Novel Dicyanoargentate Polymeric Membrane Sensors for Selective Determination of Cyanide Ions

The construction and general performance characteristics of three novel potentiometric PVC membrane sensors responsive to dicyanoargentate anion are described. The sensors are based on the use of magnesium(II)‐ and iron(II)‐phthalocyanines as neutral ionophores and iron(II)‐bathophenanthroline dicyanoargentate ion‐pair complex as an ion exchanger in plasticized PVC matrices. These sensors exhibit fast, stable and near‐Nernstian response (54–59 mV/decade) for the singly charged dicyanoargentate anion over the concentration range 1×10^?2–5.8×10^?6 M. Potentiometric responses of sensors based on metal phthalocyanines and iron(II)‐bathophenanthroline are stable over the pH ranges 5–7 and 5–12, respectively. The selectivity of the sensors are fairly good over most common anions. Use of the sensors for potentiometric determination of microgram quantities of cyanide ion after conversion into dicyanoargentate anions shows an average recovery of 99.5% and a mean standard deviation of ±0.5%. Determination of cyanide ions in some exhausted electroplating bath samples gives results that compare favourably well with data obtained using the solid‐state cyanide electrode.     

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。     

Potentiometric Determination of Chloride and Cyanide Ions in Nanoliter Samples with Capillary Indicating Electrodes

IntroductionIt is often necessary to determine some components in small volumes in vitro and in vivoin biology rapidly and accurately.Asthe ultramicroelectrode and the microelectrochemical cellcan be made in such a small dimension and with a high sensitivity,the electroanalytical meth-ods display powerful potentialitiesin this respect.In recentyears,the reports aboutthe deter-mination of samples in small volumes in vitro have aroused a more and more interest[1— 1 0 ] andthe greatprogresshas b…     

化学发光法测定氨磷汀研究

实验发现,铈(Ⅳ)可以氧化氨磷汀产生弱的发光,而罗丹明6G(Rh6G)能大大增强此发光,由此建立了一种化学发光法测定氨磷汀的新方法。该方法的线性范围为1.0×10-7~1.0×10-5mol/L,检出限为6.4×10-8mol/L。对1.0×10-6mol/L的氨磷汀进行11次平行测定的相对标准偏差为2.6%。该法用于氨磷汀注射液中氨磷汀含量的测定,获得满意结果。     

Didodecyldimethylammonium Bromide Bilayer Vesicle-Catalyzed and Uranine-Sensitized Chemiluminescence for Determination of Free Cyanide at Picogram Levels by Flow Injection Method

Abstract

A novel chemiluminescence system, didodecyldimethylammonium bromide-uranine-sodium hydroxide, is described for the determination of ultratraces of free cyanide by flow injection method. Organized surfactant assemblies(bilayer vesicles) incorporated with a sensitizer (uranine) permit the determination of free cyanide very selectively with a limit of determination of 1 pg (20-μ1 sample injection). Sulfide, the strongest CL inducer after free cyanide, provides a signal 0.1 % of that for free cyanide.     

Silver Electrodeposition from Cyanide Solutions: Effect of Lead Ions

Effect of lead hydroxy compounds on the process of electrodeposition of silver from cyanide electrolytes is studied on an electrode whose surface is renewed in solution by cutting off a thin layer of metal. This permitted to perform the study on both the freshly renewed electrode and at controlled values of the time of the electrode contact with solution t. Shown is that on the freshly renewed electrode (t<1 s) the presence in the solution of lead ions in concentrations c ₁ on the order of 10^–5 M leads to the process depolarization only in the initial portion of a polarization curve. With c ₁ increased to 10^–4 M the effect of depolarization extends on the entire polarization curve. Keeping the electrode in solution after the renewal of the metal surface magnifies depolarization, and the greater the concentration c ₁, the shorter the time period t required to achieve the same effect. These regularities are attributed to catalytic influence of lead adatoms, whose surface concentration depends on c ₁ and t, as well as on the intensity of their incorporation in the silver deposit.     

