丙酮/水混合体系合成聚苯胺的聚合过程研究

对丙酮/水体系中合成聚苯胺(PAn)的反应进行跟踪,通过聚合过程的开路电压、聚合温度、特性粘度和中间体的分子结构对聚合过程进行研究。结果表明,丙酮/水体系对控制产物的粒度和分子量都有利;当丙酮/水的体积比为0.2左右时,所得产物的各项性能较好。与水体系相比,在丙酮/水混合体系中聚合过程维持高电位的时间延长,聚合链增长时间和自加速反应时间也有延长。苯胺聚合是以头-尾连接形式进行,且中间产物由高氧化态逐渐转变成中间氧化态。     

氨苄青霉素降解产物在汞膜电极上的伏安法研究

考察了氨苄青霉素在酸、碱条件下的降解产物于玻碳汞膜电极上的伏安行为 ,降解产物在醋酸缓冲溶液 ( p H5.5)的底液中均产生了灵敏的阴极还原峰 ,以碱降解条件为好。已将方法应用于模拟样品的分析。     

Cathodic stripping voltammetric determination of anti-cancer medicine nitrocaphanum at nafion modified electrode

An electrochemical method for the determination of anti-cancer medicine nitrocaphanum was described. The reaction mechanism of nitrocaphanum at Nafion CME was also discussed. It was found, in pH 2.5 medium, a linear response was observed for nitrocaphanum in the concentration range of 2.2 × 10^–8 M to 1.3 × 10^–6 M. Detection limit of this method is 5 × 10^–9 M, relative standard deviation for 10 measurements is 1.7%. The results of nitrocaphanum determination in real samples were satisfactory.     

对乙酰氨基酚在石墨烯/壳聚糖复合膜修饰电极上的电化学行为研究

制备了石墨烯-壳聚糖复合物修饰玻碳电极(GO/CS-GCE),考察了对乙酰氨基酚(APAP)在修饰电极上的电化学行为,发现石墨烯-壳聚糖复合物能较好改善玻碳电极对APAP的电化学性能,APAP在修饰电极上的电化学反应过程是受吸附控制的2电子,2质子反应过程;进一步研究发现在pH=9.16的碳酸钠-碳酸氢钠缓冲体系中,对...     

Preparation and corrosion resistance of polyaniline and waterborne polyurethane composite coating film

Polyaniline (PANI) particles were synthesized using aniline (AN), dodecyl benzene sulfonic acid (DBSA), and ammonium persulfate (APS). The particles were analyzed using scanning electron microscope (SEM), X-ray diffraction (XRD), and fourier transform infrared spectroscopy (FTIR). A PANI/waterborne polyurethane composite material (PANI-WPU) was obtained by combining it with polyethylene glycol (PEG600), diphenylmethane diisocyanate (MDI), dimethylol propionic acid (DMPA), N-methyl pyrrolidone (NMP), and dibutyltin lauric acid (DBTDL). The structure was characterized by the FTIR spectrum. The mechanical characteristics of the coating film were evaluated with respect to the PANI content, as well as its water absorption, glossiness, electrochemical corrosion resistance, and acid and alkali resistance. The PANI/waterborne polyurethane film has a maximum tensile strength of 23 $\pm 1$ MPa, an elongation of 1012%, a pencil hardness of 5H, a flexibility of 2 mm, an impact resistance of 50 cm, the water absorption of 14.66%, and the glossiness of 99.9 $\pm 0.1$ at 60°. When the PANI content is 0.7%, the mechanical characteristics, glossiness, and anti-corrosion performance of the composite film improve. The corrosion inhibition efficiency of the aqueous polyurethane coating film with PANI can reach 99.74%, as shown by the examination of electrochemical polarization curves and impedance spectra. The tinplate is coated with a 0.7% PANI-WPU composite material and edge sealing. This coating provides excellent protection against acid and alkali resistance, as demonstrated by its ability to withstand immersion in 10% H₂SO₄ and 10% NaOH solution for 90 days without any paint peeling off.     

