Stripping Voltammetric Determination of Methyl Parathion at Activated Carbon Nanopowder Modified Electrode

An activated carbon nanopowder modified glassy carbon electrode (AC-GCE) was constructed for the sensitive determination of methyl parathion by adsorptive differential pulse anodic stripping voltammetry. The simple and rapid modification procedure included only drop-coating the electrode surface with a laponite stabilized activated carbon nanopowder suspension and drying. The modifier high adsorption ability, combined with its large electroactive surface area allowed a 30-fold signal increase to be achieved, compared to bare GCE. Under optimized experimental conditions (activated carbon to laponite ratio, pH and accumulation time), the AC-GCE exhibited a linear response to methyl parathion in two concentration ranges: from 0.01 μmol L⁻¹ to 1 μmol L⁻¹ and from 1 μmol L⁻¹ to 6 μmol L⁻¹. The LOD of 2.5 nmol L⁻¹ (S/N=3) achieved fitted with regulatory norms. It was demonstrated that the as-prepared AC-GCE is suitable for routine real samples analysis.     

Voltammetric Determination of L‐Dopa on Poly(3,4‐ethylenedioxythiophene)‐Single‐Walled Carbon Nanotube Composite Modified Microelectrodes

In the present communication, it is shown that platinum microelectrodes electrochemically coated with a composite of poly(3,4‐)ethylenedioxythiophene and single‐walled carbon nanotubes (PEDOT/SWNT) enable determinations of 3,4‐dihydroxy‐L ‐phenylalaines (L ‐dopa) in neutral phosphate buffer solutions containing an excess of ascorbic acid. The interpenetrated networked nanostructure of the composite was characterized by scanning electron microscope (SEM) and Raman spectroscopy. It is shown that the presence of the composite gives rise to an increase in the electroactive area of an order of magnitude in compared to the area for the bare microelectrodes. The composite film‐coated microelectrode, which yielded reversible cyclic voltammograms for the ferro/ferricyanide redox couple for scan rates between 0.01 and 0.10 V s^?1, also gave rise to two well‐resolved oxidation peaks for L ‐dopa and ascorbic acid (AA). The latter effect, which was not seen in the absence of the composite, enabled differential pulse voltammetric determinations of L ‐dopa in the concentration range between 0.1 to 20 μM with a detection limit of 100 nM.     

电聚合修饰碳纤维电极及乳酸脱氢酶活性的测定

用电聚合方法将亚甲基绿 (MG)修饰在碳纤维电极 (直径 7μm)上 ,并用该修饰电极测定了乳酸脱氢酶 (LDH)活性。在烟酰胺腺嘌呤二核苷酸 (NAD+ )浓度为 6 .0× 10 - 4mol L ,乳酸浓度为 5 .0× 10 - 3mol/L的pH7.0NaOH KH2 PO4 缓冲介质中 ,电位恒定在 +0 .10V下 ,用电流法测定乳酸脱氢酶活性 ,线性范围为 15～ 2 4 0U/mL ,检测限为 10U/mL ,响应时间为 15s。该修饰微电极稳定性好、灵敏度高、测定干扰小     

Voltammetric Determination of Urinary 1‐Hydroxypyrene Using Molecularly Imprinted Polymer‐Modified Screen‐Printed Carbon Electrodes

A two step non‐competitive affinity method for the trace determination of 1‐hydroxypyrene (1‐OHP) using a disposable molecularly imprinted polymer (MIP) modified screen‐printed carbon electrode (MIP‐SPCE) has been developed. The MIP was synthesized according to a novel strategy, which is described, and is capable of rebinding the phenolic analyte, 1‐hydroxypyrene (1‐OHP), from high pH aqueous organic media, via ionic interactions. In the first step of our method 1‐OHP was accumulated at the MIP‐SPCE from 35% aqueous methanol containing 0.014 M NaOH and 0.14 M NaCl, at open circuit. In the second step, the resulting SPCE with accumulated 1‐OHP was then transferred to fresh, clean phosphate buffered aqueous methanol, and subjected to cyclic voltammetry (CV) or differential pulse voltammetry (DPV). The latter technique proved to be more sensitive at detecting 1‐OHP, with a limit of detection of 182 nM and a linear range to 125 μM on unmodified electrodes. The possible effects of interference by related phenolic compounds in the MIP‐SPCE of 1‐OHP were investigated. Finally the method was evaluated by carrying out 1‐OHP determinations on spiked human urine samples; the recovery of 1‐OHP was 79.4% and the coefficient of variation was found to be 7.7% (n= 4) using a separate MIP‐SPCE for each determination. Therefore, the performance data suggests that the method is reliable at the concentrations examined in this study. The method was found to be superior to the direct determination of 1‐OHP in human urine by DPV alone, which was greatly affected by interference from uric acid.     

