聚苯胺炭复合载体制备的钯催化剂对甲酸的电催化氧化

制备了导电高分子聚苯胺与活性炭的复合载体(PAnC),用PAnC作为载体制备的钯催化剂性能优于单独活性炭作为载体制备的催化剂。此外掺杂十二烷基磺酸钠制备的聚苯胺碳载体(PAnC-S)具有比PAnC更低的电荷传递电阻,10~25 nm的介孔数量明显增加,比表面积增大到94.9 m²/g。PAnC-S与PAnC粒径均匀,粒径均在30 nm左右。以PAnC-S和 PAnC为载体制备的钯催化剂比活性炭作载体制备的钯催化剂具有更大的电化学比表面积,分别为84.7和62.6 m²/g。对甲酸的氧化具有更高的电化学活性和稳定性。     

甲苯胺蓝修饰电极的电化学性质及对抗坏血酸的测定

研究了甲苯胺蓝(TB)聚合膜修饰金电极的制备及其电化学性质,并用于抗坏血酸(AA)的测定。在pH 6.5的磷酸盐缓冲溶液中,AA在甲苯胺蓝修饰金电极上产生一灵敏的氧化峰,峰电流与AA的浓度在3.9×10-5~1.0×10-2mol/L范围内呈良好的线性关系,检出限为1.3×10-5mol/L。该电极重现性良好,已用于实际样品中AA的测定。     

Synthesis of self-doped conducting polyaniline bearing phosphonic acid

As a self-doped conducting polyaniline bearing phosphonic acid, poly(2-methoxyaniline-5-phosphonic acid) (PMAP) was synthesized via oxidative polymerization of 2-methoxyaniline-5-phosphonic acid. The pyridinium salt of thus-obtained PMAP was water-soluble and its film exhibited conductivity.     

Electrochemical synthesis of polyaniline in surface-attached poly(acrylic acid) network, and its application to the electrocatalytic oxidation of ascorbic acid

Acrylic acid was first electropolymerized on the surface of a gold electrode. Then, polyaniline (PANI) was electrodeposited on the poly(acrylic acid) (PAA) network to give a PANI–PAA composite film. Scanning electron microscopy and electrochemical studies confirmed the formation of PANI–PAA composite which exhibited excellent electroactivity over a wide pH range. The electro-oxidation of ascorbic acid (AA) was studied in detail. The modified electrode exhibits significantly reduced oxidation overpotential. The response towards AA is linear in the range 1.0 μM to 9.3 mM (R?=?0.9997, n?=?33) at a potential of 0.1 V (vs. SCE). The sensitivity is 207 μA mM^-1 cm^-2, and the detection limit is 1.0 μM (S/N?=?3). Interferences by uric acid and dopamine are negligible. The electrode thus enables sensitive and selective determination of AA, with a performance superior to many other PANI–based ascorbate sensors.     

Nanostructured platinum as an electrocatalyst for the electrooxidation of formic acid

Nanostructured platinum prepared by the chemical reduction of hexachloroplatinic acid dissolved in aqueous domains of the liquid crystalline phases of oligoethylene oxide surfactants, was examined as an electrocatalyst for the electrooxidation of formic acid. The electrocatalytic properties of the catalyst combining highly specific surface areas and a periodic mesoporous nanostructure were accessed in sulfuric acid solution containing 0.5 mol dm⁻³ formic acid using cyclic voltammetry (CV) and chronoamperometry. The electrocatalytic activity of the material at 60 °C, is characterised by a mass activity of 8.6 A g⁻¹ and a specific surface area activity of 26 μA cm⁻² at 0.376 V (vs. RHE). The resistance to CO poisoning was found to depend upon electrode potential. At hydrogen adsorption potentials, the material is easily poisoned, while the material shows high resistance to CO poisoning at potentials positive of the hydrogen region. These facts suggest that the decomposition of HCOOH on the mesoporous platinum is likely to proceed through a dual-path mechanism and the high surface area material is a potential electocatalyst towards the electrooxidation of small organic molecules.     

聚茜素红功能化碳纳米管修饰电极对多巴胺和抗坏血酸的电化学研究

采用电聚合方法将茜素红非共价修饰到碳纳米管上,制备了聚茜素红/碳纳米管修饰电极.以多巴胺(DA)和抗坏血酸(AA)为模型化合物,研究该修饰电极的电催化作用.结果表明:电聚合法使茜素红牢固地修饰到碳纳米管上,能显著提高电极的灵敏度和分子识别性能.DA和AA的氧化峰位分离达240 mV.在AA的存在下,DA的差分脉冲伏安法峰电流在1×10-7～1×10-5 mol/L范围内呈良好的线性关系,检测下限达1×10-7 mol/L.     

