金属离子Cu~(2+)，Co~(2+)，Ni~(2+)的微芯片电泳分离及化学发光检测

根据流动注射－化学发光的通用实验装置图，设计并通过标准光刻技术，湿化 学刻蚀及热键合技术制作了玻璃微芯片。在该芯片上将毛细管电泳分离与化学发光 检测相联用，鲁米诺和H_2O_2化学发光反应溶液通过实验室自制的微流泵输送。对 所用电压，缓冲溶液和发光试剂流速等实验条件进行了优化。在所选的最佳条件下 ，成功地实现了金属离子Cu~(2+)，Co~(2+)，Ni~(2+)的电泳分离－化学发光检测， 过渡金属离子。     

丙酮—H2O2—ClO^—化学发光反应的研究

化学发光是指由于某一化学反应而导致的一种光辐射。丙酮是一种常用的有机试剂。本文首次报道了丙酮-H_2O_2-ClO~-体系的化学发光反应,对反应试剂浓度的影响,金属离子和卤素离子的催化作用及有机物的影响进行了实     

过渡金属离子的掺杂对TiO2光催化活性的影响

考察了过渡金属离子对TiO₂ 光催化性能的影响,结果发现:第二过渡系列金属离子对TiO₂ 膜的修饰作用比第一过渡系列金属离子的修饰作用更加明显;第二、六副族的金属离子对TiO₂ 膜的修饰效果较好.通过X射线衍射(XRD)、电镜分析 (SEM)、光电能谱分析 (XPS)及差热分析 (DTA)对催化剂表面进行了表征,结果表明:TiO₂ 的晶型为锐钛矿型,粒子半径为 32.58nm.     

利用H2O2-KI-鲁米诺体系化学发光法测定痕量钼

钼(Ⅵ)可以催化H₂O₂氧化I^-的反应,生成的I₂在碱性水溶液中能氧化鲁米诺而产生化学发光^[1],本文将这两个反应结合起来,建立了铝的化学发光分析法,方法有较高的灵敏度,检出限为6×10^-10g/cm³Mo,测定的相对标准偏差小于6%,工作曲线的线性范围是1×10^-9～1×10^-7g/cm³Mo,用EDTA作掩蔽剂,排除了大多数金属离子的干扰,方法有较好的选择性,应用此法对一些粮食样品中的痕量钼进行了测定,结果比较满意。     

邻菲啉-H2O2-CTMAB-Cu(II)化学发光体系的研究及其应用

本文用改进的单纯形优化法研究了邻菲啉-H2O2-CTMAB-Cu(II)化学发光体系的最佳反应条件,较为祥细地研究了该化学发光反应的机理,较为合理地解释了表面活性剂在该体系中的作用.同时选择适当的掩蔽剂,大大提高了反应的选择性.据此拟定了新的化学发光测定痕量铜的方法,经试用于天然水的分析获得较为满意的结果.本法的检测限达0.09ppb,水样测试的精密度良好,回收率91.4-108.0%,与石墨炉原子吸收法测定的结果甚为一致.     

高锰酸钾-鲁米诺反应体系中碱土金属离子Mg2+,Ca2+,Sr2+,Ba2+化学发光行为研究

将被认为没有化学发光活性的第二主族(碱土金属)离子Mg^2 ,Ca^2 ,Sr^2 ,Ba^2 溶液注入到已充分反应的高锰酸钾与鲁米诺混合液中时,又发生了新的化学发光反应,并检测到强的化学发光信号．在对有关反应的动力学性质、化学发光光谱、紫外可见光谱及其它一系列实验研究的基础上,提出了可能的化学发光反应机理．同时,优化了反应条件,评价了这一反应用于Mg^2 ,Ca^2 ,Sr^2 ,Ba^2 分析的可行性．     

低压离子分离-化学发光在线检测过渡金属离子

 研究了低压离子 (LPIC)分离 柱后鲁米诺化学发光 (CL)检测方法 ,并分离测定了Cu2 + ,Co2 + ,Cr3 + ,Fe2 + ,Mn2 + 等 5种过渡金属离子。以草酸 柠檬酸混合溶液作为洗脱液 ,Luminol H2 O2 Mn + 作为化学发光检测体系 ,对过渡金属离子进行在线检测。测定的线性范围分别为 (mg·L-1) :Co2 + ,0 0 0 1～ 0 .1;Cu2 + ,0 1～ 6 ;Mn2 + ,0 0 6～ 4 ;Fe2 + ,0 0 3～ 5 ;Cr3 + ,0 0 2 5～ 1。检测限分别为 (μg·L-1) :Co2 + ,0 85 ;Cu2 + ,85 ;Mn2 + ,4 2 ;Fe2 + ,2 1;Cr3 + ,2 0。     