Preparation and Characterization of Antibacterial Polyacrylonitrile-based Activated Carbon Fiber Supporting Nano-ZnO

Polyacrylonitrile(PAN)-based activated carbon fiber(PACF) supporting nano-ZnO(PACF /nano-ZnO) was prepared by spin, pretreatment, carbonization, and KOH chemical activation at an activation temperature of 950 ℃ for 40 min. Nano-ZnO content, distribution and antibacterial properties of the PACF/nano-ZnO were studied. The pore structure and surface properties of the PACF/nano-ZnO were studied by Brunauer-Emmett-Teller(BET), N₂/77 K isothermal adsorption. The specific surface area increased markedly after the activation process and it was several hundred times greater than that before the process. The PACF/nano-ZnO shows a strong adsorption for Staphylococcus aureus(S. aureus) and Escherichia coli(E. coli) and antibacterial activity against them. As an experimental result, antibacterial properties of PACF/nano-ZnO increased with increasing the concentration of nano-ZnO particles, which suggests it is a promising antibacterial material.     

Voltammetric Determination of Xanthine with a Single‐Walled Carbon Nanotube‐Ionic Liquid Paste Modified Glassy Carbon Electrode

Single‐walled carbon nanotube (SWNT) and room temperature ionic liquid (i.e., 1‐butyl‐3‐methylimidazolium hexaflourophosphate, BMIMPF₆) were used to fabricate paste modified glassy electrode (GCE). It was found that the electrode showed sensitive voltammetric response to xanthine (Xt). The detection limit was 2.0×10^?9 M and the linear range was 5.0×10^?9 to 5.0×10^?6 M. The electrode also displayed good selectivity and repeatability. In the presence of uric acid (UA) and hypoxanthine (Hx) the response of Xt kept almost unchanged. Thus this electrode could find application in the determination of Xt in some real samples. The analytical performance of the BMIMPF₆‐SWNT/GCE was demonstrated for the determination of Xt in human serum and urine samples.     

Gd掺杂TiO2/活性炭纤维复合材料的制备及表征

以TiCl4和Gd(NO3)3·6H2O为主要原料,采用酸催化水解法制备Gd掺杂TiO2光催化剂并通过浸涂法将其负载在活性炭纤维(ACF)表面,制得Gd掺杂TiO2/ACF复合材料。 以气相苯为模型物,考察材料的光催化活性。 利用XRD、FTIR及GC-MS对催化剂的晶相结构、光谱特征等进行了表征。 结果表明,Gd掺杂能有效抑制TiO2的晶粒生长。 Gd掺杂量、浸涂次数影响TiO2/ACF光催化活性,Gd2O3掺杂质量分数为0.48%、浸涂2次的TiO2/ACF活性最高。 在苯光催化氧化后的Gd掺杂TiO2/ACF复合材料表面未发现醌类中间产物的存在。 Gd的掺入能减缓催化剂失活,光催化反应100 min后仍能表现出较高活性。     

Voltammetric Determination of Phenoxybenzyl‐Type Insecticides at Chemically Modified Conducting Polymer‐Carbon Nanotubes Coated Electrodes

