Characterization of platinum nanoparticle-embedded carbon film electrode and its detection of hydrogen peroxide

A method for the highly sensitive determination of acetylcholine (ACh) and choline (Ch) that employs a graphite-like carbon film electrode containing 6.5% platinum (Pt) nanoparticles was developed for use as a detector in microbore liquid chromatography (LC) with a postcolumn enzyme reactor. The film electrode was prepared by RF cosputtering carbon and Pt, which requires only a one-step formation process. This method can control the Pt content of the film at a relatively low deposition temperature (below 200 degrees C). The average size of the Pt nanoparticles was 2.5 nm. The film electrode showed excellent electrocatalytic activity, high sensitivity, and negligible baseline drift when detecting hydrogen peroxide. The electrode was modified with glucose oxidase and responded rapidly to glucose with a much more stable baseline current than at a Pt bulk electrode based sensor. Therefore, it is appropriate to employ the electrode to detect trace amounts of biomolecules, such as neurotransmitters and hormones combined with various oxidase enzymes. We used the electrode as a detector for microbore LC and observed a low detection limit of 2.5 and 2.3 fmol (10-microL injection) for ACh and Ch, respectively, which is approximately 1 order of magnitude lower than that of a Pt bulk electrode.     

Ionic liquid modified carbon paste electrode and investigation of its electrocatalytic activity to hydrogen peroxide

. This paper reports on the preparation and advantages of novel amperometric biosensors in the presence of hydrophobic ionic liquid (IL), 1-methyl-3-butylimidazolium bromide ([MBIB]). Carbon paste biosensor has been constructed by entrapping horseradish peroxidase in graphite and IL mixed with paraffin oil as a binder. The resulting IL/graphite material brings new capabilities for electrochemical devices by combining the advantages of ILs composite electrodes. Amounts of H₂O₂ were amperometrically detected by monitoring current values at reduction potential (–0·15 V) of K₃Fe(CN)₆. Decrease in biosensor responses were linearly related to H₂O₂ concentrations between 10 and 100 μM with 2 s response time. Limit of detection of the biosensor were calculated to be 3·98 μM for H₂O₂. In the optimization studies of the biosensor some parameters such as optimum pH, optimum temperature, enzyme amount, interference effects of some substances on the biosensor response, reproducibility and storage stability were carried out. The promising results are ascribed to the use of an ionic liquid, which forms an excellent charge-transfer bridge and wide electrochemical windows in the bulk of carbon paste electrode.     

Voltammetric reduction and determination of hydrogen peroxide at an electrode modified with a film containing palladium and iridium

Cyclic voltammetry of a mixture containing 0.2 mM Na2IrCl6, 0.1 mM PdCl2, 0.2 M K2SO4, and 0.1 M HCl between 1.2 and -0.3 V vs Ag/AgCl for five cycles at 50 mV s-1 yields a stable film on a glassy carbon electrode. The reduction of hydrogen peroxide in 0.1 M KCl is diffusion controlled at that modified electrode. Calibration curves obtained at a 100 mV s-1 scan rate are linear in the range 0.2-1.8 mM H2O2. The slope, 28 microA L mmol-1, is independent of film thickness. Since dissolved oxygen is reduced at about the same potential as H2O2, -0.3 V, at the modified electrode, it will act as an interferent in solutions that are not deaerated; however, the currents are additive. A second limitation of the described procedure is that with the KCl electrolyte the immobilized film must be reoxidized prior to each measurement. Preliminary data are described which suggest that this problem is alleviated by switching to a basic supporting electrolyte.     

Preparation of RF sputtered AZO/Au thin film hydrogen peroxide sensitive electrode for utilization as a biosensor

In this study, hydrogen peroxide (H₂O₂) sensitive Al doped ZO(AZO)/Au thin film electrode has been developed for the utilization as a biosensor. A preferred c-axis oriented AZO/Au thin film was deposited on quartz substrate by RF magnetron sputtering at room temperature. Structural, morphological and optical properties of the AZO film were analyzed by X-ray diffraction, atomic force microscopy and photoluminescence. The sensor performance was characterized by electrochemical analysis device. The sensibility of prepared thin film electrodes to H₂O₂ was studied. The dependence of amperometric response current on the glucose and cholesterol concentrations was also investigated.     

