固绿FCF共振瑞利散射法测定食品中的Al(Ⅲ)

在酸性Tris-HCl缓冲介质中,溴化十六烷基三甲基铵(CTMAB)增敏固绿FCF,与Al(Ⅲ)结合生成三元络合物使共振瑞利散射(RRS)显著增强并产生新的RRS光谱,其最大共振瑞利散射峰位于330 nm,RRS增强程度(△IRRS)与Al(Ⅲ)的质量浓度在0.02～0.49 mg/L成正比,方法有很高的灵敏度,检出限是0.0096 mg/L.方法用于面制食品中Al(Ⅲ)的测定,结果满意.     

Effect of Cationic Micelles on the Kinetics of Interaction of [Cr（Ⅲ）-Gly-Gly]^2＋ with Ninhydrin

The effect of cationic micelles of cetyltrimethylammonium bromide (CTAB) on the interaction of chromium dipeptide complex ([Cr(Ⅲ)-Gly-Gly]2 ) with ninhydrin under varying conditions has been investigated. The rates of the reaction were determined in both water and surfactant micelles in the absence and presence of various organic and inorganic salts at 70 ℃ and pH 5.0. The reaction followed first- and fractional-order kinetics with respect to [Cr(Ⅲ)- Gly-Gly2 ] and [ninhydrin]. Increase in the total concentration of CTAB from 0 to 40×10-3 mol·dm-3 resulted in an increase in the pseudo-first-order rate constant (kψ) by a factor of ca 3. Quantitative kinetic analysis of kψ-[CTAB] data was performed on the basis of the pseudo-phase model of the micelles. As added salts induce structural changes in micellar systems that may modify the substrate-surfactant interactions, the effect of some inorganic (NaBr, NaCl, Na2SO4) and organic (NaBenz, NaSal, NaTos) salts on the rate was also explored. It was found that the tightly bound counterions (derived from organic salts) were the most effective.     

As（Ⅲ）和As（V）与牛血清白蛋白的结合平衡研究

在模拟动物体生理条件下,研究As（Ⅲ）和As（V）与牛血清白蛋白（BSA）的相互作用．用氢化物发生．超低温捕集塬子吸收分光光度法测定平衡透析后As（Ⅲ）或As（V）的浓度,用Scatchard方法分别处理实验数据,确定结合部位和结合常数．发现当As（Ⅲ）浓度（CAs（Ⅲ）：CBsA≤1：1）较低时,在BSA中有1．3个强结合部位,结合常数为1．7×10^6,为强结合;当As（Ⅲ）的浓度（cAs（Ⅲ）：cBSA≥2：1）较高时,没有明显的特征结合点,表现为弱结合．而As（V）与BSA无任何结合作用．     

Binding studies of DNA with Co(Ⅲ) coordination compound

The binding of Co(bpy)2dppz3+ to calf thymus DNA was investigated by using absorption and emission spectroscopy,DNA melting techniques,cyclic voltammetry,viscosity and electro-phoresis measurements,where bpy is 2,2'-bipyridyl,dppz is dipyrido[3,2-o:2',3'-c] phenazine.The binding compound shows absorption hypochromicity,fluorescence enhancement,and increasing of DNA melting temperature and the specific viscosity.CV measurement shows the shifts in oxidation-reduction potential and change in peak current with addition of DNA.The compound is also shown to be more efficient photosensitisers for strand breaks in plasmid DNA.     

丙酮酸在悬汞电极上的电化学行为及其与Al(Ⅲ)的相互作用

研究了酸性、中性、碱性范围内丙酮酸在悬汞电极上的电化学行为，对实验条件进行了优化，在最佳条件下丙酮酸的还原峰电流和浓度有良好的线性关系。同时在不同pH值条件下研究了Al(Ⅲ)和丙酮酸的相互作用，结果表明，不同pH值范围内Al(Ⅲ)和丙酮酸的相互作用均为弱作用，弱作用强度为酸性>碱性>中性。这种作用强度的差别可能来自于不同条件下Al(Ⅲ)的存在形态不同。     

对乙酰氨基酚在Fe（Ⅲ）／草酸盐体系中的光降解

药品和个人护理用品(Pharmaceuticals and Personal Care Products,简称PPCPs)作为潜在环境污染物,在近几年成为新的环境热点问题[1,2].对乙酰氨基酚(APAP)作为一种典型的药品和个人护理用品被用作阿司匹林的替代物,主要起到减轻疼痛的作用.     