The electrochemical reduction of three common insecticides such as cypermethrin (CYP), deltamethrin (DEL) and fenvalerate (FEN) was investigated at glassy carbon electrode (GCE), multiwalled carbon nanotubes modified GCE (MWCNT‐GCE), polyaniline (herein called as modifier M₁) and polypyrrole (herein called as modifier M₂) deposited MWCNT/GCE using cyclic voltammetry. Influences of pH, scan rate, and concentration were studied. The surface morphology of the modified film was characterized by scanning electron microscopy (SEM) and X‐ray diffraction analysis (XRD). A systematic study of the experimental parameters that affect differential pulse stripping voltammetry (DPSV) was carried out and the optimized experimental conditions were arrived at. The calibration plots were linear over the insecticide's concentration range 0.1–100 mg L^?1 and 0.05–100 mg L^?1 for all the three insecticides at MWCNT‐GCE and MWCNT(M₁)‐GCE respectively. The MWCNT(M₂)‐GCE performed well among the three electrode systems and the determination range obtained was 0.01–100 mg L^?1 for CYP, DEL and FEN. The limit of detection (LOD) was 0.35 μg L^?1, 0.9 μg L^?1 and 0.1 μg L^?1 for CYP, DEL and FEN respectively on MWCNT(M₂)‐GCE modified system. Suitability of this method for the trace determination of insecticide in spiked soil sample was also determined.     

Simultaneous Determination of Hydroquinone and Catechol at an Activated Glassy Carbon Electrode

A selective and very simple electrochemical method, based on anodization of a glassy carbon electrode (GCE), was developed for the simultaneous detection of hydroquinone (HQ) and catechol (CT). It was found that the activated GCE showed an excellent catalytic behavior and enhanced reversibility towards the oxidation of both HQ and CT. The redox responses from the mixture of HQ and CT were easily resolved at an activated GCE. The detection limits for HQ and CT were calculated to be 0.16 and 0.11 μM, respectively. The activated GCE was successfully examined for real sample analysis with tap water and it showed a stable and reliable recovery data.     

Electrochemical Behavior and Determination of L‐Tyrosine at Single‐walled Carbon Nanotubes Modified Glassy Carbon Electrode

Based on single‐walled carbon nanotubes (SWCNTs) modified glassy carbon electrode (GCE/SWCNTs), a novel method was presented for the determination of L ‐tyrosine. The GCE/SWCNTs exhibited remarkable catalytic and enhanced effects on the oxidation of L ‐tyrosine. In 0.10 mol/L citric acid‐sodium citrate buffer solution, the oxidation potential of L ‐tyrosine shifted negatively from +1.23 V at bare GCE to +0.76 V at GCE/SWCNTs. Under the optimized experimental conditions, the linear range of the modified electrode to the concentration of L ‐tyrosine was 5.0×10^?6–2.0×10^?5 mol/L (R₁=0.9952) and 2.7×10^?5–2.6×10^?4 mol/L (R₂=0.9998) with a detection limit of 9.3×10^?8 mol/L. The kinetic parameters such as α (charge transfer coefficient) and D (diffusion coefficient) were evaluated to be 0.66, 9.82×10^?5 cm² s^?1, respectively. And the electrochemical mechanism of L ‐tyrosine was also discussed.     

用活性炭纤维同时脱除二氧化碳中COS与H_2S的研究

采用固定床动态吸附实验考察了用NaOH、KOH、Na2CO3、K2CO3和Fe3+、CO2+等对活性炭纤维(ACF)进行改性,并分别对其脱除氧硫化碳(COS)和硫化氢(H2S)的性能进行了测试。重点是以N2和CO2为稀释气,对改性离子的种类、含量、反应气氛和反应温度等的脱硫性能进行研究,还考察了在COS和H2S同时存在的情况下,ACF脱除COS和H2S的性能。结果表明,碱改性ACF比空白ACF脱除效果好,金属离子改性ACF与碱改性ACF相比可以有效地提高活性炭纤维的硫容量。其中,用CO2+改性ACF能同时提高脱除COS和H2S的效果。     

Direct Voltammetric Determination of Redox‐Active Iron in Carbon Nanotubes

With the advances in nanotechnology over the past decade, consumer products are increasingly being incorporated with carbon nanotubes (CNTs). As the harmful effects of CNTs are suggested to be primarily due to the bioavailable amounts of metallic impurities, it is vital to detect and quantify these species using sensitive and facile methods. Therefore, in this study, we investigated the possibility of quantifying the amount of redox‐available iron‐containing impurities in CNTs with voltammetric techniques such as cyclic voltammetry. We examined the electrochemistry of Fe₃O₄ nanoparticles in phosphate buffer solution and discovered that its electrochemical behavior could be affected by pH of the electrolyte. By utilizing the unique redox reaction between the iron and phosphate species, the redox available iron content in CNTs was determined successfully using voltammetry.     

