Solid-state Electrochemistry of Gadolinium Hexacyanoferrate Modified Electrode and Electrocatalytic Properties of Gadolinium Hexacyanoferrate

A new electroactive polynuclear inorganic compound of rare earth metal, gadolinium hexacyanoferrate (GdHCF), was prepared and characterized using the techniques of FTIR spectroscopy, thermogravimetric analysis (TG), UV-Vis spectrometry, X-ray photoelectron spectroscopy (XPS), ICP atomic emission spectroscopy, and EDX. The results of ICP atomic emission spectroscopy, EDX, and TGA indicated that the prepared GdHCF sample had a stoichiometry of NaGdFe(CN)₆·12H₂O (when GdHCF was prepared in NaCl solution). The FTIR spectrum of GdHCF showed that there were two types of water molecules in the structure of GdHCF: one was the interstitial water (5 H₂O), which resulted from the association of water due to H-bonding, and the other was water coordinated with Gd (7 H₂O). The results obtained using XPS showed that the oxidation state of Fe and Gd in the GdHCF sample was +2 and +3, respectively. GdHCF was immobilized on the surface of spectroscopically pure graphite (SG) electrode forming the GdHCF/SG electrode, and the solid-state electrochemistry of the resultant electrode was studied using cyclic voltammetry. The cyclic voltammetric results indicated that the GdHCF/SG electrode exhibited a pair of well-defined and stable redox peaks with the formal potential of E^0′=(197±3) mV. The effects of the concentration of the supporting electrolyte on the electrochemical characteristics of GdHCF were studied, and the results showed that the value of E^0′ increased linearly with the activity of the cationic ion of the supporting electrolyte (lga_Na⁺), with a slope of 54.1 mV, which may become a novel method for determining the activity of Na⁺ in solution. Further experimental results indicated that GdHCF had electrocatalytic activities toward the oxidation of dopamine (DA) and ascorbic acid (AA), and the electrocatalytic current increased linearly with the concentration of DA (or AA) in the range of 1.0–10.0 mmol·L^?1 (for DA) or 0.5–20.0 mmol·L^?1 (for AA).     

同多酸和杂多酸修饰微电极的电化学研究——Ⅳ.1:2-磷钼杂多酸薄膜修饰碳纤维微电极的制备和电化性质

本文报道了1:12-磷铜杂多酸(PMo_(12)薄膜修饰碳纤维(CF)微电极的制备及其电化学性质。采用简单,快速的浸渍吸附制备的PMo_(12)薄膜修饰CF电极在酸性介质中具有很高的稳定性和氧化还原活性,电解质溶液的pH值和扫描电位范围对PMo_(12)膜的稳定性和电化学性质产生较大的影响。另一方面,PMo_(12)薄膜修饰CF微电极对酸性水溶液中的PMo_(12)和氯酸根离子(ClO)_3~-)的电催化还原作用也进行了描述。     

低电流密度下恒电流法制备的聚苯胺修饰电极

研究了低电流密度下恒电流法制备的聚苯（ＰＡ）修饰电极的性质及其影响因素，探讨了低电流密度聚合的ＰＡ膜的优点。发现此种条件下聚合的ＰＡ膜具有较好的电荷传输能力，它不仅对Ｂｒ＾－，Ｔｌ＾＋／Ｔｌ等电对的氧化还原反应有更好的电催化活性，而且对Ｈ＾＋的Ｎｅｒｎａｓｔ响应也更接近理论值。     

Simultaneous isolation and determination of esculin and rutin in natural materials using SPE and HPLC

Summary Esculin (ESC) and rutin (RUT) have been simultaneously isolated from pharmaceutical natural materials by solid phase extraction (SPE). Determination of both substances was performed by reversed phase high performance liquid chromatography (RPHPLC) with UV detection. Optimization of the separation conditions showed that simultaneous isolation and determination of rutin and esculin from pharmaceutical material was possible. The recovery obtained was not lower than 95±2%.     