用MIBK萃取Rh（Ⅲ）的硫氰酸配合物

研究了在盐酸介质中硫氰酸盐存在下Rh(Ⅲ)的萃取.Rh(Ⅲ)在0.5～1.0mol·L~(-1)盐酸介质中与1×10~3倍以上的硫氰酸盐于沸水浴中加热60min即可形成硫氰酸铑(Ⅲ)配合物.此配合物可在较宽酸度范围(0.5～4mol·L~(-1)盐酸)被MIBK(甲基异丁基酮)定量萃取.通过吸收光谱试验证实有[Rh(SCN)_xCl_(6-x)]~(3-)(x>3)配合物生成.与质子化的MIBK生成(钅羊)盐而被萃取.     

Al(Ⅲ)-槲皮素配合物的光谱分析

采用UV和IR分析手段,研究在甲醇溶剂酸性和中性条件下,槲皮素(3,3,′4,′5,7-五羟基黄酮)与A l(Ⅲ)形成配合物的构型、反应配比及在配位反应过程中配体分子中各个配位点的配位能力大小及优先配位的顺序。实验结果表明:在酸性介质中,槲皮素与A l(Ⅲ)所形成配合物的反应配比为A l(Ⅲ)∶Q=1∶1,其配位点为3-羟基-4-酮,配位构型中心为A l(Ⅲ)与一个槲皮素分子形成五元环四配位的配合物。在中性介质中发生两步配位反应,第一步配位反应发生在3-羟基-4-酮配位点其反应配比为1∶2,配位构型为中心A l(Ⅲ)与两个槲皮素分子形成两个五元环之间四配位的配合物;第二步配位反应发生在3,′4′-二羟基配位点其反应配比为2∶1,两个A l(Ⅲ)离子分别在上述两个配位点与一个槲皮素分子形成五元环四配位构型的配合物。     

以氯化钠-碘化钾-丙醇体系萃取分离金（Ⅲ）

试验在氯化钠存在下,碘化钾-丙醇体系萃取分离以AuI-4络阴离子状态存在的金(Ⅲ)的最佳条件,结果表明:当溶液中碘化钾、氯化钠和丙醇的浓度分别为每升中0.3 g,200 g和300 mL,且溶液的酸度为pH 3.5时,能使AuI-4定量萃取,即在总体积为10 mL的溶液中,含碘化钾3 mg,氯化钠2 g和丙醇3 mL.萃取分离50 μg金(Ⅲ)时,1 mg铁(Ⅱ)、镍(Ⅱ)、锰(Ⅱ)、铝(Ⅲ)、锌(Ⅱ)、钴(Ⅱ)、镓(Ⅲ)等离子基本不被萃取,而与上述离子分离,金(Ⅲ)的萃取率达99.7%以上.     

Studies on the effects of Al(III) on the lactate dehydrogenase activity by differential pulse voltammetry

In this paper, differential-pulse voltammetry (DPV) was applied to study the effects of aluminum (Al(III)) on the lactate dehydrogenase (LDH) activity, and ν_max in the enzyme promoting catalytic reaction of “” by monitoring DPV reduction current of NAD⁺. The changes of Al's influence on the LDH activities caused by the concentration of LDH, pH, temperature as well as Al speciation including Al hydroxide (Al-OH), Al fluoride (Al-F) and organically complexing Al (Al-Org) compounds have been investigated. The results showed that the effects of Al on the LDH activity exhibited two kinds of behaviors under different conditions, i.e. inhibitory effects or slightly increased LDH activity at low concentrations and inhibited at high concentrations. To analyze the values of and ν_max of LDH reaction system in the absence and presence of 0.04 mmol/L Al(III), it was found that the types of the inhibition of Al(III) varied with experimental conditions. The comparisons of effects of Al(III) with Pb(II), Cd(II) and Cr(III) on the LDH activities were also inspected.     