Square‐Wave Voltammetric Determination of Paraquat at Carbon Paste Electrode Modified with Hydroxyapatite

The voltammetric behavior of paraquat was investigated at hydroxyapatite‐modified carbon paste electrode HAP‐CPE in K₂SO₄. A method was developed for the detection of the trace of this herbicide, based on their redox reaction. The reduction peaks of paraquat were observed around ?0.70 V and ?1.00 V (vs. SCE) in square‐wave voltammetry. Experimental conditions were optimized by varying the accumulation time, apatite loading and measuring solution pH. Calibration plots were linear under the optimized parameters over the herbicide's concentration range 8–200×10^?7 mol L^?1, with a detection and quantification limits about 1.5×10^?8 mol L^?1 and 6.4 10^?8 mol L^?1, respectively.     

Sensitive Determination of Nitrofurantoin by Flow Injection Analysis Using Carbon Nanofiber Screen Printed Electrodes

In this work, a new method to quantify nitrofurantoin in aqueous media using a flow injection system connected to commercially available screen‐printed carbon nanofibers was developed. A pretreatment of the screen‐printed carbon nanofibers electrode with Britton? Robinson buffer/N,N‐dimethylformamide was applied to enhance the nitrofurantoin peak current signal in one step. The developed method was demonstrated to be sensible, reproducible, easy, and inexpensive. With a low detection limit, it is applicable to real samples. The results indicate that it is highly applicable for the detection of nitrofurantoin in several matrices. When urine samples without any pretreatment were analyzed, the method proved reproducible and sensible and had a low detection limit. The use of screen‐printed electrodes has advantages over other modified electrodes as a glassy carbon due to its versatility.     

Nafion修饰电化学活化碳纤维微电极测定去甲肾上腺素

本用自制的碳纤维微电极，经过适当的电化学预处理以后，测定神经递质去甲肾上腺素时，表现出较高的灵敏度，用Ｎａｆｉｏｎ修饰后，能有效地消除脑中去甲肾上腺素的主要干扰物抗坏血酸的干扰，线性范围５×１０＾－５－２×１０＾－４ｍｏｌ／Ｌ，检出下为２×１０＾－８ｍｏｌ／Ｌ，用这种微电极对注射液中的去甲肾上腺素进行测定，回收率在９７．２％－１０２．８５之间，可用于活体分析。     

Stripping Voltammetric Determination of Zirconium with Complexing Preconcentration of Zirconium(IV) at a Morin‐Modified Carbon Paste Electrode

A sensitive, selective and economic stripping voltammetry is described for the determination of trace amounts of zirconium at a morin‐modified carbon paste electrode (morin‐MCPE). Zirconium(IV) can be preconcentrated on the surface of the morin‐MCPE due to forming the Zr(IV)–morin complex. The complex produces two second‐order derivative anodic peaks at 0.69 V (vs. SCE) and 0.75 V when linear‐scanning from 0.0 to 1.0 V. The optimum analytical conditions are: 2.2 mol L^?1 HCl, 0.0 V accummulation potential, 90 s accummulation time, 250 mV s^?1 scan rate. A linear relationships between the peak currents at 0.75 V and the Zr(IV) concentration are in the range of 2.0×10^?8 to 3.0×10^?6 mol L^?1. The detection limit is 1.0×10^?8 mol L^?1 (S/N=3) for 120 s accumulation. The RSD for determination of 4.0×10^?7 mol L^?1 Zr(IV) is 4.8% (n=8). The proposed method has been applied to determine zirconium in ore samples, unnecessarily extracted.     

Sensitive Voltammetric Response of p‐Nitroaniline on Single‐Wall Carbon Nanotube‐Ionic Liquid Gel Modified Glassy Carbon Electrodes