抗坏血酸在聚阿魏酸修饰玻碳电极上的电化学行为研究

研究了抗坏血酸(AA)在聚阿魏酸修饰电极上的电化学性质。在AA存在的条件下,电极过程由扩散控制,测得扩散系数为8.18×10-8cm2/s。AA浓度在0.01~5.0 mmol/L范围内与峰电流呈现良好的线性关系。通过计时安培法测得催化速率常数为8.6×103mol-1.L.s-1。     

Electrochemical study of methylene blue incorporated into mordenite type zeolite and its application for amperometric determination of ascorbic acid in real samples

Methylene blue (MB) was incorporated into mordenite zeolite by ion exchange reaction in aqueous phase. The dye is strongly retained and not easily leached from the zeolite matrix. The solid was characterized by XRD prior to using it for the electrode preparation. This compound was incorporated into a carbon paste electrode for cyclic voltammetric and amperometric measurements. Methylene blue immobilized on the support underwent a quasi-reversible electrochemical redox reaction. In various electrolyte solutions and changing the pH between 2.0 and 7.0, the midpoint potential remained practically constant, i.e. 153.7±0.8 mV. This is not the usual behavior of MB, because in solution phase its midpoint potential changes considerably as the pH changes. The electrode made with this material was used for the mediated oxidation of ascorbic acid. The anodic peak current observed in cyclic voltammetry was linearly dependent on the ascorbic acid concentration. At a fixed potential under static conditions, the calibration plot was linear over the ascorbic acid concentration range 2.0×10⁻⁵ to 8.0×10⁻⁴ M. The detection limit of the method is 1.21×10⁻⁵ M, low enough for trace ascorbic acid determination in various real samples.     

Attempt to incorporate ferrocenecarboxylic acid into polypyrrole during the electropolymerization of pyrrole in chloroform: its application to the electrocatalytic oxidation of ascorbic acid

 In this work, polypyrrole films with ferrocenecarboxylic acid incorporated (PPy/FCA) were prepared on a glassy carbon (GC) electrode in chloroform as an aprotic solvent with low dielectric constant, convenient for the preparation of the films by a precipitation mechanism. The electrochemical behaviour of the PPy/FCA-coated GC electrode was studied by cyclic voltammetry in aqueous solution with low pH. The results obtained show that the electrochemical response of FCA incorporated in polypyrrole is consistent with a reversible surface oxidation. An obvious electrocatalytic effect of PPy/FCA on the oxidation of ascorbic acid is observed in aqueous solution. Received: 30 July 1998 / Accepted: 3 March 1999     

Flow-injection spectrophotometric determination of ascorbic acid by reduction of vanadotungstophosphoric acid

Ascorbic acid may be determined spectrophotometrically at 360 nm based on reduction of vanadotungstophosphoric acid using flow-injection analysis. The carrier stream was distilled water and the reagent streams were buffer solution (pH 3.0), 1.735 × 10^?3 M dodecatungstophosphoric acid and 1.735 × 10^?3 M sodium vanadate. The injection rate was 80 h^?1. The calibration graph was linear up to 80 μg ml^?1 ascorbic acid and the relative standard deviation for the determination of 20 μg ml^?1 ascorbic acid was 1.5% (n=10). The detection limit was 1.0 μg ml^?1 ascorbic acid, based on an injection volume of 250 μl. The system was applied to the determination of ascorbic acid in vitamin C tablets.     

