青霉素对乳酸-丙酮-溴酸钾-硫酸锰-硫酸开放化学振荡体系的扰动

在连续搅拌反应器(CSTR)中,利用分析物脉冲微扰技术(APP)研究了青霉素对锰离子催化Belousov-Zhabotinsky(B-Z)开放化学振荡体系的影响。结果表明,青霉素浓度在2.97×10-7～5.50×10-5mol/L范围内,周期和振幅的变化率与所加入青霉素浓度的负对数呈良好的线性关系,相关系数分别为0.9981和0.9985;检出限为5.9×10-8mol/L。所建立的方法简便易行,每小时可进样15次。对可能的反应机理也进行了讨论。锰属于生命元素,在体内参与生物酶的合成与转化,研究青霉素对锰催化振荡反应体系的扰动对于理解生命运动更为有利。     

超痕量H2O2对MnSO4-KBrO3-乙酰丙酮化学振荡体系的扰动

化学振荡波和生物体内的生物振荡及生物形态现象的相似性促使人们认识到生命现象和非生命现象之间遵循着某些相同的规律, 因而化学振荡反应非线性动力学一直是物理化学研究的热点[1, 2]. 近年来它在分析化学中的应用使其研究扩展到了一个新的领域, 但仍停留在10-7 mol/L的水平上[3]. 显然, 以这个量去研究包含众多基元反应和反应中间体的振荡反应, 得到的是数目庞大的反应物种群体行为, 而这种行为并不足以说明生命现象的猝发病变、代谢功能衰竭及运动寿命终止的原因.     

超痕量H_2O_2对MnSO_4-KBrO_3-乙酰丙酮化学振荡体系的扰动

化学振荡波和生物体内的生物振荡及生物形态现象的相似性促使人们认识到生命现象和非生命现象之间遵循着某些相同的规律 ,因而化学振荡反应非线性动力学一直是物理化学研究的热点 [1,2 ] .近年来它在分析化学中的应用使其研究扩展到了一个新的领域 ,但仍停留在 1 0 - 7mol/L的水平上 [3] .显然 ,以这个量去研究包含众多基元反应和反应中间体的振荡反应 ,得到的是数目庞大的反应物种群体行为 ,而这种行为并不足以说明生命现象的猝发病变、代谢功能衰竭及运动寿命终止的原因 .　　我们在研究 H2 O2 对 Mn SO4 - KBr O3-乙酰丙酮宏观振荡规…     

Determination of Ascorbic Acid Using a New Oscillating chemical System of Lactic Acid—Acetone—BrO3^— —Mn^2 —H2SO4

ＩｎｔｒｏｄｕｃｔｉｏｎＯｓｃｉｌｌａｔｉｎｇｒｅａｃｔｉｏｎｓａｒｅｃｏｍｐｌｅｘｄｙｎａｍｉｃｓｙｓｔｅｍｓｔｈａｔｉｎｖｏｌｖｅｐｅｒｉｏｄｉｃｃｈａｎｇｅｓｉｎｔｈｅｃｏｎｃｅｎｔｒａｔｉｏｎｏｆｓｏｍｅｉｎｇｒｅｄｉｅｎｔｓ (ｗｈｅｔｈｅｒａｒｅａｃｔａｎｔ,ａｐｒｏｄｕｃｔｏｒａｎｉｎｔｅｒｍｅ ｄｉａｔｅ)ｗｉｔｈｔｉｍｅ .Ｔｈｅｓｉｍｉｌａｒｉｔｉｅｓｂｅｔｗｅｅｎｌｉｆｅｐｒｏｃｅｓｓｅｓｔｈａｔｅｘｈｉｂｉｔｏｓｃｉｌｌａｔｉｎｇｂｅｈａｖｉｏｒａｎｄｏｓｃｉｌｌａｔｉｎｇｃｈ…     