Differential pulse voltammetric determination of arsenic(III,V) and antimony (III,V) in glasses

Summary Analytical methods based on differential pulse voltammetry (DPV) have been described for the determination of total As, As(III), As(V), total Sb and Sb(III) as trace to minor constituents in complex glasses. For total As, the sample is decomposed with HF-H₂SO₄-KMnO₄. The As(V) is chemically reduced to As (III) by hypophosphite and a DPV scan is carried out at the dropping mercury electrode from –0.2 to –0.7 Vvs. SCE (E _p –0.41V). As(V) is determined by decomposing the sample in HF-H₂SO₄ and volatilizing the As(III) as AsF₃. The chemical reduction of As(V) and the DPV scan are then applied. If the glass can be decomposed with cold HF, the As(III) present in the glass can be determined by applying the DPV scan after cold sample-dissolution. For Sb(III), the sample is decomposed with HF-H₂SO₄, diluted, and adjusted to 1M in HCl. A DPV scan is conducted from –0.03 to –0.5 V (E _p –0.15 V). Sb(V) is not reduced in the 1M HCl supporting electrolyte. Total Sb is determined by using an aliquot of the sample solution adjusted to 6M in HCl. The DPV sweep is carried out from –0.5 to –0.1 V [E _p for Sb(V) and Sb(III) is –0.30 V]. The methods have been applied to a wide range of glass compositions and the results compared with values obtained by spectrophotometry and coulometric titration.

---

Bestimmung von Arsen(III, V) und Antimon(III, V) in Gläsern mit Hilfe der Differential-Puls-Voltammetrie

Zusammenfassung Analytische Methoden auf der Grundlage der Differential-Puls-Voltammetrie (DPV) für die Bestimmung des gesamten Arsens, As(III), As(V), des gesamten Antimons und Sb(III) als Spuren in komplexen Gläsern wurden beschrieben. Zwecks Bestimmung des Gesamt-As wird die Probe mit Flußsäure +Schwefelsäure + Permanganat aufgeschlossen. As(V) wird mit Hypophosphit reduziert und die DPV wird an einer Quecksilber-Tropfelektrode zwischen –0,2 und –0,7V gegen eine ges. Kalomelelektrode (E _p =–0,41V) durchgeführt. Zur Bestimmung von As(V) wird die Probe mit HF-H₂SO₄ unter Verflüchtigung des As(III) als AsF₃ aufgeschlossen. Dann erfolgt die Reduktion des As(V) und die DPV. Wenn sich das Glas mit kalter HF lösen läßt, wird anwesendes As(III) mittels DPV in dieser Lösung bestimmt. Zur Bestimmung des Sb(III) wird die Probe mit HF-H₂SO₄ zersetzt, verdünnt und bis zur 1-Molarität mit HCl versetzt. Dann wird mit DPV zwischen –0,03 und –0,5V gemessen (E _p =–0,15V). Sb(V) wird in 1M salzsaurer Lösung nicht reduziert. Das Gesamt-Sb wird in einem Aliquot der Probelösung bestimmt, das dazu mit HCl bis zur 6fachen Molarität versetzt wird. Der DPV-Bereich wird von –0,5 bis –0,1 V ausgenützt (E _p f:ur Sb(V) und Sb(III) ist –0,30 V). Das Verfahren wurde für Gläser verschiedenster Zusammensetzung angewendet. Die Ergebnisse wurden mit den Resultaten der Spektrophotometrie und der coulometrischen Titration verglichen.