Study of vibrational spectra of polyaniline doped with sulfuric acid and phosphoric acid

Vibrational spectra of insulator emeraldine base (EB) form of polyaniline and electrical conductive sulfuric acid-and phosphoric acid-doped emeraldine salts (ES) were studied in the region of 4000-400 cm⁻¹ at ambient temperature by Fourier transform infrared spectroscopy. Infrared transmittance spectra of EB and ES were investigated to understand the bonding behavior of different organic and inorganic groups present in the polymeric chains and their structural variations on protonation by sulfate or phosphate ion inclusion in the polymer salt network. These studies revealed the para-coupling of deformed disubstituted benzenoid (B) and quinoid (Q) rings with ends capped predominantly by (B4Q1) units. The deformation of B and Q rings was confirmed by the appearance of many weak bands, very weak bands, and satellite structures in strong transmittance peaks of polymeric chain-constituting groups. Protonation takes place at the nitrogen sites of Q rings and forms semiquinone radical ions in ES. The vibrational bands pertaining to B rings, Q rings, B4Q1 units, semiquinone segment, sulfate ions, and phosphate ions were observed and assigned from these measurements. The shift in peak position of some bands with gain or loss in intensity and appearance of some new bands were observed in sulfuric acid-and phosphoric acid-doped ES spectra. These variations are attributed to the formation of new structural groups in ES on protonation and a change in crystalline field by sulfate and phosphate ion doping for crosslinking the polymeric chains.     

Facile synthesis of graphene hybrid tube-like structure for simultaneous detection of ascorbic acid,dopamine, uric acid and tryptophan

In the present work, a tube-like structure of graphene hybrid as modifier to fabricate electrode for simultaneous detection of ascorbic acid (AA), dopamine (DA), uric acid (UA) and tryptophan (Trp) was reported. The hybrid was synthesized by a simple method based on graphene sheets (GS) and 3,4,9,10-perylenetetracarboxylic acid (PTCA) via π–π stacking interaction under ultrasonic condition. The combination of GS and PTCA could effectively improve the dispersion of GS, owing to PTCA with the carboxylic-functionalized interface. Comparing with pure GS or PTCA modified electrode, GS–PTCA displayed high catalytic activity and selectivity toward the oxidation of AA, DA, UA, and Trp. Moreover, cyclic voltammetry, different pulse voltammetry and scanning electron microscopy were employed to characterize the sensors. The experiment results showed that the linear response range for simultaneous detection of AA, DA, UA, and Trp were 20–420 μM, 0.40–374 μM, 4–544 μM and 0.40–138 μM, respectively, and the detection limits were 5.60 μM, 0.13 μM, 0.92 μM and 0.06 μM (S/N = 3). Importantly, the proposed method offers promise for simple, rapid, selective and cost-effective analysis of small biomolecules.     

Preparation of silver hexacyanoferrate nanoparticles and its application for the simultaneous determination of ascorbic acid, dopamine and uric acid

A silver hexacyanoferrate nanoparticles/carbon nanotubes modified glassy carbon electrode was fabricated and then successfully used for the simultaneous determination of ascorbic acid, dopamine and uric acid by cyclic voltammetry. A detailed investigation by transmission electron microscopy (TEM) and electrochemistry was performed in order to elucidate the preparation process and properties of the nanocomposites. The size of silver hexacyanoferrate nanoparticles was examined by TEM around 27 nm. Linear calibration plots were obtained over the range of 4.0 × 10⁻⁶-7.8 × 10⁻⁵, 2.4 × 10⁻⁶-1.3 × 10⁻⁴ and 2.0 × 10⁻⁶-1.5 × 10⁻⁴ mol L⁻¹ with detection limits of 4.2 × 10⁻⁷,1.4 × 10⁻⁷ and 6.0 × 10⁻⁸ mol L⁻¹ for ascorbic acid, dopamine and uric acid, respectively. The practical analytical utilities of the modified electrode were demonstrated by the determination of ascorbic acid, dopamine and uric acid in urine and human blood serum samples.     

聚苯胺Langmuir－Blodgett膜的电聚合制备及电化学性质

在加有苯胺的亚相上,铺展硬脂酸分子,在气液界面上可形成苯胺－硬脂酸Ｌａｎｇｍｕｉｒ膜．随膜压增大至５．０×１０￣（－６）Ｎ时,苯胺与硬脂酸间的氢键会发生重排,形成另外一种构型的Ｌａｎｇｍｕｉｒ膜,分子所占面积减小,膜增加一个苯环的厚度．将膜转移到ＳｎＯ＿２导电玻璃基底上,制成硬脂酸－苯胺Ｌａｎｇｍｕｉｒ－Ｂｌｏｇｄｅｔｔ膜,经电化学氧化,苯胺可聚合成薄膜。膜夹在两层硬脂酸分子间,它的电化学行为不仅受到离子膜中传输过程的影响,同时受到硬脂酸极性亲水端（－ＣＯＯ￣－）的作用．     

流动注射抑制电化学发光法测定维生素C

将在线恒电流电解产生ClO-与Luminol构成了较强的化学发光体系,基于维生素C对该化学发光体系有强抑制作用,结合流动注射技术,建立了测定维生素C的流动注射抑制电化学发光新方法.该方法在维生素C的浓度为2.0×10-10～1.5×10-8 mmol/mL之间分段回归,呈良好的线性,检出限达到5.0×10-11 mmol/mL.     