流动注射后化学发光法测定Ca~(2+)

实验发现Ca2+在铁氰化钾-钙黄绿素化学发光反应体系中的后化学发光反应.优化了反应条件,建立了一种利用后化学发光反应测定Ca2+的流动注射化学发光分析法.方法的线性范围为1.0×10-6～1.0×10-4 g/mL,检出限为3.0×10-7 g/mL, 相对标准偏差为1.8%(2.0×10-5 g/mL Ca2+,n=11).此法已用于自来水中Ca2+含量的测定,结果与标准方法测定值一致.     

流动注射-[Cu(HIO6)2]5-配离子化学发光法测定兽药制剂中恩诺沙星

基于恩诺沙星对 [Cu(HIO6)2]5- 配离子-H3PO4 体系化学发光信号的增敏作用,提出了流动注射-化学发光测定恩诺沙星的新方法.考察了[Cu(HIO6)2]5- 配离子的光谱特性,优化了影响化学发光强度的条件.恩诺沙星质量浓度在4.0×10-8～1.0×10-5g/mL 范围内,化学发光强度与恩诺沙星的浓度之间呈现良好的线性关系.检出限为1.54×10-8g/mL,RSD为1.2%.方法已用于兽药制荆中恩诺沙星的测定,回收率为 90.0%～112%.     

化学发光消耗型锰传感器

化学和生物发光是由化学反应产生的一种光辐射,不需要任何光源。又由于它们具有高灵敏度、宽线性范围和相对比较便宜的仪器等优点,因而在化学和生物传感器领域引起了广泛的兴趣。已用于H_2O_2、乳酸和胆固醇等多种生物活性物质的测定,但未见有金属离子传感器的报道。本文发展了一种新型的全固态模式的消耗型锰离子化学发光传感器。该传感器将除待测物外的所有化学发光反应试剂全部固定在阴离子交换树脂Amberlyst A-27上,于化学发光反应之前,将一定量化学发光试剂从固定化试剂柱上洗脱,与样品中的锰离子产生化学发光。已成功地应用于水样中痕量锰离子的测定。每个固定化试剂柱可连续使用100次以上。 1 实验部分 1.1 仪器和试剂 化学发光传感器由流动系统和检测系统两部分组成。其中流动系统主要由蠕动泵、六通阀、固定化试剂柱和流通池组成。检测系统由光电信增管、负高压、放大器和记录仪组成(图1)。     

High-performance liquid chromatography of micelle-solubilized complexes-IV Reversed-phase ion-pair chromatography of metal-3,5-diBr-PADAP-Triton X-100 complexes

The micellar solubilization complex systems of V(V), Cu(II), Zr(IV), Pd(II), Fe(III), Ni(II) and Co(II) with 3,5-diBr-PADAP and Triton X-100 have been investigated by HPLC on an ODS (5 x 250 mm) column with a ternary eluent of methanol-acetone-acetone-water containing TBA(+) and acetate buffer (pH 3.0) at 600 or 572 nm wavelength for the detection of the complexes. An HPLC-spectrophotometric method for determination of seven metal ions has been developed. The peak height calibration curves are linear up to 50-100 mu/1, metal ion concentration. The relative standard deviations for the determination of 30.0 mu/1 metal ion were 0.9-1.6% and the detection limits (S/N = 3) were 1.1-3.6 mug/1.     