An ionic liquid (i.e., 1‐butyl‐3‐methylimidazolium hexafluorophosphate, BMIMPF₆)‐single‐walled carbon nanotube (SWNT) gel modified glassy carbon electrode (BMIMPF₆‐SWNT/GCE) is fabricated. At it the voltammetric behavior and determination of p‐nitroaniline (PNA) is explored. PNA can exhibit a sensitive cathodic peak at ?0.70 V (vs. SCE) in pH 7.0 phosphate buffer solution on the electrode, resulting from the irreversible reduction of PNA. Under the optimized conditions, the peak current is linear to PNA concentration over the range of 1.0×10^?8–7.0×10^?6 M, and the detection limit is 8.0×10^?9 M. The electrode can be regenerated by successive potential scan in a blank solution for about 5 times and exhibits good reproducibility. Meanwhile, the feasibility to determine other nitroaromatic compounds (NACs) with the modified electrode is also tested. It is found that the NACs studied (i.e., p‐nitroaniline, p‐nitrophenol, o‐nitrophenol, m‐nitrophenol, p‐nitrobenzoic acid, and nitrobenzene) can all cause sensitive cathodic peaks under the conditions, but their peak potentials and peak currents are different to some extent. Their peak currents and concentrations show linear relationships in concentration ranges with about 3 orders of magnitude. The detection limits are 8.0×10^?9 M for p‐nitroaniline, 2.0×10^?9 M for p‐nitrophenol, 5.0×10^?9 M for o‐nitrophenol, 5.0×10^?9 M for m‐nitrophenol, 2.0×10^?8 M for p‐nitrobenzoic acid and 8.0×10^?9 M for nitrobenzene respectively. The BMIMPF₆‐SWNT/GCE is applied to the determination of NACs in lake water.     

活性炭吸附-石墨炉原子吸收光谱法测定土壤样品中铊

土壤试样用经盐酸-硝酸-高氯酸-氢氟酸混合酸溶解后,以活性炭吸附分离样品溶液中痕量铊,用热的草酸铵溶液进行淋洗分离,采用石墨炉原子吸收光谱法测定土壤中痕量铊。以0.06μg·L~(-1)氯化钯溶液作为基体改进剂,选择灰化温度、原子化温度分别为700℃和1 700℃。铊质量浓度在0.006～200μg·L~(-1)范围内与吸光度呈线性关系,方法检出限(3s/k)为0.2 pg。方法用于分析土壤样品,回收率在93.3%～106.2%之间,相对标准偏差(n=6)在0.6%～1.8%之间。     

Adsorptive Stripping Differential Pulse Voltammetric Determination of Risperidone with a Multi‐Walled Carbon Nanotube‐Ionic Liquid Paste Modified Glassy Carbon Electrode

A new composite electrode has been fabricated based on coating multi‐walled carbon nanotubes (MWCNTs) and n‐octylpyridinum hexafluorophosphate (OPPF₆) ionic liquid composite on a glassy carbon (GC) electrode (OPPF₆‐MWCNTs/GCE). This electrode shows very attractive electrochemical performances for electrooxidation of risperidone (RIS) compared to conventional electrodes using carbon and mineral oil, notably improved sensitivity and stability. The oxidation peak potentials in cyclic voltammogram of RIS on the OPPF₆‐MWCNTs/GCE was occurred around 230 mV vs. SCE at Britton–Robinson (B–R) buffer (pH 4.0) at scan rate of 100 mV s^?1. The electrochemical parameters such as diffusion coefficient (D), charge transfer coefficient (α) and the electron transfer rate constant (k/_s) were determined using cyclic voltammetry. Under the optimized conditions, the peak current was linear to risperidone concentration over the concentration range of 10–200 nM with sensitivity of 0.016 μA/nM^?1 using differential pulse voltammetry. The detection limit was 6.54 nM (S/N = 3). The electrode also displayed good selectivity and repeatability. In the presence of clozapine (CLZ) the response of RIS kept almost unchanged. Thus this electrode could find application in the determination of RIS in some real samples. The analytical performance of the OPPF₆‐MWCNTs/GCE was demonstrated for the determination of RIS in human serum and pharmaceutical samples.     

5-羟色胺在碳纤维微电极上的电化学测定及伏安行为研究

本文研究了5 羟色胺在Na2HPO4 KH2PO4(pH6.0)缓冲溶液中,于自制的碳纤维微电极上的伏安行为。在此缓冲溶液中5 羟色胺有一对氧化还原峰,峰电位分别为0.2V和0.4V。峰电流与5 羟色胺的浓度分别在4.0×10-6～4.0×10-5mol/L和5.0×10-6～5.0×10-5mol/L范围内呈良好的线性关系,检出限分别为4.70×10-6mol/L和1.76×10-6mol/L。同时利用多种电化学方法求出了动力学参数。