Pulsed excitation source multiplexed fluorometry for the simultaneous measurement of multiple analytes. Continuous measurement of atmospheric hydrogen peroxide and methyl hydroperoxide

Presently, solid-state sources such as light-emitting diodes (LEDs) provide for intense, nearly monochromatic light. They are available over a broad range of emission wavelengths. Unlike incandescent and discharge lamps, LEDs can be turned on and off at high speeds. The resulting light pulses are highly reproducible. This allows the use of a single photomultiplier tube (PMT), often the most expensive component in a high-sensitivity measurement system, as a multiplexed detector with multiple, fiber-optic-coupled, fluorescence-detection cells excited by solid-state sources. A time resolution of 1 min is adequate in many continuous detection schemes. This enables multiple-channel single-detector multiplexed measurement without any loss of S/N. On the basis of this principle, we describe a new automated continuous instrument for the simultaneous measurement of atmospheric hydrogen peroxide and methyl hydroperoxide (MHP). A Nafion membrane diffusion scrubber (DS) is used with hematin-catalyzed oxidation of thiamine to thiochrome for the measurement of H2O2, and an expanded poly(tetrafluoroethylene) (ePTFE) DS is used with a H2O2 destruction catalyst and horseradish peroxidase-catalyzed oxidation of thiamine to thiochrome for the measurement of MHP. The respective limits of detection are 25 pptv and 15 pptv. Design, performance details, and illustrative results from a field campaign (Philadelphia NEO3PS study, 2001) are presented.     

表面活性剂改性的大孔径介孔炭对电极染料敏化太阳电池(英文)

以大孔径的介孔炭(MC)为催化层材料经低温热处理构建出炭对电极,着重探讨了在炭浆料中添加Triton X100对其组装的染料敏化太阳电池(DSCs)光电性能的影响,并引入分形维数(DF)用于定量评估炭膜形貌的差异。结果表明,当炭浆料中Triton X100的含量增加到0.1 mL(相应MC含量为0.6 g)时,DSCs的光电转换效率增加至5.65%,其值比活性炭对电极DSCs高46.5%,且达到Pt对电极DSCs的95.4%。Triton X100改性的介孔炭对电极的高性能归功于高品质的炭膜和介孔炭本身合理的孔结构(如大尺寸孔径和大比表面积等)。相对于未添加Triton X100的纯介孔炭对电极,Triton X100改性的介孔炭对电极具有分布更均匀的炭膜和更小的分形维数,是对电极欧姆串阻减小及相应器件效率改善的一个重要因素。     

Detection of hydrogen peroxide using photofragmentation laser-induced fluorescence

Photofragmentation laser-induced fluorescence (PF-LIF) is for the first time demonstrated to be a practical diagnostic tool for detection of hydrogen peroxide. Point measurements as well as two-dimensional (2D) measurements in free-flows, with nitrogen as bath gas, are reported. The present application of the PF-LIF technique involves one laser, emitting radiation of 266 nm wavelength, to dissociate hydrogen peroxide molecules into OH radicals, and another laser, emitting at 282.25 nm, to electronically excite OH, whose laser-induced fluorescence is detected. The measurement procedure is explained in detail and a suitable time separation between photolysis and excitation pulse is proposed to be on the order of a few hundred nanoseconds. With a separation time in that regime, recorded OH excitation scans were found to be thermal and the signal was close to maximum. The PF-LIF signal strength was shown to follow the same trend as the vapor pressure corresponding to the hydrogen peroxide liquid concentration. Thus, the PF-LIF signal appeared to increase linearly with hydrogen peroxide vapor-phase concentration. For 2D single shot measurements, a conservatively estimated value of the detection limit is 30 ppm. Experiments verified that for averaged point measurements the detection limit was well below 30 ppm.     

