalyst samples are predominantly microporous and the variations in surface characteristics are discussed. V _I-t plots reveal the presence of two groups of pore sizes in some cases.     

Aqueous nickel-nitrilotriacetate modified Fe(3)O(4)-NH(3)(+) nanoparticles for protein purification and cell targeting

A comprehensive totally aqueous phase synthesis of nickel-nitrilotriacetate (Ni-NTA) modified superparamagnetic Fe(3)O(4) nanoparticles is presented. The Fe(3)O(4)-NTA-Ni nanoparticles are able to perform efficient and specific purification of 6-His tagged proteins from crude cell lysates, as evidenced by sodium dodecyl sulphate polyacrylamide gel electrophoresis (SDS-PAGE) and Western blot analysis. The average binding capacity, as demonstrated by streptopain (M(W) 42?kDa), is 0.23?mg/mg (protein/Fe(3)O(4)-NTA-Ni). Considering the high affinity and specificity of the binding between hexahistidine motif and Ni-NTA, Ni-NTA modified nanoparticles could act as a module to carry 6-His tagged proteins on the particle surface with molecular orientation control, since only the 6-His domain could be attached. These modularly designed functional nanoparticles enhance cancer cell targeting, as supported by the in vitro receptor mediated targeting assay using RGD-4C-6-His fusion peptide. The nanoparticles show no significant hemolysis for human blood and could be investigated further for their in vivo functional imaging applications.     

Enhanced removal of Cr(VI) from aqueous solution using polypyrrole/Fe3O4 magnetic nanocomposite

Fe(3)O(4) coated polypyrrole (PPy) magnetic nanocomposite was prepared via in situ polymerization of pyrrole monomer for the removal of highly toxic Cr(VI). Structure and morphology of the prepared nanocomposite were characterized by attenuated total reflectance Fourier transform infrared spectroscopy (ATR-FTIR), X-ray diffraction pattern, Field emission scanning electron microscopy (FE-SEM) and high resolution transmission electron microscopy (HR-TEM). Electron spin resonance (ESR) studies confirmed that the nanocomposite is magnetic in nature. Up to 100% adsorption was found with 200mg/L Cr(VI) aqueous solution at pH 2. Adsorption of Cr(VI) on the surface of the adsorbent was confirmed by the ATR-FTIR and X-ray photoelectron spectroscopy (XPS). XPS studies also suggested that ion exchange and reduction on the surface of the nanocomposite may be the possible mechanism for Cr(VI) removal by the PPy/Fe(3)O(4) nanocomposite. Adsorption results showed that Cr(VI) removal efficiency by the nanocomposite decreased with an increase in pH. Adsorption kinetics was best described by the pseudo-second-order rate model. Isotherm data fitted well to the Langmuir isotherm model. Thermodynamic study revealed that the adsorption process is endothermic and spontaneous in nature. Desorption experiment showed that in spite of the very poor recovery of the adsorbed Cr(VI); the regenerated adsorbent can be reused successfully for two successive adsorption-desorption cycles without appreciable loss of its original capacity.     

Kinetics of Fe(3)O(4)-CoO/Al(2)O(3) catalytic ozonation of the herbicide 2-(2,4-dichlorophenoxy) propionic acid

The presence of Fe(3)O(4)-CoO/Al(2)O(3) can improve degradation efficiency significantly during the ozonation of the herbicide 2-(2,4-dichlorophenoxy) propionic acid (2,4-DP). The main factors affecting degradation efficiency, such as pH, the catalyst concentration and addition of the scavenger, were investigated. The kinetics of the catalytic ozonation are also discussed. The results indicate that two factors, the oxidation after adsorption of 2,4-DP and the oxidation of hydroxyl radicals (OH), lead to a great enhancement in ozonation efficiency during the catalytic ozonation of 2,4-DP in the presence of Fe(3)O(4)-CoO/Al(2)O(3), in which the oxidation of the OH plays an important role. Under controlled conditions, the apparent reaction rate constants for the degradation of 2,4-DP were determined to be 2.567 × 10(-4)s(-1) for O(3) and 1.840 × 10(-3)s(-1) for O(3)/Fe(3)O(4)-CoO/Al(2)O(3). The results from the analysis of the reaction kinetics using the relative method showed that O(3)/Fe(3)O(4)-CoO/Al(2)O(3) possessed a larger R(ct) (R(ct) is defined as the ratio of the ·OH exposure to the O(3) exposure, R(ct) = ∫C(t)(OH) dt/C(t)O(3)dt) than O(3), indicating that O(3)/Fe(3)O(4)-CoO/Al(2)O(3) produced more hydroxyl radicals.     