海洛因对别洛索夫-扎鲍京斯基振荡化学反应的影响及其分析应用

研究了海洛因对Belousov Zhabotinsky(B Z)振荡反应的影响 ,结果表明 :海洛因的加入明显地改变了振荡体系的周期和振幅 ,即对振荡体系产生扰动 ,扰动的浓度范围为 1.8× 10 -8～ 2 .1× 10 -3 mol/L ,且海洛因的浓度分别在 3.8× 10 -6～ 2 .8× 10 -5mol/L和 0 .9× 10 -6～ 2 .9× 10 -5mol/L范围内与振荡周期改变值ΔT和振幅改变值ΔA均呈现良好的线性关系 ,相关系数分别为 0 .9931和 0 .974 6。据此 ,建立了测定海洛因的新方法。     

Determination of sulfanilamide based on the Mn(II)-catalyzed oscillating chemical reaction

A convenient and sensitive method for determination of sulfanilamide (SNA) was described based on the Mn(II)-catalyzed oscillating chemical reaction. Under optimum conditions, a linear relationship existed between the changes of oscillating period or amplitude and the negative of logarithm of SNA concentration in the range of 4.27 × 10⁻⁸ mol ·L⁻¹ ∼ 7.41 × 10⁻⁶ mol ·L⁻¹ (RSD, 0.85%) and 9.33 × 10⁻⁸ mol ·L⁻¹ ∼ 3.02 × 10⁻⁶ mol ·L⁻1 (RSD, 1.08%), respectively. The lower limit of detection was found to be 2.69 × 10⁻⁸ mol ·L⁻¹ and 6.03 × 10⁻⁸ mol ·L⁻¹, respectively.      

Differential Pulse Voltammetric Determination of Uric Acid on Carbon‐Coated Iron Nanoparticle Modified Glassy Carbon Electrodes

A carbon‐coated iron nanoparticles (CIN, a new style fullerence related nanomaterial) modified glassy carbon electrode (CIN/GCE) has been developed for the determination of uric acid (UA). Electrochemical behaviors of UA on CIN/GCE were explored by cyclic voltammetry (CV) and differential pulse voltammetry (DPV). It was found that the voltammetric response of UA on CIN/GC was enhanced dramatically because of the strong accumulation effect of CIN and the large working area of the CIN/GC electrode. The parameters including the pH of supporting electrolyte, accumulation potential and time, that govern the analytical performance of UA have been studied and optimized. The DPV signal of UA on CIN/GCE increased linearly with its concentration in the range from 5.0×10^?7 to 2.0×10^?5 M, with a detection limit of 1.5×10^?7 M (S/N=3). The CIN/GCE was used for the determination of UA in samples with satisfactory results. The proposed CIN/GCE electrochemical sensing platform holds great promise for simple, rapid, and accurate detection of UA.     

Determination of Copper by an Adsorption Differential Pulse Stripping Method with Naphthol Derivative

ABSTRACT

A simple, sensitive and selective method is proposed for the determination of copper(II) by adsorption-differential pulse stripping method. This method is based on the selective accumulation of the complexes of Cu(II) with l-(2-pyridylazo)-2-Naphthol and then reduction of the complex on a HMDE. The reduction current of the complex is about 0.0V vs. Ag/AgCl reference electrode at p8543146=4.0. The influences of various experimental parameters on the current peak were completely studied. The calibration graph was linear up to 50.0 ng/ml for a deposition time of 60 sec. The relative standard deviation was 2.3% (n=5) for Cu(II) concentration of 10.0 ng/ml, with a limit of detection of 0.2 ng/ml. The influence of potentially interfering ions was completely studied. The method has been applied for the determination of Cu(II) in water samples.     

氢甲酰化反应溶剂效应的量子化学研究

在B3LYP/6-31G(d, p)(Rh和P采用LANL2DZ + Polar)水平下,利用自洽反应场（SCRF）的Onsager模型,系统研究了C6H12、C6H6、THF、CH2Cl2、CH3OH和H2O（相对介电常数ε分别为2.02、2.25、7.58、8.93、32.63和78.39）六种溶剂对乙烯氢甲酰化反应中各驻点的结构和反应机理的影响.分别在上述溶剂中优化了反应物、产物、中间体和过渡态的结构,并计算了自由能和活化自由能.计算结果表明,不同溶剂对反应势能面上各驻点的结构和能量均有一定的影响,而且随着相对介电常数ε的增加,反应的活化自由能下降.水是以上六种溶剂中最佳的溶剂,这与大量的实验研究结果一致.     