A pulse amperometric sensor for the measurement of atmospheric hydrogen peroxide

Gaseous H(2)O(2) is sampled through a Nafion membrane diffusion scrubber while 1 mM HCl is maintained stationary in the scrubber. After a preselected preconcentration time (typically, 5-10 min), a valve is opened to allow the scrubber liquid to flow by gravity over an electrochemical H(2)O(2) sensor for a brief period. The miniature flow-over sensor consists of a Pt/Rh wire working electrode and a Pt wire counter electrode wound respectively on separate segments of a Nafion solid polymer electrolyte tubing supported on a Ag/AgCl wire reference electrode. A simple electronic interface and a personal computer are used to control and record the electrochemical measurement. The liquid phase detection limit for this sensor is ～30 nM H(2)O(2) in the anodic oxidation mode. For a 9 min gas sample preconcentration period, the LOD (S/N = 3 criterion) is 0.11 ppbv H(2)O(2)(g). Ambient H(2)O(2) data obtained with this instrument were in excellent agreement with those obtained by an established fluorometric technique in a blind intercomparison.     

Photo-assisted oxidation of an oily wastewater using hydrogen peroxide

The primary objective was to study the purification of an oily wastewater from a lubricant production unit using ultraviolet irradiation and hydrogen peroxide. The influence of hydrogen peroxide concentration, initial pH of the solution and of the addition of ferric ions on the chemical oxygen demand (COD) was examined. In each case, the concentration of the compounds contained in the oily wastewater was determined. It was shown that a 20-45% COD removal was achieved with 830-1660 mg l(-1) H(2)O(2). Gas chromatography-mass spectrometry analysis showed that the organic compounds of the wastewater decomposed to organic acids that were very resistant to photo-oxidation. Among these compounds, ethylene glycol remained almost unchanged by the attack from hydroxyl radicals. Acidic pH and Fe(III) addition enhanced significantly the photo-oxidation of the wastewater.     

Preparation of vermiculite nanoparticles using thermal hydrogen peroxide treatment

Powdered natural Mg-vermiculite (Letovice, Czech Republic), with the formula (Mg0.35K0.02Ca0.01) (Mg2.39Fe0.51(3+)Fe0.02(2+)Al0.08) (Si2.64Al1.33Ti0.03) O10(OH)2 x 4.97H2O and particle size < 5 microm, was used for the investigation of exfoliation after hydrogen peroxide and/or microwave treatment (600 W). A sample heated in the microwave oven for 40 min exhibits a 11% mass loss and reduction of the 001 peak intensity in the X-ray diffraction pattern. The basal 001 peak intensity of untreated Mg-vermiculite sample (/001 = 100%) drops to 35% in the microwave treated sample. Only the sample treated for 5 h at 80 degrees C fully rehydrated after 120 min at room temperature. A more pronounced reduction of the 001 peak intensity (to 8%) was observed after hydrogen peroxide treatment of the sample at 25 degrees C. The combination of a five-hour hydrogen peroxide treatment at 80 degrees C and subsequent microwave heating leads to an effective extinction of the 001 diffraction in the XRD pattern. The 001 diffraction profile becomes very diffuse with peak intensity less than 1%. The degree of reduction of the 001 diffraction intensity also depends on the time and temperature of hydrogen peroxide treatment and on the peroxide concentration. An even more pronounced reduction of the peak intensity is caused by exfoliation of particles to nano-domains coupled with a randomization of the c-axes.     

A hydrogen peroxide biosensor based on peroxidase activity of hemoglobin in polymeric film

A Hydrogen peroxide (H2O2) biosensor, based on hemoglobin (Hb) and ortho-phenylenediamine (o-PD) gold electrode, was fabricated. Hb was immobilized onto the electrode surface by electrochemical polymerize method with o-PD. The designed biosensor showed a well defined redox peak which was attributed to the direct electrochemical response of Hb. The immobilized Hb exhibited an excellent electrocatalytical response to the reduction of hydrogen peroxide, enabling the sensitivity determination of H2O2. Factors and performances such as pH, potential, influencing the designed biosensor, were studied carefully. The amperometric detection of H2O2 was carried out at -300 mV in phosphate buffer solution (PBS) (0.1 M) with pH 6.0. This biosensor showed a fast amperometric response (less then 5 s) to H2O2. The levels of the (Relative standard deviation) RSDs (< 3.5%) for the entire analyses reflected a highly reproducible sensor performance. Using the optimized conditions, the detection limit of the biosensor was 1 x 10(-7) M and linear range was from 5 x 10(-6) to 1.25 x 10(-4) M. In addition, this sensor showed long-term stability and good sensitivity.     