Na3V2(PO4)3/CN/Rgo复合正极材料的构筑及储钠性能研究

Na3 V2(PO4)3具有理论容量高、钠离子超导体(NASlCON)结构等优势,被认为是一种值得研究和大规模应用的新型钠离子电池正极材料.然而低的电导率导致其电化学性能在大电流充放电条件下不理想.本实验采用固相法制备了一种由氮掺杂碳与还原氧化石墨烯(rGO)共修饰的Na3V2(PO4)3/CN/rGO(NVP/CN/rGO)复合正极材料,并借助材料表征手段、电化学分析技术等对不同含量rGO掺入的NVP/CN/rGO正极材料的微观形貌和电化学性能进行了系统研究.结果显示,NVP/CN/rGO-2复合材料颗粒分布均匀,并表现出较高的可逆容量和优越的循环稳定性.在0.2 C、10 C下可逆容量分别为116.9 mAh·g-1和99.4 mAh·g-1,且在10 C下循环1500次后,容量保持率为97.2％.复合材料表现优异性能的主要原因是:rGO特殊的导电网络结构将孤立的NVP/CN连接起来,提升了颗粒之间的接触电导,使其导电性进一步提高,从而显著提升其电化学性能.     

Determination of superoxide in seawater using 2-methyl-6-(4-methoxyphenyl)-3,7- dihydroimidazo[1,2-a]pyrazin-3(7H)-one chemiluminescence

Superoxide, the one-electron reduced form of dioxygen, is known to be generated in marine environments by photochemical and biological processes. Because of its selective reaction with only a few commonly occurring compounds, superoxide is expected to approach concentrations in the high picomolar or low nanomolar range in seawater. Most currently existing methods do not have both the necessary sensitivity and selectivity to measure naturally occurring concentrations. In contrast, we demonstrate here that the chemiluminescence reagent 2-methyl-6-(4-methoxyphenyl)-3,7-dihydroimidazo[l,2-a]pyrazin-3(7H)-one (MCLA) is selective for superoxide in seawater and can be used with a detection limit of around 50 pM. Although a wide range of potential interferences were shown not to react with MCLA directly, some care must be taken when analyzing samples containing nanomolar concentrations of Fe(II), Cu(I), Mo(V), V(III), or V(IV), since these compounds can react with oxygen to produce superoxide during analysis that is subsequently detected. We describe two methods for calibrating the system, one employing photochemically generated superoxide standards and the other employing the superoxide-generating xanthine/xanthine oxidase system and discuss limitations on the use of each. The method was successfully used in the field to determine steady-state superoxide concentrations in the water column in the eastern equatorial Pacific Ocean.     

Fe(CN)6 incorporation on Poly(3,4-ethylenedioxythiophene) films: Preparation and X-ray Photoelectron Spectroscopy characterization of the modified electrodes

Poly(3,4-ethylenedioxythiophene) (PEDOTh) films were potentiodynamically deposited on platinum from tetrabutylammonium hexafluorophosphate/acetonitrile solutions. Polymers prepared with different number of cycles showed reversible redox behaviour and the X-ray Photoelectron Spectroscopy (XPS) characterization revealed the existence of zones with different conductivity and confirmed the presence of PF₆⁻. The incorporation of the metallic complex Fe(CN)₆³⁻ in the PEDOTh films was made in one step, after the electrosynthesis of a film grown with a given number of potential cycles, and by means of polymerization/incorporation sequences. XPS data confirmed the presence of the inorganic species and the highest Fe 2p_3/2 peak intensity was observed for thin films (30 cycles) when the one step incorporation has been used. The XPS results suggest a partial dissociation of the Fe-(C-N) bond of the complex in the modified electrodes.     

Photoluminescence and electrochemistry behavior of well-dispersible poly-N-[5-(8-quinolinol)ylmethyl]aniline/nano-TiO2 composite

Well-dispersible poly-N-[5-(8-quinolinol)ylmethyl]aniline/nano-TiO₂ composite was synthesized by the surface modification of nano-TiO₂ particles using poly-N-[5-(8-quinolinol)ylmethyl] (PANQ), and it was characterized by Fourier-transform infrared spectroscopy, photoluminescence spectroscopy, thermogravimetric analysis and scanning electron microscope, as well as conductivity and cyclic voltammogram were given. The conductivity of this composite was 2.1 × 10⁻² S cm⁻¹ at 25 °C, and showed good redox reversibility. It was easy to cast a transparent conducting film with photoluminescent property.