Development of an Amperometric Biosensor for β‐N‐Oxalyl‐L‐α,β‐Diaminopropionic Acid (β‐ODAP)

An amperometric method for the determination of the neurotoxic amino acid β‐N‐oxalyl‐L ‐α,β‐diaminopropionic acid (β‐ODAP) using a screen printed carbon electrode (SPCE) is reported. The electrode material was bulk‐modified with manganese dioxide and used as a detector in flow injection analysis (FIA). The enzyme glutamate oxidase (GlOx) was immobilized in a Nafion‐film on the electrode surface. The performance of the biosensor was optimized using glutamate as an analyte. Optimum parameters were found as: operational potential 440 mV (vs. Ag/AgCl), flow rate 0.2 mL min^?1, and carrier composition 0.1 mol L^?1 phosphate buffer (pH 7.75). The same conditions were used for the determination of β‐ODAP. The signal was linear within the concentration range 53–855 μmol L^?1 glutamate and 195–1950 μmol L^?1 β‐ODAP. Detection limits (as 3σ value) for both analytes were 9.12 and 111.0 μmol L^?1, respectively, with corresponding relative standard deviations of 3.3 and 4.5%. The biosensor retained more than 73% of its activity after 40 days of on‐line use.     

Voltammetric behavior and determination of bismuth on sodium humate modified carbon paste electrode

The preconcentration and voltammetric behavior of Bi^III on a sodium humate modified carbon paste electrode was studied by means of cyclic voltammetry (CV) and differential pulse stripping voltammetry (DPSV). The proposed measurement involves an initial nonelectrolytic preconcentration step in which Bi^III is complexed by the surface modifier in a solution of 0.05 M KNO₃-0.0106 M HNO₃ (pH 2.0) and a subsequent electrochemical scan step in which the preconcentrated Bi^III was reduced and then oxidized promptly in supporting electrolyte of 0.5 M HNO₃. The resulting DPSV anodic current was proportional to the concentration of Bi^III ion over the range of 4.78 × 10⁻⁸–1.44 × 10⁻⁵ M. The detection limit was 4.78 × 10⁻⁸ M. The proposed method was used to determine bismuth in various samples. Various factors affecting the electrode behavior were also investigated at the same time.     

Study on electrochemical behavior of tryptophan at a glassy carbon electrode modified with multi-walled carbon nanotubes embedded cerium hexacyanoferrate

Electrochemical behavior of cerium hexacyanoferrate (CeHCF) incorporated on multi-walled carbon nanotubes (MWNTs) modified GC electrode is investigated by scanning electron microscopy (SEM) and electrochemical techniques. The CeHCF/MWNT/GC electrode showed potent electrocatalytic activity toward the electrochemical oxidation of tryptophan in phosphate buffer solution (pH 7.0) with a diminution of the overpotential of 240 mV. The anodic peak currents increased linearly with the concentration of tryptophan in the range of 2.0 × 10⁻⁷ to 1.0 × 10⁻⁴ M with a detection limit of 2.0 × 10⁻⁸ M (at a S/N = 3). And the determination of tryptophan in pharmaceutical samples was satisfactory.     

氧化物载负型沸石催化剂的阈值效应

用一系列氧化物，如Ｂ２Ｏ３，Ｓｂ２Ｏ３和ＭｇＯ，对ＨＺＳＭ－５沸石以及用Ｓｂ２Ｏ３对Ｈβ沸石进行改性。实验结果表明，这些氧化物可在沸石上自发单层分散且大部分分散的氧化物处于沸石孔内。用ＸＲＤ及ＸＰＳ方法测得它们的分散阈值。实验中发现，在甲苯烷基化反应中，对二甲苯选择性随氧化物含量增加而迅速提高；当氧化物在ＨＺＳＭ－５上的载量接近其分散阈值时，对二甲葳选择性达到最大，对某些体系可高达９５％左右，百在     

CH4, CO2和H2O在非金属原子修饰石墨烯表面的吸附

煤层气(矿井瓦斯)是一种有望替代传统化石燃料，如煤、石油和天然气的非常规气体. 作为可得的清洁能源，它的利用被认为是节能和经济的选择. 在本工作中，非金属原子X(X=H，O，N，S，P，Si，F，Cl)修饰的石墨烯(Gr)被用来代表具有结构异性的煤表面模型. 通过密度泛函理论系统地研究了煤层气组分Y(Y=CH₄，CO₂，H₂O)在非金属原子修饰石墨烯上的吸附作用. 结果表明Y在非金属原子修饰石墨烯上的吸附均为物理吸附. 态密度和差分电荷密度共同表明了这种弱的相互作用.其中，H和Cl对CH₄的作用较大； N、O、F、Cl对CO₂的作用较强； N，Cl对H₂O的影响不容忽视. 总的来说，吸附能大小依次为：H₂O>CO₂>CH₄. 因此，在CH₄富集的煤层里注入H₂O或CO₂可以与CH₄形成竞争吸附，进而提高煤层气采收率. 本工作提供了在分子水平下煤层气与非金属原子修饰石墨烯之间的相互作用的详情，并为煤层瓦斯的开采与分离提供了有用的信息.     