Elaboration of a new hydrogen peroxide biosensor using microperoxidase 8 (MP8) immobilized on a polypyrrole coated electrode

A novel strategy for elaborating a new biosensor for hydrogen peroxide has been developed by combining the known properties of microperoxidase 8 (MP8) as an oxidation catalyst, and the interesting properties of conducting polypyrrole as a supporting matrix to allow a good bioelectrochemical interface and a large dispersion of MP8 on the modified glassy carbon electrode.

MP8 was immobilized into the conducting polypyrrole by entrapment during the electrochemical polymerization, and the modified electrode was characterized both by electrochemical and FT-IR measurements. We demonstrated that MP8 could be immobilized into polypyrrole and could undergo an efficient electron transfer.

The obtained modified electrode showed a high catalytic activity toward H₂O₂ without the need for an electron mediator. A linear calibration curve was obtained by amperometric measurement at a potential of − 0.1 V/ECS for concentrations of H₂O₂ ranging from 1 to 10 μM. The detection limit obtained was 1 nM which constituted a real improvement, by about three orders of magnitude, when compared to the values reported for other systems using an electrochemical detection.     

纳米TiO2薄膜微阵列电极的制备与紫外光电阻特性表征

采用溶胶凝胶法在叉指型微阵列电极表面制备了TiO2纳米薄膜，并对薄膜形貌、厚度以及溶胶粒子尺寸进行了表征，研究了温度、紫外光照对纳米TiO2薄膜微阵列电极的电阻的影响。结果表明，溶胶粒子平均粒径在9nm，单次提拉制备的TiO2纳米薄膜膜厚为120nm，两次提拉薄膜厚度200nm，纳米TiO2薄膜微阵列电极电阻呈现半导体特性，大气环境中，紫外光照下纳米薄膜微电极的低温电阻较无光照时明显减小，表现出紫外光敏感特性。随着温度的升高，紫外光照下的电阻与无光照时电阻差值逐步减小，表明温度对纳米薄膜电阻有更大的影响。     

Continuous determination of high-vapor-phase concentrations of tetrachloroethylene using on-line mass spectrometry

A method was developed to determine the vapor concentration of tetrachloroethylene (PCE) at and below its equilibrium vapor-phase concentration, 168 000 microg/L (25 degrees C). Vapor samples were drawn by vacuum into a six-port sampling valve and injected through a jet separator into an ion trap mass spectrometer (MS). This on-line MS can continuously sample a vapor stream and provide vapor concentrations every 30 s. Calibration of the instrument was done by creating a saturated stream of PCE vapor, sampling the vapor with the on-line MS and with thermal desorption tubes, and correlating the peak area response from the MS with the vapor concentration determined by automated thermal desorption gas chromatography mass spectrometry. Dilution of the saturated stream provided lower concentrations of PCE vapor. The method was developed to monitor the vapor concentration of PCE that was sparged from a two-dimensional flow chamber and for determination of the total PCE mass removed during each sparge event. The method has potential application for analysis of gas-phase tracers.     

Continuous on-line monitoring of extracellular ascorbate depletion in the rat striatum induced by global ischemia with carbon nanotube-modified glassy carbon electrode integrated into a thin-layer radial flow cell

This study describes a novel analytical system integrating in vivo microdialysis sampling with a radial thin-layer flow cell with a single-walled carbon nanotube (SWNT)-modified glassy carbon electrode as working electrode for continuous and on-line monitoring of ascorbate depletion in the rat striatum induced by global ischemia. The SWNTs, especially those after vacuum heat treatment at 500 degrees C, are found to be able to enhance the electron-transfer kinetics of ascorbate oxidation at a low potential (ca. -50 mV) and possess a strong ability against electrode fouling. These properties essentially make it possible to determine ascorbate with a good stability and high selectivity against catecholamines and their metabolites and other electroactive species of physiological levels. While being integrated with in vivo microdialysis to assemble an on-line analytical system, the electrode is proved useful for continuous and sensitive monitoring of the basal dialysate level of ascorbate and its depletion in the rat striatum induced by global ischemia. The basal dialysate level of ascorbate is determined to be 5.0 +/- 0.5 microM (n = 5) and a 50 +/- 10% (n = 3) depletion is recorded for the basal ascorbate after 4 h of global ischemia.     