Kinetic Parameters of Gold Dissolution in Cyanide Solutions: The Effect of Complex Cyanide Ions of Mercury

The kinetics of the gold dissolution in cyanide solutions is studied at constant values of the coverage () of the gold surface by mercury atoms. The constancy of is ensured by maintaining an identical value of the duration (t) of contact of electrode with solution (after renewing its surface by cutting off a thin surface layer of metal) at a potential of –1.3 V, at which the discharge of mercury ions is limited by their diffusion to the electrode. At t = const kinetic dependences of the gold dissolution process correspond to the Tafel equation. Effective values of exchange current i ₀, transfer coefficient , and reaction order by cyanide ions P are determined. With increasing value of their magnitude increases from values 10^–5 A cm^–2, 0.1, and 0.17 that are characteristic of purely cyanide solutions (composition 0.1 M KCN, 0.1 M KOH, and 0.01 M KAu(CN)₂) to i ₀ 2 × 10^–4 A cm^–2, = 0.46, and P 1 at t = 270 s. These results are compared with the data obtained earlier during similar investigations in solutions containing thallium, lead, and bismuth. Common and individual features in the behavior of mercury-containing electrolytes are revealed. It is shown that the possible mechanism of the acceleration of the gold dissolution process in the presence of catalytically active atoms, which had been proposed in these works, may be used also for explaining the action of mercury atoms on this process.     

Flow-injection Chemiluminescence Determination of Catecholamines

Catecholaminesarenowwidelyusedinthetreatmentofbronchialasthma,hypertension,heartfailureassociatedwithorganicheartdiseases,andcardiacsurgery'.Thedeterminationofcatacholaminesinpharmaceuticalpreparationshasappearedespeciallyattractive.Chemiluminescence(CL)hasbeenexploitedinanumberofanalyticalapplicationsowingtoitsgreatsensitivity.SomeCLreactionshavenotfoundmanyapplicationsduetotheinstabilityofoxidationreagentssuchashypochlorite.WeproposedthatunstablereagentsrequiredforCLreactioncanbegenerated…     

流动注射-抑制化学发光法测定克百威

基于在碱性介质中,克百威抑制鲁米诺-过氧化氢-叶绿素铜钠体系的化学发光,提出了流动注射-抑制化学发光法测定克百威含量的方法。试验结果表明:叶绿素铜钠对克百威荧光猝灭过程是静态猝灭过程,叶绿素铜钠与克百威结合形成物质的量比为1比1的稳定配合物,平衡常数(K0)为3.41×105L.mol-1(25℃),结合距离(r)为0.39 nm。克百威质量浓度在0.08～2.00 mg.L-1范围内与其发光强度呈线性关系,方法检出限(3σ/k)为0.03 mg.L-1。此法用于克百威杀虫剂样品的分析,测得方法的平均加标回收率为101.5%。     

Flow-Injection Chemiluminescence Determination of Fluoroquinolones

ABSTRACT

A new flow-injection CL method was developed for the determination of fluoroquinolones including ofloxacin, norfloxacin, ciprofloxacin and lomefloxacin in pharmaceutical preparations, based on the chemiluminescence reaction of sulphite with cerium(IV) sensitized by these compounds. The linear ranges are 0.04 to 4.0 μg ml^?1 for ofloxacin and 0.4 to 40.0 μg ml^?1 for norfloxacin, ciprofloxacin and lomefloxacin, respectively. The detection limits are 0.016 μg ml^?1 for ofloxacin and 0.16 μg ml ^?1 for norfloxacin, ciprofloxacin and lomefloxacin, respectively. The relative standard deviations (RSD) are 2.1 to 2.6% (n=10) for these fluoroquinolones. The analytical procedure has been applied to the determination of the fluoroquinolones in pharmaceutical commercial formulations. The results are in agreement with those obtained by the official methods.     

Chemiluminescence Determination of Monopersulfuric Acid

A procedure for the chemiluminescence determination of trace amounts of monopersulfuric acid was developed. The procedure is based on the oxidation of luminol with monopersulfuric acid in alkaline solutions. The detection limit is 6 ng/mL.     

一种无氰化物测定血红蛋白的分光光度法

在pH 2.3～5.2的酸度条件下,红色的氯磺酚S能与血红蛋白作用,生成蓝色离子缔合物,其最大吸收波长为637 nm,摩尔吸收系数(为2.8×105L·mol-1·cm-1;最小吸收波长为560 nm,摩尔吸收系数(为3.5×105 L·mol-1·cm-1,线性范围均为0～100 mg/L.优化了反应条件,测定了主要分析参数并探讨了初步反应机理.该法克服了使用KCN剧毒和高白细胞、高球蛋白血症干扰的弱点.用于临床人血液中血红蛋白含量的测定,结果满意.     

Sulfonium Boranes for the Selective Capture of Cyanide Ions in Water

Going fishing ! The sulfonium borane [ 1 ]⁺ complexes cyanide in pure water at the maximum allowable concentration of 50 ppb recommended by the European Union. The high cyanide ion affinity displayed by this compound arises from favorable Coulombic effects augmented by a direct bonding interaction between the cyano and sulfonio groups.