聚苯胺分子印迹膜电化学传感器检测氯霉素

以苯胺为功能单体和交联剂,氯霉素(chloramphenicol,CAP)为模板分子,采用电化学聚合法(循环伏安法)在金电极上合成了对CAP具有快速响应能力的聚苯胺分子印迹膜;结合差示脉冲伏安法建立了针对氯霉素的检测方法,并将所制备的聚苯胺分子印迹膜用作电化学传感器以测定氯霉素眼药水中的氯霉素.结果表明,所制备的聚苯胺分子印迹膜具有制备简单、响应快速、灵敏度高、再生性能良好等特点;其对氯霉素眼药水中的氯霉素的检测结果令人满意,有望用于实际样品中氯霉素的检测.     

Electrochemical determination of iodide by poly(3-aminophenylboronic acid) film electrode at moderately low pH ranges

A new potentiometric sensor for the determination of iodide based on poly(3-aminophenylboronic acid) (PAPBA) film electrode was constructed. Poly(3-Aminophenylboronic acid) films were synthesized electrochemically on platinum electrode by cyclic voltammetry. The effect of film thickness, pH, and preconditioning parameters on the electrode performance were examined. The analytical performance was evaluated and linear calibration graphs were obtained in the concentration range of 10⁻⁶ to 10⁻¹ M iodide ion. The limit of detection was found to be 8 × 10⁻⁷ M. The response time of the sensor was 5 s and its lifetime is about one week. To check the selectivity of the PAPBA film for iodide ion, potential interferences such as Cl⁻, Br⁻, F⁻, CN⁻, IO₃⁻, Ca²⁺, and Mg²⁺ were tested. The PAPBA electrode was also employed as a sensing platform for the determination of iodide ions in commercial table salt.     

Nickel foam-supported porous NiO/polyaniline film as anode for lithium ion batteries

Nickel foam-supported porous NiO film was prepared by a chemical bath deposition technique, and the NiO/polyaniline (PANI) film was obtained by depositing the PANI layer on the surface of the NiO film. The NiO film was constructed by NiO nanoflakes, and after the deposition of PANI, these nanoflakes were coated by PANI. As an anode for lithium ion batteries, the NiO/PANI film exhibits weaker polarization as compared to the NiO film. The specific capacity after 50 cycles for NiO/PANI film is 520 mAh g⁻¹ at 1 C, higher than that of NiO film (440 mAh g⁻¹). The improvement of these properties is attributed to the enhanced electrical conduction and film stability of the electrode with PANI.     

Effect of reaction conditions on film morphology of polyaniline composite membranes for gas separation

Composite membranes combining polyaniline as an active layer with a polypropylene support have been prepared using an in situ deposition technique. The protonated polyaniline layer with a thickness in the range of 90–200 nm was prepared using precipitation, dispersion, or emulsion polymerization of aniline with simultaneous deposition on top of the porous polypropylene support, which was immersed in the reaction mixture. Variables such as temperature, concentration of reagents, presence of steric stabilizers, surfactants, and heteropolyacid were found to control both the formation and the quality of the polyaniline layers. Both morphology and thickness of the layers were characterized using scanning electron microscopy. Selective separation of carbon dioxide from its mixture with methane is used to illustrate potential application of these composite membranes. © 2012 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2012     

Alpha-glucosidase based bismuth film electrode for inhibitor detection

A biosensing system based on α-glucosidase (AG) activity was developed by using bismuth film modified glassy carbon electrode (BiFE). AG enzyme was immobilized on the BiFE by means of gelatin membrane and the activity was measured by the following of liberated 4-nitrophenol from the 4-nitrophenyl-α-d-glucopyranoside (PNPGP) which is the synthetic substrate of the enzyme at the working potential of −950 mV. The proposed system was used as an AG based biosensing system. Experimental data showed that the response current of 4-nitrophenol obtained at the BiFE was linear in concentration range between 0.033 and 0.33 mM of PNPGP. Before examining the analytical characteristics, pH optimization of the AG-biosensor was also performed. Furthermore, the proposed method was applied to analyze two different AG inhibitors (Amaryl and Acorbose) which are important in Noninsulin-dependent diabetes mellitus (NIDDM).     