---

---

Presented at the 8th International Microchemical Symposium, Graz, August 25–30, 1980.     

Differential pulse voltammetric studies of ethidium bromide binding to DNA

The interaction of ethidium bromide (EtBr) with calf thymus DNA is investigated electrochemically with the use of differential pulse voltammetry (DPV) at two different ionic strengths of a solution (0.154 M and 0.02 M [Na+], pH 7.0). It is revealed that EtBr binds with DNA in more than one way. The appropriate values of constants (K) and number site sizes (n) of EtBr binding to DNA are determined. The values of binding constants are equal to 1.9 x 10(6) and 5.6 x 10(5) M(-1), and number site sizes to 9 and 3.6 for strong interactions at ionic strengths of solutions 0.02 and 0.154 M Na+ at 28 degrees C, respectively. For a weaker interaction, these parameters are equal to 7 x 10(4) and 8 x 10(4) M(-1) and 1.5 and 1 at the mentioned ionic strengths of solutions, respectively. Thus, EtBr interacts with DNA in more than one way--intercalative and electrostatic at low ionic strength, and semi-intercalative and electrostatic at a higher strength of the solution. These results are in good accordance with the ones obtained by spectroscopic (absorption and fluorimetric) methods.     

Differential pulse voltammetric determination of famotidine

A differential pulse voltammetric method for the determination of famotidine in pharmaceutical preparations is described. The method is based on electrochemical oxidation of famotidine at a glassy carbon or platinum electrode. The proposed method shows good reproducibility, and sample preparation is simple.     

Differential pulse anodic stripping voltammetric determination of ziram (a dithiocarbamate fungicide)

A d.c. polarographic technique has been used previously for the determination of the pesticide, ziram, in aqueous samples, this paper reports differential pulse anodic stripping voltammetric determination of ziram zinc in rice samples using a static mercury drop electrode. The procedure developed distinguishes inorganic zinc and ziram zinc in sodium acetate-sodium chloride media. The procedure developed is suitable for the determination of concentrations as low as 10 ppb of ziram with a precision of 2.1% for five successive determinations of 150 ppb of ziram.     

Differential pulse voltammetric assay of lercanidipine in tablets

Lercanidipine in ethanol-0.04M Britton-Robinson buffer (20 + 80) gives an irreversible anodic response on a glassy carbon electrode in a broad pH range (2-12) that depends on pH. This signal can be attributed to oxidation of the 1,4-dihydropyridine ring to give the corresponding pyridine derivative. For analytical purposes, differential pulse voltammetry at pH 4 was selected. Under these conditions, good values of both within- and interday reproducibility were obtained, with coefficient of variation (CV) values of 1.56 and 1.70%, respectively, for 10 successive runs. For quantitation, the calibration curve method was used for lercanidipine concentrations ranging from 1 x 10(-5) to 1 x 10(-4) M. The detection and quantitation limits were 1.39 x 10(-5) and 1.49 x 10(-5), respectively. A liquid chromatographic method with electrochemical detection was used for comparison. The voltammetric method showed good selectivity with respect to both excipients and degradation products. The recovery study exhibited a CV of 0.94% and an average recovery of 98.3%, and it was not necessary to treat the sample before the analysis. The method was successfully applied to the individual tablet assay of lercanidipine in commercial tablets.     

Polarographic and voltammetric studies of tetrabutylammonium hexacyanoferrate(III) and tetrabutylammonium hexacyanomanganate(III) in non-aqueous solvents