     

Simultaneous Determination of Selenocyanate and Thiocyanate Ions in the Presence of Cyanide by Oxidation with bis (Trifluoroacetoxy) iodobenzene

Abstract

An investigation of the use of potentiometric titrations of selenocyanate and thiocyanate aqueous solutions, in the presence of cyanide ions, with bis (trifluoroacetoxy) iodobenzene in acetonitrile and then the gravimetric determination of the products of the reactions, elemental selenium and sulphate ions, has been carried out.

Selenocyanates are first oxidized to selenium and then thiocyanates are oxidized to sulphate ions. Break point curves are identified. The rose-pink precipitate is filtered and the clear filtrate is warmed on a hot plate for evaporation of acetonitrile. A solution of barium chloride is added to the hot solution in order to precipitate the sulphate ions.     

化学发光法测定三氯生

1引言三氯生(2,4,4′-三氯-2-羟基二苯醚)是常用消毒剂,广泛应用于日化产品中。三氯生的大量应用,对河流、湖泊等带来的污染问题受到关注。另外,三氯生合成过程中还可能产生有害的二噁英类物质。定量测定日化产品中三氯生的方法报道较少,有电化学法、高效液相色谱法、紫外分光光度法、毛细管区带电泳法等,未见有化学发光法测定三氯生的报道。研究表明,在荧光素存在下三氯生溶液经光照后,可与氧化剂反应产生化学发光。曲拉通X-100可极大地增强化学发光信号。据此建立了三氯生的化学发光测定新方法。2实验部分2.1仪器与试剂IFFM-D型流动注…     

葡萄糖的流动注射化学发光法测定

葡萄糖在浓盐酸中降解后,其产物羟甲糖醛可与Ce(Ⅵ）反应产生化学发光,罗丹明6G对该反应有较强的增敏作用。据此,建立了流动注射化学发光测定葡萄糖的新方法。该法的线性范围为0．2－90mg/L,检出限为0．08mg/L,相对标准偏差(n=11,ρ=10.0mg/L）为1．0％。方法用于血清中葡萄糖含量的测定,结果与标准方法一致,回收率为96％－106％。     

雌二醇的流动注射阻抑化学发光法测定

基于碱性介质中雌二醇对N-溴代丁二酰亚胺-钙黄绿素化学发光体系的阻抑作用,建立了雌二醇的流动注射化学发光分析新方法,优化了其分析条件,并初步探讨了该化学发光反应的机理。该方法测定雌二醇的线性范围为0.02~0.1、0.1~8.0 mg/L,检出限为0.008 5 mg/L。对0.1 mg/L的雌二醇标准溶液进行11次平行测定,相对标准偏差为1.2%。将该法用于注射液中雌二醇的测定,结果满意。     

能量转移化学发光法测定洛美沙星

洛美沙星(LFLX)在紫外光照射下易发生光化学降解反应,光解产物(ILFLX)与Tb3 形成的配合物对Ce(Ⅳ)-SO32-化学发光体系有较强的增敏作用,与光解前体系的化学发光强度相比,增大近5倍。据此,建立了光化学-能量转移化学发光法测定LFLX的新方法。该方法的线性范围为8.0×10-10～2.0×10-5mol/L;检出限为2.5×10-10mol/L;相对标准偏差(n=11,Cs=5.0×10-8mol/L)为2.8%。利用该法测定了生物样品中LFLX的含量,结果满意。并在实验的基础上,对其光化学增敏反应机理进行了合理的推测。     

测定核黄素的化学发光新方法

研究了核黄素的化学发光性质，建立了一种测定核黄素的化学发光新方法，并应用于实际样品中核黄素的测定，与文献相比，本方法无需避光，而且分析体系和样品处理简单；干扰小，牛血清白蛋白、抗坏血酸、天冬氨酸等８种生物有机物质和 Ｃｕ（Ⅱ）、Ｚｎ（Ⅱ）、Ｆｅ（Ⅲ）等１５种常见金属离子的允许量较大；核黄素溶液浓度在０． １０～５０ ｍｇ／Ｌ范围内，与化学发光强度成正比，方法线性范围宽；测定１．０ｍｇ／Ｌ核黄素溶液１２次，求得相对标准偏差为２．９％，方法精密度高；方法的检测限为０．０７５ ｍｇ／Ｌ，灵敏度高。