Determination of Imidacloprid in Tomato Grown in Greenhouse Based on Copper(II) Phthalocyanine Modified Carbon Ceramic Electrode by Differential Pulse Voltammetry

A new sol‐gel derived electrocatalytic carbon ceramic electrode was prepared by incorporating copper(II) phthalocyanine (CuPc) in a carbon ceramic network. This electrode was used as a sensitive electrochemical sensor for determination of the insecticide Imidacloprid (1‐(6‐chloro‐3‐pyridylmethyl)‐N‐nitro‐imidazolidin‐2‐ylideneamine) by differential pulse voltammetry (DPV). The resulting modified electrode exhibits a cathodic peak potential shifted positively and an increasing in cathodic peak current in comparison with unmodified electrode. The redox properties of this modified electrode at various pH values and CuPc percentage were investigated. The catalytic current obtained from differential pulse voltammetry is linearly dependent on Imidacloprid concentration over the two linear ranges of 0.67‐17 μM and 17‐93 μM with correlation coefficient of R² = 0.9999 and R² = 0.990, respectively. The detection limit for Imidacloprid was found to be 0.28 μM according to lower linear range. Possible interferences from several common pesticides were also evaluated. The inherent stability, high sensitivity, low detection limit and low cost for each preparation are advantages of this sensor. Determination of Imidacloprid in commercial formulation and residual Imidacloprid in tomato grown in greenhouse (protected cultivation) was also conducted. The results obtained from commercial formulation were completely consistent with those obtained through the standard high‐performance liquid chromatography (HPLC) method.     

头孢唑啉钠的荷移分光光度法测定

研究了头孢唑啉钠与７，７，８，８－四氰基对二次甲基苯醌（ＴＣＮＱ）的荷移（ＣＴ）反应，确立了荷移反应的最佳条件。结果表明：在丙酮－甲醇介质中，两者于３０℃水浴中恒温３０ｍｉｎ即可形成１∶２的络合物，在其最大吸收波长７４３ｎｍ处表观摩尔吸光系数ε＝１７６×１０４Ｌ·ｍｏｌ－１·ｃｍ－１，在０～２４ｍｇ／Ｌ范围内符合比尔定律线性关系。方法的相对标准偏差小于３％（ｎ＝１０）。对形成ＣＴ络合物的机理进行了探讨。并应用拟定的方法对样品注射用头孢唑啉钠进行了含量测定，结果与标准方法一致，回收率符合要求     

苯-卤素(X2, X=F, Cl, Br, I)相互作用本质的对称性匹配微扰理论研究

在MP2水平下对被定义为"电荷转移复合物(CTC)"的苯(C6H6)-卤素分子X2(X＝F, Cl, Br, I)相互作用体系进行了量子化学研究. 在优化所得C6H6-X2(X＝F, Cl, Br, I)复合物的平衡几何结构中, 卤素分子X2接近垂直指向苯环上碳-碳双键的中心. 自然键轨道(NBO)分析结果表明, 苯-卤素体系中电荷转移的数量很少. 对称性匹配微扰理论(Symmetry-adapted perturbation theory, SAPT) 能量分解结果显示, 在4个复合物体系中, 静电作用的贡献相对较小(只占总吸引作用的20%左右), 对于C6H6-F2体系, 色散作用是其主要吸引作用, 对于C6H6-Cl2, C6H6-Br2和C6H6-I2 体系, 诱导作用则是其主要的吸引作用, 从F到I, 色散作用逐渐减弱, 诱导作用逐渐增强, 表明在电子相关水平上将苯-卤素体系称为"电荷转移复合物"的说法并不确切.     