Tetrabutylammonium hexacyanomanganate(III) [(bu₄N)₃Mn(CN)₆] has been studied by polarography and cyclic voltammetry in formamide, methanol, ethanol, N-methylformamide, dichloromethane, dimethylsulfoxide, acetonitrile, N,N-dimethylformamide, propylenecarbonate, butyrolactone, N-methylthiopyrrolidone(2), N,N-dimethylthioformamide, 1.2-dichloroethane, N-methylpyrrolidone(2) and tetramethylenesulfone. Similar studies have been carried out for tetrabutylammonium hexacyanoferrate(III) [(bu₄N)₃ Fe(CN)₆] in the solvents formamide, N-methylformamide, dichloromethane, butyrolactone, N-methylthiopyrrolidone(2) and tetramethylenesulfone. The half-wave potentials of the reductions (bu₄N)₃Mn(CN)₆ to (bu₄N)₄Mn(CN)₆ and (bu₄N)₃Fe(CN)₆ to (bu₄N)₄Fe(CN)₆ versus bisbiphenylchromium(I)/bisbiphenylchromium(0) as a reference redox system were found to vary with the nature of the solvent. Comparison with data previously obtained for the respective tetraethylammonium salts of hexacyanoferrate(III) and hexacyanomanganate(III) have shown that the redox behaviour of these compounds is influenced by both the solvent and the tetraalkylammonium ions. Correlations exist between the half-wave potentials of (bu₄N)₃Mn(CN)₆ and (bu₄N)₃Fe(CN)₆ and both the acceptor number of the solvents and the free enthalpies of transfer of the chloride ion. The results are discussed in the concept of donor-acceptor interactions.     

Differential scanning calorimetry studies on aged iron(III)-chromium(III)-hydroxide coprecipitates

DSC measurements in air from 20 to 800° are reported on aged iron(III)-chromium(III) coprecipitated hydroxides (with Fe³⁺Cr³⁺ wt% ratios of 91, 73, 11, 37 and 19). A comparison of the DSC profiles of aged coprecipitates with the thermal behaviour of freshly precipitated and well characterized samples provided information on the modification occurring in the structure and reactivity of the coprecipitates on prolonged aging.

---

Zusammenfassung Es werden DSC-Messungen an gealterten kogefällten Eisen(III)Chrom(III)-hydroxiden (mit Fe³⁺Cr³⁺ Gewichtsanteilen von 91, 73, 11, 37 und 19) im Temperaturbereich von 20 bis 800° beschrieben. Ein Vergleich der DSC-Profile von gealterten Kofällungen mit dem thermischen Verhalten frisch gefällter und gut definierbarer Proben lieferte Informationen über die Veränderungen in Struktur und Reaktivität der Koniederschläge bei längerem Altern.

---

---

Dedicated to Professor Wahid U. Malik, Founder-President, Indian Council of Chemists, India, with profound regards and fond memories of his youthful enthusiasm and ceaseless and pioneering efforts towards the development of chemical education and research activities at the University of Roorkee, Roorkee, India, on the occasion of his 70th birthday.

---

Paper presented at the World Conference on Thermal Analysis, Capri (Italy), 1989.

---

We thank Professor J. Pescia, Dr.G. Ablart and N. Favillier of Laboratoire de Magnétisme et d'Electronique Quantique for their interest in this work. A. C. Vajpei expresses his gratefulness to C.N.R.S. and C.N.O.U.S., Paris, for financial support of this work.     

Differential pulse voltammetric enzyme-linked immunoassay for the determination of Helicobacter pylori specific immunoglobulin G (IgG) antibody

A differential pulse voltammetric enzyme-linked immunoassay for the determination of helicobacter pylori (H. pylori) specific IgG antibody in human serum has been developed. The method is based on coupling the oxidation reaction of 3,3',5,5'-tetramethylbenzidine (TMB)-H(2)O(2) that is catalysed by horseradish peroxidase-IgG(HRP-IgG) conjugate with the electro-reduction of the enzymatic product to measure the activity of HRP-IgG. The latter reaction exhibits a sensitive differential pulse voltammetric response at 0.1 V (versus Ag AgCl ) in pH 4.0 acetate buffer solution. So, the H. pylori specific IgG antibody could be detected. The detection limit of present method for H. pylori specific IgG antibody was 1.0 units ml(-1), which was about seven times lower than that obtained by traditional spectrophotometric ELISA procedure.