Separation and determination of trace amounts of beryllium(II), aluminium(III) and chromium(III) with chromotrope 2C chelates by RP-HPLC

A reversed-phase high-performance liquid chromatographic separation and determination of beryllium(II), aluminium(III) and chromium(III) with chromotrope 2C chelates on a C18-bonded stationary phase is reported. Methanol-water (45:55 v/v) containing 6 x 10(-3)M tetra-n-butylammonium bromide (TBAB) and 2 x 10(-2)M acetate buffer solution (pH 6.0) as mobile phase and with spectrophotometric detection at 530 nm was applied. The method has high sensitivity, the detection limits being 0.2 ppb for beryllium(I), 1 ppb for aluminium(III) and 2 ppb for chromium(III). Under the optimum conditions, most other metal ions did not interfere, e.g. up to 2 mg of Hg(II), Sn(II, IV), Pb(II), Bi(III), Ag(I), Zn(II), Cd(II), Cu(II), 1.5 mg of Fe(II), Co(II), Ni(II), 1.2 mg of Ca(II), Mg(II), Sr(II), Ba(II), 1 mg of Ga(III), In(III), 0.5 mg of Fe(III), 1 mg of Ga(III), In(III), 0.5 mg of Fe(III), 0.4 mg of Th(IV), Zr(IV). The method can be applied to the simultaneous determination of trace amounts of beryllium(II), aluminium(III) and chromium(III), in water, rice, flour and human hair samples.     

Artificial neural networks for simultaneous spectrophotometric differential kinetic determination of Co(II) and V(IV)

A method for simultaneous analysis of V(IV) and Co(II) has been developed by using artificial neural network (ANN). This method is based on the difference of the chemical reaction rate of V(IV) and Co(II) with Fe(III) in the presence of chromogenic reagent, 1,10-phenanthroline. The reduced product of the reaction, Fe(II), can form a colored complex with 1,10-phenanthroline and make a visible spectrophotometric signal for indirect monitoring of the V(IV) and Co(II) concentrations. Feed forward neural networks have been trained to quantify considered metal ions in mixtures under optimum conditions. The networks were shown to be capable of correlating reduced spectral kinetic data using principal component analysis (PCA) of mixtures with individual metal ion. In this way an ANN containing three layers of nodes was trained. Sigmoidal and linear transfer functions were used in the hidden and output layers, respectively, to facilitate nonlinear calibration. Both V(IV) and Co(II) were analyzed in the concentration range of 0.1-4.0 μg ml⁻¹. The proposed method was also applied satisfactorily to the determination of considered metal ions in several synthetic and water samples.     

Determination of Metal Ions by High Performance Liquid Chromatography

The mixture of metal ions [Bi(III), Fe(III), Fe(II), Cu(II), Zn(II), Ni(II), Co(II), Pb(II), Cd(II), Mn(II)] were separated in the bonded-phase strong cation exchange column (Vydac-401 SA) and monitored at 540 nm after a postcolumn reaction with 4-(2-pyridylazo)-resorcinol (PAR). Citrate, tartrate, lactate and α-hydroxyisobutyrate buffer were used as eluent and it has been found that the elution order of some metal ions were changed with different eluents. The detection limits and the calibration curves of metal ions were also studied.     

Ion flotation behaviour of thirty-one metal ions in mixed hydrochloric/nitric acid solutions

The ion flotation of 31 metal ions in hydrochloric/nitric acid solution with the cationic surfactant cetylpyridinium chloride was investigated. A 25-ml portion of 0.27-2.87 x 10(-4)M metal ion and 1.8-6.0 x 10(-4)M cetylpyridinium chloride solution in 0.17-3.4M acid mixture ([HCl]:[HNO(3)] = 2.4:1) was subjected to flotation in a cell, 22.5 cm high and 4.0 cm in diameter, for 5 min, with nitrogen bubbles. Ir(IV), Pt(IV), Ge(IV), Sn(IV), Bi(III), Au(III), Tl(III), Pd(II) and Sn(II) were floated from solution in 95-100% yield; Ru(III), Rh(III), Ir(III), Hg(II), Ag(I) and Tl(I) were partly floated, while Cr(VI), Ti(IV), Zr(IV), Ga(III), In(III), Fe(III), Sb(III), Al(III), Mn(II), Fe(II), Co(II), Ni(II), Cu(II), Zn(II), CD(II) and Pb(II) were floated with less than 20% yield. The flotation behaviour of these metal ions in the mixed acid system was compared with that in hydrochloric acid. The flotation is more efficient in the mixed acid system.     