Differential Pulse Polarographic Determination of Cd(II) and Pb(II) in Milk Samples after Solid‐Phase Extraction Using Amberlite XAD‐2 Resin Modified with 2,2′‐DPED3P

In the present paper novel column solid phase extraction procedure was developed for the determination of Cd(II) and Pb(II) in cows', goats', ewes', buffalos' and humans' milk samples using newly synthesized reagent 2,2′‐DPED₃P (2,2′‐{[1,2‐diphenylethane‐1,2‐diylidene]dinitrilo}diphenol) for preconcentration and separation prior to differential pulse polarography using amberlite XAD‐2 in the ranges of pH 4.0–5.0. The sorbed elements were subsequently eluted with 10 mL of 2 M HCl elutes were analysed by differential pulse polarography (DPP). The interference of foreign ions has also been studied. Effects of various instrumental parameters are investigated and received conditions are optimized. The total metal concentration of the milk samples in the study area were in the following ranges 0.030–0.090 μg L^?1 of Cd(II), 0.009–0.026 μg L^?1 of Pb(II) respectively. The limits of detections were found to be 0.020 and 0.024 μg L^?1 for Cd(II) and Pb(II) respectively by applying a preconcentration factor ～40. The proposed enrichment method was applied successfully for the determination of metal ions in cows', goats', ewes', buffalos' and humans' milk samples.     

基于纳米银/多壁碳纳米管修饰电极的电化学法测定磺胺甲唑

以表面处理多壁碳纳米管(MWCNTs)和硝酸银为原料,利用硼氢化钠还原法制备了纳米银/多壁碳纳米管复合材料(AgNPs/MWCNTs),并通过紫外-可见吸收光谱、红外光谱、拉曼光谱和X射线衍射进行表征。采用滴涂法将该纳米复合材料修饰至玻碳电极表面,得到纳米银/多壁碳纳米管修饰电极(AgNPs/MWCNTs/GCE)。以AgNPs/MWCNTs/GCE为工作电极,研究了缓冲溶液、pH值、支持电解质和扫描速度对磺胺甲■唑(SMZ)电化学反应活性的影响。结果表明,与多壁碳纳米管、纳米银单独修饰电极相比,该纳米复合材料修饰电极对SMZ显示了更高的电催化活性。优化条件下,SMZ浓度在3.0×10~(-7)～5.0×10~(-5) mol/L范围内与峰电流呈线性关系,检出限(S/N=3)为6.4×10~(-8) mol/L。该方法操作简单、快速,可用于河水样品中SMZ的检测。     

Indirect Spectrophotometric Determination of Vanadium(IV) by Flow Injection Analysis Based on the Redox Reaction with Copper(II) in the Presence of Neocuproine

Abstract

An indirect photometric method with a continuous-flow analysis is presented for the determination of trace amounts of vanadium(IV). It is based on the redox reaction of copper(II) with vanadium(1V) in the presence of neocuproine. In the presence of neocuproine, copper(I1) is reduced easily by vanadium(I V) to a copper(1)-neocuproine complex, which shows a n absorption maximum at 454 nm. By measuring t h e absorbance of the complex at this wavelength, vanadium(1V) in t h e range 2×10^?6 - 8 × mol dm^?5 mol dm^?3 can be determined at a rate of 120 samples h^?1. The fractional determination of vanadium(1V) and iron(I1) is also studied.     

A New Turbidimetric Method for Determination of Melamine Based on its Reaction with Mercury(II)

A turbidimetric technique based on a reaction between Hg(II) and melamine is described for the measurement of melamine content of wastewater of a petrochemical company. The present technique is rapid and simple, uses a small amount of reagent and is set up with low‐cost equipment, making this system economically viable. The experimental conditions such as volume of reagent, pH of buffer, stirring time, stirring speed, ionic strength, etc. were optimized and used in plotting the calibration curve. The linear dynamic range was 1–70 mg/L with a limit of detection of 0.3 mg/L. Repeatability of the proposed method is good, and the relative standard deviation (RSD%) is less than 1.5%. Interferences studies showed that the common compounds existing in wastewater have no negative effect on the efficiency of the method at relatively high concentrations. Finally, the proposed method has been successfully used in determination of melamine in wastewater of Urmia Petrochemical Company.     