聚天青A膜修饰电极的电化学特性及其对亚硝酸根的电催化性能

在玻碳电极上以循环伏安法制备了聚天青A膜修饰电极(PAAE) ,天青A能够在玻碳电极上形成稳定的聚合膜 ;通过正交试验确定了电聚合天青A的最佳条件 ,研究了该修饰电极的电化学特性 ,并讨论了其对亚硝酸根的电催化还原作用 ;结果表明 ,亚硝酸根在PAAE上有很好的电流响应 ,催化峰电流与亚硝酸根浓度在1.0×10-5 ～4.0×10-3 mol/L之间呈良好的线性关系     

Fabrication of Poly(allylamine)ferrocene Monolayer Based on Electrostatic Interaction and Its Electrocatalytic Oxidation of Ascorbic Acid

A poly(allylamine)ferrocene monolayer was built on the surface of gold electrode modified with negatively charged alkanethiol based on electrostatic interaction. The electrochemical behavior of the modified electrode was characterized by cyclic voltammetry in detail. The modified electrode was shown to exhibit excellent electrocatalytic response to the oxidation of ascorbic acid. The anodic overpotential was reduced by about 170 mV compared with that obtained at a bare gold electrode. The modified electrode possesses several attractive features, such as simple preparation, fast response and good chemical and mechanical stability.     

The aqueous cationic system sodium undecenoate-dodecyltrimethylammonium bromide at low concentration

The aqueous sodium undecenoate (SUD) –dodecyltrimethylammonium bromide (DTAB) catanionic system was studied at low concentration. The system did not precipitate, even at a 1:1 SUD:DTAB proportion, but showed the formation of a coacervate in a range of surfactant mixture compositions. Micelles have a preferential composition of 0.37 mole fraction of SUD. This behavior is attributed to the presence of the double bond at the distal extreme of the SUD molecule, which can form hydrogen bonds with water. Consequently, the –CH=CH₂ group is situated at the interface between the hydrocarbon micelle core and water, reducing the interfacial free energy. Structural computations demonstrate that the mentioned SUD proportion produces complete coverage of the micelle surface by the double bonds.     

Amperometric detection of hydrazine by cyclic voltammetry and flow injection analysis using ruthenium modified glassy carbon electrodes

Glassy carbon electrodes modified with (5-amino-1,10-phenanthroline)bis(bipyridine)ruthium(II) chloride hydrate, [(bpy)₂Ru(5-phenNH₂)]Cl₂·H₂O, are shown to oxidize hydrazine with excellent sensitivity. The presence of an amine group on the ruthenium complex facilitates electropolymerization onto the electrode surface. Using cyclic voltammetry, a large catalytic current is observed upon oxidation of hydrazine in phosphate buffer (pH 5.0), compared to the current obtained from the ruthenium-modified electrode with no hydrazine present. The sensitivity of cyclic voltammetry is sufficient for obtaining a linear calibration curve for hydrazine over the range of 10⁻⁵ to 10⁻² M. Hydrodynamic amperometry was used to determine the working potential for flow injection analysis. The limit of detection for hydrazine was determined to be 8.5 μM using FIA. The thickness of these films was shown to increase linearly with the number of electropolymerization cycles, in the range of 1000-2500 nm for 5-20 cycles, respectively, using Rutherford backscattering spectrometry (RBS). RBS analysis also suggests that the film is multilayered with the outermost layers containing a high ruthenium concentration, followed by layers where the concentration of ruthenium decreases linearly and approaches zero at the electrode surface.     

Chemically Sensitive Field‐Effect Transistors and Chemiresistors: New Materials and Device Structures

Electronic sensor technology remains of widespread and intense interest. There are compelling needs to detect chemical species ranging from small molecules dispersed in the gas phase to complex biopolymers in aqueous solution. This review describes some recent advances in three main areas: chemically sensitive resistors (chemiresistors, CRs) including inorganic and organic based devices, field effect transistors (FETs) with semiconducting layers and/or gates with chemical sensitivity, and sensors based on the differential conductivity of nanotubes and nanowires. Results reported in the last two to three years are emphasized, highlighting some current trends in the development of sensors for applications such as diagnostics, process monitoring, and security.