动力学荧光法测定抗坏血酸

基于在硫酸介质中 ,抗坏血酸能活化钒 ( )催化溴酸钾氧化藏红 T的反应 ,使其荧光猝灭 ,建立了动力学荧光法测定抗坏血酸的新方法。方法的检出限为 5 .8× 1 0 -3 μg/m L,线性范围为 0～ 0 .5 6μg/m L。可用于药品、蔬菜、尿液中抗坏血酸含量的测定     

The application of conducting polymer nanoparticle electrodes to the sensing of ascorbic acid

An ascorbic acid sensor was fabricated via the drop-casting of dodecylbenzene sulphonic acid (DBSA)-doped polyaniline nanoparticles onto a screen-printed carbon-paste electrode. The modified electrode was characterised with respect to the numbers of drop cast layers, optimum potential and operating pH. The sensor was found to be optimal at neutral pH and at 0 V vs. Ag/AgCl. Under these conditions, the sensor showed good selectivity and sensitivity in that it did not respond to a range of common interferents such as dopamine, acetaminophen, uric acid and citric acid, but was capable of the detection of ascorbic acid at a sensitivity of 0.76 μA mM⁻¹ or 10.75 μA mM⁻¹ cm⁻² across a range from 0.5 to 8 mM (r² = 0.996, n = 6), and a limit of detection of 8.3 μM (S/N = 3). The sensor was compared to a range of other conducting polymer-based ascorbate sensors and found to be comparable or superior in terms of analytical performance.     

A quick method for the simultaneous determination of ascorbic acid and sorbic acid in fruit juices by capillary zone electrophoresis

A method of quickly determining ascorbic acid and sorbic acid by capillary zone electrophoresis with ultraviolet detection was developed. The choice of background electrolyte, wavelength, injection time and applied voltage were discussed. Ascorbic acid and sorbic acid were well separated in 80 mmol L⁻¹ boric acid-5 mmol L⁻¹borax (pH = 8.0) in 5 min at the detecting wavelength of 270 nm. Under the optimum condition, the method has linear ranges of 2.54-352.00 mg L⁻¹ for ascorbic acid and 1.08-336.39 mg L⁻¹ for sorbic acid with the detection limit of 1.70 mg L⁻¹ for ascorbic acid and 0.54 mg L⁻¹ for sorbic acid, respectively. Other organic acids in fruit juices have no effect on the detection. This method is very feasible and simple and can be used to detect ascorbic acid and sorbic acid in fruit juices.     

l-Ascorbic acid in organic synthesis: DBU-catalysed one-pot synthesis of tetramic acid derivatives from 5,6-O-isopropylidene ascorbic acid

Reaction of 5,6-O-isopropylidene-2,3-bis-O-alkyl ascorbic acid with different amines in the presence of DBU at ambient temperature resulted in the formation of 3,4-bis-O-alkyl-1-alkyl-5-(2-hydroxy ethyl)-5-hydroxy-1,5-dihydropyrrol-2-ones in moderate yields.     

聚亚甲基蓝修饰金电极对抗坏血酸电催化氧化及其电分析方法研究

研究了亚甲基蓝(methylene blue,MB)聚合物膜修饰金电极(PMB/Au)的制备及其性质,通过电化学阻抗谱图对PMB/Au进行了表征,并对抗坏血酸(ascorbic acid,AA)在PMB/Au上的电化学行为进行了研究。结果表明,PMB/Au对AA的氧化具有良好的电催化作用,使AA的过电位降低约200 mV,氧化峰电流明显增大。测得AA在PMB/Au上的电荷转移系数为0.70,催化反应速率常数为5.99×103mol-1.L.s-1。用方波伏安法(Square Wave Voltammetry,SWV)测得氧化峰电流与AA浓度在2.0×10-5~6.0×10-3mol/L范围内呈良好线性关系,检出限为1.0×10-5mol/L。将PMB/Au应用于Vc片剂和Vc注射液中AA的测定。