Fabrication of multi-wall carbon nanotube film on glassy carbon electrode surface and the determination of tyrosine

A novel chemically modified electrode has been prepared on the basis of the attachment of multi-wall carbon nanotubes (MWNT) onto the surface of a glassy carbon electrode (GCE) in the presence of a hydrophobic surfactant, dihexadecyl phosphate (DHP). This MWNT film was characterized by transmission electron microscopy images (TEM) and scanning electron microscopy (SEM). The electrochemical behavior of tyrosine at the MWNT film coated GCE was examined and it is found that this MWNT-modified GCE greatly enhances the oxidation peak current of tyrosine. Effects of some important factors, including pH, scan rate and amount of modifier, on the oxidation process of tyrosine were investigated. When the signal to noise ratio (SNR) is 3, the detection limit is 1 x 10(-7) M. The low relative standard deviations of the detection of tyrosine in human morning urine (3.3%) and white wine (5.2%) suggest a good reproducibility of the modified electrode.     

Accumulation and trace measurement of paraquat at kaolin-modified carbon paste electrode

The carbon paste electrode modified by kaolin (KCPE) has been utilized for the determination of pesticides with high sensitivity based on their redox behavior. The experiment is performed on the use of cyclic and square wave voltammetry. Experimental conditions were optimized by varying the accumulation time, kaolin loading and measuring solution pH. Square wave voltammetric response showed a linear calibration curve in the range from 3.9 × 10^? 9 to 9 × 10^? 5 mol L^? 1 with a detection limit of 2 × 10^? 10 mol L^? 1 at kaolin-modified carbon paste electrode. As a result, it was found that there was feasibility in the use of kaolin to improve the carbon paste electrode properties.     

Disposable biosensor based on a hemoglobin colloidal gold-modified screen-printed electrode for determination of hydrogen peroxide

A disposable reagentless hydrogen peroxide biosensor based on the direct electrochemistry of hemoglobin immobilized on a colloidal gold-modified screen-printed carbon electrode (Hb-Au-SPCE) was proposed. The electrochemical behavior of immobilized Hb at a SPCE was studied for the first time. The electrode reaction of immobilized Hb showed a surface-controlled process with an electron transfer rate constant of (0.40 /spl plusmn/ 0.02) s/sup -1/ determined in the scan rate range from 25 to 200 mV s/sup -1/. The Hb-Au-SPCE exhibited an electrocatalytic activity toward the reduction of hydrogen peroxide with a K/sub M//sup app/ value of 1.8 mM, which was allowed to be used as a disposable sensor for determination of hydrogen peroxide with a linear range from 1.0 /spl times/ 10/sup -5/ M to 3.2 /spl times/ 10/sup -4/ M, a detection limit of 5.5 /spl times/ 10/sup -6/ M at 3/spl sigma/, a high sensitivity, fast response, and good selectivity, accuracy, and reproducibility. The disposable reagentless sensor was stable, low cost, and simple to use for detection of hydrogen peroxide in real samples.     

壳聚糖-多壁碳纳米管/二茂铁修饰玻碳电极的电催化研究

利用多壁碳纳米管(MWCNTs)分散在壳聚糖/二茂铁形成的混合溶液,采用滴涂法对玻碳电极进行修饰,对多巴胺(DA)进行测定。结果表明,修饰后的玻碳电极能够有效促进DA在电极表面的电子传递速率,并且修饰电极对DA具有很好的催化氧化作用。DA氧化峰电流与其浓度在0.5～25μmol/L范围内呈良好的线性关系,检出限为3.89×10-7mol/L,并且常见物质对DA检测无干扰,DA注射液样品检测回收率为98.1%～100.9%。