Sensitive Chemiluminescence Determination of Three Thiol Compounds Based on Cu(II)-Catalyzing Luminol Reaction in the Absence of an Oxidant

Abstract

A simple and sensitive flow-injection chemiluminescence method was proposed for the determination of three thiol compounds, namely cysteine, acetylcysteine, and glutathione. Weak chemiluminescence was produced directly by the reaction of these mentioned compounds with luminol in an alkaline solution without adding any special oxidants. The chemiluminescence signal could be significantly enhanced by Cu(II). The proposed method allows the determination of 4.0 × 10^?9 to 1.0 × 10^?7 g/mL cysteine, 7.0 × 10^?10 to 1.0 × 10^?7 g/mL acetylcysteine, and 4.0 × 10^?9 to 1.0 × 10^?6 g/mL glutathione with the detection limits of 8 × 10^?10 g/mL, 2 × 10^?11 g/mL, and 7 × 10^?10 g/mL, respectively. The proposed method was applied to the analysis of some commercial formulations containing acetylcysteine.     

聚(三聚氰胺)与金纳米粒共修饰玻碳电极用于芦丁的电化学测定

通过电聚合和电沉积方法首次制得聚(三聚氰胺)和金纳米粒共修饰的电极(PMel/Au/GCE),并对修饰电极进行交流阻抗电化学分析。采用循环伏安法研究了芦丁在修饰电极上的电化学行为,发现其氧化峰电流和还原峰电流较裸玻碳电极(GCE)以及聚(三聚氰胺)修饰的电极(PMel/GCE)明显增强,提高了检测的灵敏度。对溶液的pH值、金纳米粒子电沉积时间、三聚氰胺电聚合时间和扫描速率等实验条件进行了优化。采用示差脉冲伏安法对芦丁进行定量分析,芦丁浓度分别在7.8×10-9~1.2×10-6mol/L和1.2×10-6~1.5×10-5mol/L范围内与峰电流呈线性,其相关系数(r2)分别为0.997和0.993,检出限(S/N=3)为5.5×10-9mol/L。将该电极用于市售芦丁片检测,回收率为96.4%~101.8%。     

Determination of Enzymatic Activities Based on an Optical Flow-Through p-Nitrophenol Sensor

Abstract

An optical flow-through biosensor based on the transient retention of p-nitrophenol on an ion-exchange support packed in the flow cell is presented. The approach was applied to the determination of the activity of some enzymes which catalyze the conversion of p-nitrophenyl-derivatives into p-nitrophenol. The method was first developed for determination of p-nitrophenol yielding a linear range between 0.1–5 μg/mL (r² = 0.9922, r.s.d.% less than 2.5), then, it was also applied to the determination of β-D-glucuronidase activity in serum, with a linear range between 0.1–20 U/L (r² = 0.9976, r.s.d.% less than 3.0), and a sampling frequency of 20 h^?1. The application of the method to the determination of the enzyme activity in serum samples provided results consistent with those obtained by a conventional method and recoveries within 95–104%.     

A Novel Electrochemical Sensor Based on Modified Carbon Paste Electrode with ZnO Nanorods for the Voltammetric Determination of Indole-3-acetic Acid in Plant Seed Extracts

Detection of indole-3-acetic acid (IAA), as a phytohormone, is important for precision farming, plant phenotyping, and crop management. Herein, IAA was detected in bean and wheat plant seeds extractions using zinc oxide nanorods/carbon paste electrode (ZnO NRs/CPE). ZnO NRs/CPE showed excellent electrocatalytic activity, high sensitivity, and selectivity toward the oxidation of IAA. The linearity range was from 30.×10⁻⁸ to 5.0×10⁻⁶ M (r²=0.996, n=10), with a detection limit of 1.7×10⁻⁸ M. Moreover, ZnO NRs/CPE exhibited high reproducibility, with a standard deviation of 1.0 % for six successive measurements of IAA.