Determination of Manganese by Cathodic Stripping Voltammetry on a Microfabricated Platinum Thin–film Electrode

In this work, we report on the determination of trace manganese (Mn) using cathodic stripping voltammetry (CSV) using a microfabricated sensor with a Pt thin‐film working electrode. While an essential trace metal for human health, prolonged exposure to Mn tends to gradually impair our neurological system. The potential sources of Mn exposure make it necessary to monitor the concentration in various sample matrices. Previous work by us and others suggested CSV as an effective method for measuring trace Mn. The analytical performance metrics were characterized and optimized, leading to a calculated limit of detection (LOD) of 16.3 nM (0.9 ppb) in pH 5.5, 0.2 M acetate buffer. Further, we successfully validated Mn determination in surface water with ∼90% accuracy and >97% precision as compared with inductively coupled plasma mass spectrometry (ICP‐MS) “gold standard” measurement. Ultimately, with stable, accurate and precise electrochemical performance, this Pt sensor permits rapid monitoring of Mn in environmental samples, and could potentially be used for point‐of‐use measurements if coupled with portable instrumentation.     

The electrochemical behavior and characterization of the anodic oxide film formed on titanium in NaOH solutions

Titanium dissolution and passivation were studied in NaOH aqueous solution using open-circuit potential, potentiodynamic and potentiostatic techniques. Potentiodynamic data showed that the active-passive transition involves active metal dissolution followed by formation of a poorly conducting passive oxide film that passivates the electrode. The critical current density varied with pH as d log<I> j</I><SUB>m</SUB>/d pH=-0.098 in the pH range 11.00–14.00, while the passivation potential is changed according to the following two features: at pH 10.55–13.00, d<I>E</I><SUB>m</SUB>/d pH=-0.06 V; and at pH 13.50–14.00, d<I>E</I><SUB>m</SUB>/d pH=-0.40 V. The apparent activation energy, E*, was calculated from the slope of the Arrhenius plot and was found to be 12.6 kJ mol^–1. Current-time transients showed that the growth of titanium oxide passive film is a diffusion-controlled process. XPS measurements indicated that the passive oxide film consists mainly of TiO₂ and a mixture of suboxides of Ti₂O₃ and TiO. Electronic Publication     

Molecular dynamics simulation of surface morphology and thermodynamic properties of polyaniline nanostructured film

To develop predictive models in nanostructured films, there is an ongoing research to validate molecular dynamics (MD) simulation results with experimental data. The morphology and surface topography of polyaniline (PANI) nanostructured film coated on a TiO₂ nanocrystalline surface were investigated by scanning electron microscopy and atomic force microscopy, respectively. The atomistic model of the simulated PANI was generated using energy minimization with a condensed‐phase optimized molecular potential for atomistic studies force field function to reach a thermodynamic equilibrium state. Various parameters of PANI such as density, energy, cavity size, and free volume distributions are calculated. MD simulation has also been used to obtain specific volume (V) as a function of temperature (T). It is demonstrated that this V–T curve can be used to determinate glass transition temperature T_g, reliably. Although experimental data available for the PANI film are very limited, simulation results such as density and T_g are in good agreement with the experimental values reported in the literature. Comparison of the surface topography of PANI demonstrates a reasonable trend between atomic force microscopy image analysis and the MD simulation results at various temperatures. Copyright © 2014 John Wiley & Sons, Ltd.     

Wide-range regulation of polyaniline conduction by interphase doping of a polyaniline film

The not-sufficient-enough conductance of semioxidized protonated polyaniline (PANI) is usually attributed to the presence of ordered quasi-metallic domains surrounded by a poorly conducting amorphous phase. The paper presents experimental results testifying to the existence, in semioxidized PANI, of multilevel redox heterogeneity that crucially effects the conductance magnitude in view of specific topology at which higher-oxidized (conducting) domains are surrounded by less oxidized (poorly conducting) domains and because the PANI conduction is extremely sensitive to the oxidation degree. It is shown experimentally that the interphase doping with metals and degenerate semiconductors of a semioxidized salt of PANI and poly(2-acrylamide-2-methyl-1-propanesulfonic acid) (PAMPSA) with a 1: 2 ratio between PANI and PAMPSA raises the PANI-PAMPSA conductivity by 3–8 orders of magnitude due to the formation near the interface of thin layers whose conductance depends on the work function of the material in contact with PANI-PAMPSA and in extreme cases substantially exceeds the conductance of gold and copper at room temperature.     