停流流动注射-诱导动力学光度法同时测定微量铁和锑

依据诱导反应的基本原理, 提出了一种同时测定多元素的方法; 研究了Fe(II)、Sb(III)诱导的Cr(VI)-I^-氧化还原反应体系, 并据此建立了停流-诱导动力学光度法同时测定微量铁和锑的工作条件。线性范围分别为0~1.2μg.mL^-1Fe(II)和0~2.0μg.mL^-1Sb(III); 检测限为0.012μg/mL^-1Fe(II)和0.014μg.mL^-1Sb(III)。除Ti(III)、V(IV)及As(III)外, 其余共存离子不影响测定。用本法测定了锌标准物及模拟样品中的铁和锑含量, 结果满意。     

A new chemiluminescence system for determination of cobalt

The chemiluminescence of the reaction of tartaric acid with hydrogen peroxide in the presence of Co(II) in alkaline buffer media has been examined. The maximum emission wavelength is 460 nm. The kinetic curve of the chemiluminescence system has been modelled with a computer, and the reaction conditions have been optimized. Foreign ions, such as Fe(II), Cr(III) and Mn(II), interfere when present in more than 10-fold ratio to Co(II), but several ions can be tolerated when present in higher ratios to Co(II). The concentration range of linear response is from 3.5 x 10(-9) to 2.0 x 10(-6) g/ml, and the detection limit is 4 x 10(-11) g/ml. The procedure has been satisfactorily applied to determine trace cobalt in human blood serum.     

Reversed-phase ion-pair high performance liquid chromatographic determination of Co(III)-, Ni(II)-, V(V)- and Fe(III)-2-(2-benzothiazolylazo)-5-(3-sulforpropyl)aminophenol chelates

The separation and determination of Co(III), Ni(II), V(V) and Fe(III) chelates with 2-(2-benzothiazolylazo)-5-(3-sulfopropyl)aminophenol (BTASPAP) by reversed-phase ion-pair HPLC was investigated. In the presence of the oxidant potassium iodate, BTASPAP reacts with Co(III), Ni(II), V(V) and Fe(III) to form stable, negatively charged, water-soluble chelates. The chelates were separated on a C(18) siloxane bonded phase and eluted within 7 min with acetonitrile-acetate-water (36:1:63 v/v) containing 0.2 mol 1(-1) acetic acid-sodium acetate buffer (pH 3.0) and 1.0 mmol 1(-1) tetrabutylammonium bromide. The detection limits of Co(III), Ni(II), V(V) and Fe(III) at 565 nm are 0.3, 0.8, 0.3 and 1.0 ng (signal-to-noise ratio = 2), respectively. The method was applied to the determination of Co, Ni, V and Fe in four samples of standard alloys.     

Analytical possibilities of pyridine-2-acetaldehyde benzoylhydrazone as a chromogenic reagent

With a view to the use of pyridine-2-acetaldehyde benzoylhydrazone is an analytical reagent, a study of the physical properties and fundamental solution chemistry of the complexes formed by PABH with Fe(II), Fe(III), Ni(II), Pd(II), V(V), Ti(IV), Hg(II), Mn(II), Zn(II), Bi(III), Co(II), Cu(II), Pb(II), and Ga(III) metal ions has been carried out. A critical comparison of pyridine-2-carbaldehyde and pyridine-2-acetaldehyde salicyloylhydrazones and pyridine-2-acetaldehyde benzoylhydrazone as analytical reagents is given.     

Rapid automated in-situ monitoring of total dissolved iron and total dissolved manganese in underground water by reverse-flow injection with chemiluminescence detection during the process of water treatment

Measurement of iron and manganese is very important in evaluating the quality of natural waters. We have constructed an automated Fe(II), total dissolved iron(TDI), Mn(II), and total dissolved manganese(TDM) analysis system for the quality control of underground drinking water by reverse flow injection analysis and chemiluminescence detection(rFIA-CL). The method is based on the measurement of the metal-catalyzed light emission from luminol oxidation by potassium periodate. The typical signal is a narrow peak, in which the height is proportional to light emitted and hence to the concentration of metal ions. The detection limits were 3 x 10(-6)mug ml(-1) for Fe(II) and the linear range extents up to 1.0 x 10(-4) and 5 x 10(-6)mug ml(-1) for Mn(II) cover a linear range to 1.0 x 10(-4)mug ml(-1). This method was used for automated in-situ monitoring of total dissolved iron and total dissolved manganese in underground water during water treatment.