Electrocatalytic oxidation of hydrazine at cobalt hexacyanoferrate- modified glassy carbon, Pt and Au electrodes

The electrocatalytic oxidation of hydrazine has been studied on glassy carbon, Pt and Au electrodes modified by cobalt hexacyanoferrate (CoHCF) using cyclic voltammetry and rotating disc techniques. It has been shown that the oxidation of hydrazine to nitrogen occurs at the potential coinciding with that of Co(II) to Co(III) transformation in a CoHCF film, where no oxidation signal is observed at a bare glassy carbon electrode. A Tafel plot, derived from RDE voltammograms, exhibits a slope of 150 mV, indicating a one-electron charge transfer process to be the rate-limiting step. The electrocatalytic efficiency of the modified electrode towards hydrazine oxidation depends on solution pH, and the optimum range was found to be located between pH 5 and pH 7. The kinetic behaviour and location of the electrocatalytic process were examined using the W.J. Albery diagnosis table, and it was concluded that the reaction has either a “surface” or a “layer” reaction mechanism. Pt- and Au-CoHCF-modified electrodes show no significant electrocatalytic activity towards hydrazine oxidation. Received: 25 April 1997 / Accepted: 12 August 1997     

酵母核糖核酸在碳纳米管修饰电极上的电化学行为及其分析测定

研究了酵母核糖核酸（yRNA）在碳纳米管（MWNT）修饰电极上的电化学行为，优化了测定参数，在此基础上建立了一种直接测定yRNA的电分析测试方法。yRNA在碳纳米管修饰电极上于磷酸盐缓冲溶液中在0．758V处产生不可逆的氧化电流峰，峰电流与yRNA的质量浓度在1～10mg／mL之间有良好的线性关系，线性回归方程为：Iρ=0．0813ρ＋0．1807，相关系数r为0．9980，检出限为0．6mg／mL。     

The electrocatalytic examination of cephalosporins at carbon paste electrode modified with CoSalophen

The electrocatalytic oxidation of cephalexin and cefazolin has been studied at a carbon paste electrode modified with cobalt salophen (CoSal) by cyclic voltammetry. The selectivity of the carbon paste modified with CoSal in detecting cephalexin and cefazolin was examined. To suggest the electrocatalytic mechanism for electro-oxidation of cefazolin, the electrochemical behavior of ceftriaxone was investigated which has a thiol group out of the beta lactam ring. The electrocatalytic oxidation of these antibiotics is shown to be irreversible at the CoSal modified electrode. Scan rate dependence of cefazolin, which is a sulfur-containing compound, has been examined. The results indicated that the electrocatalytic oxidation of the compounds is diffusion controlled. The responses of the modified electrode were compared with those of unmodified electrode and it has shown that the modified electrode has better sensitivity than unmodified electrode to the detection of cefazolin. The overall number of electrons contributed to the oxidation of cefazolin is obtained 1 by chronoamperometry; the number of electron involved in the rate-determining step was 1. The results of differential pulse voltammetry (DPV) using the modified electrode with high sensitivity were applied for the determination of cefazolin in human synthetic serum samples. The linear range was obtained from 1 × 10⁻⁵ to 1 × 10⁻³ M for DPV determination of cefazolin in buffered solutions (pH 3.0).     

Voltammetric determination of L-dopa using an electrode modified with trinuclear ruthenium ammine complex (Ru-red) supported on Y-type zeolite

The L-dopa is the immediate precursor of the neurotransmitter dopamine. Unlike dopamine, L-dopa easily enters the central nervous system and is used in the treatment of Parkinson’s disease. A sensitive and selective method is presented for the voltammetric determination of L-dopa in pharmaceutical formulations using a carbon paste electrode modified with trinuclear ruthenium ammine complex [(NH₃)₅Ru^IIIORu^IV(NH₃)₄ORu^III(NH₃)₅]⁶⁺ (Ru-red) incorporated in NaY zeolite. The parameters which influence on the electrode response (paste composition, potential scan rate, pH and interference) were also investigated. The optimum conditions were found to an electrode composition (m/m) of 25% zeolite containing 6.7% Ru, 50% graphite and 25% mineral oil in acetate buffer at pH 4.8. Voltammetric peak currents showed a linear response for L-dopa concentration in the range between 1.2×10⁻⁴ and 1.0×10⁻² mol l⁻¹ (r=0.9988) with a detection limit of 8.5×10⁻⁵ mol l⁻¹. The variation coefficient for a 1.0×10⁻³ mol l⁻¹ L-dopa (n=10) was 5.5%. The results obtained for L-dopa in pharmaceutical formulations (tablet) was in agreement with compared official method. In conclusion, this study has illustrated that the proposed electrode modified with Ru-red incorporated zeolite is suitable valuable for selective measurements of L-dopa.     

有机硅改性丙烯酸酯共聚乳液合成方法及胶膜性能的研究

用一次投料法、单体乳液滴加法和引发剂滴加法有机硅改性丙烯酸酯共聚乳液，聚合过程、胶粒形态及乳液稳定性的观测结果表明：单体乳液滴加法是合成该类乳液的最佳方法，研究了单体乳液滴加法中有机硅含量与聚合反及胶膜性能的关系，结果表明：有机硅含量在１５％以下时，聚合反应可以顺利进行，胶膜性能不仅依赖于聚合时有机硅单体的总量，而且还依赖于有机硅单体中活性硅氧烷所占的比例。