Absorption spectra of thin film of polyaniline

The absorption spectra of thin film of polyaniline (PANI) on slide glass coated by a spin coater were measured as a function of the protonation state of PANI, the concentration of solution of PANI in NMP, drying temperature, and atmosphere. The absorbance value of the 950 nm peak and the ratio of the absorbance value at 950 nm to that of the 630 nm peak increases with increasing the protonation state of PANI. This is consistent with the observation of varying the conductivity with the protonation state. A modified molecular structure of PANI is proposed: where y and x are defined as the oxidation and the protonation states of PANI, respectively.     

Formation of Calcareous Deposit during CathodicProtection and Its Properties

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Cathodic reduction of hydroxycarbonyl compound trichloroacetyl esters

New coumarins and new 2-(2′,2′-dichlorovinyl) phenols have been prepared by cathodic reduction under potentiostatic conditions of trichloroacetyl esters of o-hydroxyketones and o-hydroxyaldehydes in aprotic media. Electroreductions of trichloroacetyl esters of α-hydroxy-1,4-naphthoquinone, 3-hydroxy-2-methyl-4-pyrone, methyl salicylate and benzoin have also been investigated.     

碳糊电极阴极吸附伏安法测定橙皮甙

在0.4mol/L的NH4Cl-NH3(pH9.0)缓冲液中,使用JP-303极谱分析仪,橙皮甙在碳糊电极(CPE)上有一灵敏的吸附伏安还原峰,峰电位为-1.2V(vs.SCE).该还原峰的二阶导数峰电流与橙皮甙的浓度在2.0×10-8～1.0×10-6mol/L(富集90s)范围内成良好的线性关系,相关系数为0.9963,检出限为1.0×10-8mol/L(S/N=3,富集110s).探讨了橙皮甙在碳糊电极上的伏安性质和电极反应机理,并且成功应用于中草药桔皮中橙皮甙含量的测定.     

Bismuth film electrode for anodic stripping voltammetric determination of tin

The bismuth film electrode (BiFE), in combination with anodic stripping voltammetry, offers convenient measurement of low concentrations of tin. The procedure involves simultaneous in situ formation of the bismuth film electrode on a glassy carbon substrate electrode, together with electrochemical deposition of tin, in a non-deaerated model solution containing bismuth ions, catechol as complexing agent and the metal analyte, followed by an anodic stripping scan. The BiFE is characterized by an attractive electroanalytical performance, with two distinct voltammetric stripping signals corresponding to tin, accompanied with low background contributions. Several experimental parameters were optimized, such as concentration of bismuth ions and catechol, deposition potential, deposition time and pH of the model solution. In addition, a critical comparison is given with bare glassy carbon and mercury film electrodes, revealing the superior characteristics of BiFE for measurement of tin. BiFE exhibited highly linear behavior in the examined concentration range from 1 to 100 μg L⁻¹ of tin (R² = 0.997), an LoD of 0.26 μg L⁻¹ tin, and good reproducibility with a calculated R.S.D. of 7.3% for 10 μg L⁻¹ tin (n = 10). As an example, the practical applicability of BiFE was tested with the measurement of tin in a real sample of seawater.     

Determination of subnanomolar concentrations of cobalt by adsorptive stripping voltammetry at a bismuth film electrode

Procedures for trace cobalt determinations by adsorptive stripping voltammetry at in situ and ex situ plated bismuth film electrodes are presented. These exploit the enhancement of the cobalt peak obtained by using the Co(II)–dimethylglyoxime–cetyltrimethylammonium bromide–piperazine-N,N-bis(2-ethanesulfonic acid) system. The calibration graph for an accumulation time of 120 s was linear from 2 × 10^–10 to 2 × 10^–8 mol L^–1. The relative standard deviation from five determinations of cobalt at a concentration of 5 × 10^–9 mol L^–1 was 5.2%. The detection limit for an accumulation time of 300 s was 1.8 × 10^–11 mol L^–1. The proposed procedure was applied to cobalt determination in certified reference materials and in tap and river water samples.