Analytical study of a cadmium ion-selective ceramic membrane electrode

Summary A cadmium ion-selective membrane electrode has been developed by applying a hot-pressing method. The membrane contains cadmium sulphide, silver sulphide, and copper(I)-sulphide.The best response was obtained with a membrane containing less than 30% of copper(I) sulphide and more than 5% of cadmium sulphide. The Nernstian slope was secured over an activity range of 10^–1 to 10^–6 M, and potentiometric analysis could be carried out over a concentration range of 10^–1-10^–7 M. The potentials were maintained at constant values over more than 6 months. Also, the potentials satisfied the Nernst's factor 2.303 RT/2F at the temperature range between 0 and 95°C. Among the common ions, silver, copper(II), iron(III), mercury(II), sulphide, and iodide ions interfered seriously. However, about 10–100 times of lead and bromide ions and more than 1000 times of alkali metal, alkaline earth metal, zinc, aluminium, nickel, cobalt, manganese(II), perchlorate, and nitrate ions did not interfere at all.

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Analytische Untersuchung einer cadmiumionenselektiven keramischen Membranelektrode

Zusammenfassung Die Membran wurde durch Pressen von Cd-, Ag und Cu(I)-sulfid bei 200–500°C und 3–7 t/cm² hergestellt. Die beste Ansprechempfindlichkeit ergab sich bei einem Gehalt von <30% Cu₂S und >5% CdS. Die Nernstsche Gleichung war gültig im Bereich von 10^–1–10^–6 M, der analytische Bereich war 10^–1–10^–7 M. Die Potentiale konnten mehr als 6 Monate auf einem konstanten Wert gehalten werden. Sie entsprachen dem Nernstschen Faktor, 2,303·R·T/2 F, im Temperaturbereich von 0–95°C. Erhebliche Störungen werden durch Ag⁺-, Cu²⁺-, Fe³⁺-, Hg²⁺-, S^2– und J^–-Ionen verursacht. Jedoch verursachen etwa 10–100fache Mengen von Pb²⁺- und Br^–-Ionen sowie mehr als 1000fache Mengen von Alkali-, Erdalkali-, Zn²⁺-, Al³⁺-, Ni²⁺-, Co²⁺-, Mn²⁺-, ClO₄ ^–- und NO₃ ^–-Ionen keine Störungen.

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The authors thank Dr. S. Kisaka, Dr. K. Sugihara, Dr. S. Hayakawa and Dr. S. Mori for their encouragement in this work.     

Analytical use of neutron-capture gamma-rays

Certain elements which are not possible to detect with conventional neutron activation analysis can be measured using thermal neutron-capture gamma-ray analysis. The use of a curved neutron guide at the High Flux Reactor, Grenoble, with a thermal neutron flux of 1.5·10¹⁰n·cm⁻²·sec⁻¹ and the advantage of a low-background counting system (Ge(Li) detector) far from the reactor core are described. Experimental detection limits of a number of elements are given for the low-energy and the high-energy regions. Some applications of the capture gamma-ray method in the whole energy range are studied and are briefly discussed.     

Analytical use of immobilized glucose oxidase

With the aim of immobilizing glucose oxidase (GO) for routine determination of glucose, a covalent bond immobilization method on titanium (IV) chloride activated silica supports was used (1). Several parameters were studied in order to optimize the residual activity upon immobilization and during operation. The immobilized enzyme can be reutilized at 25°C for several h a day alternating with storage (4°C) for at least 3,300 h.     

Analytical use of proton-induced X-ray emission

Proton-induced X-ray emission, PIXE, is capable of simultaneous quantitative determination of 10–15 elements. An introduction to the physical properties of the method is given and detection limits are shown for a routine analysis of a thin aerosol sample. Examples of applications to both thick and thin samples are presented. Human tooth dentine is analysed for lead, with simple sample preparation, indicating lead values of a few ppm for Swedish children. Quantitative analyses of several other elements are obtained simultaneously. Cascade impactors are used for sampling aerosols in work environment during welding operations giving information of size distribution and concentrations of the elements present. The aerosol is dominated by particle sizes between 0.5 and 2 μm as measured by the impactor, but the size distributions are different for different elements and welding techniques and depend on the distance from the welding source. The relative abundance of the elements found in the aerosol indicates the presence of fractionation mechanisms.     

Analytical use of alpha-source induced gamma-ray emission

Summary A non-destructive multi-element method based on nuclear reactions and Coulomb excitation induced by alpha-sources and the measurement of prompt gamma-rays is described. The method is suitable for light and medium Z elements and is particularly sensitive to light elements. The experimental set-up necessary for the prompt measurements is quite simple. With 0.34 mCi ²⁴¹Am source, the sensitivity of the method is discussed for the light elements Li, Be, F and Na. The influence of sample size, air pressure etc. on the thick target yield has been investigated. Monte-Carlo calculations have been performed to study the modification of the isotropic behaviour of the alpha-source due to the protective covering and to calculate the average energy loss. The lithium determination in some minerals has been carried out.

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Analytische Anwendung der -induziertcn -Emission

Zusammenfassung Eine zerstörungsfreie Multielement-methode, die auf Kernreaktionen und Coulombanregung induziert durch -Quellen beruht, sowie die Messung prompter -Strahlung werden beschrieben. Die Methode eignet sich für leichte und mittelschwere Elemente und ist besonders empfindlich bei leichten Elementen. Der für Promptmessungen notwendige experimentelle Aufbau ist recht einfach. Die Empfindlichkeit der Methode bei Benutzung eines 0,34 mCi starken ²⁴¹Am-Präparats wird für die leichten Elemente Li, Be, F und Na diskutiert. Der Einfluß von Probengröße, Luftdruck usw. auf die Ausbeute eines dicken Targets wurde untersucht. Monte-Carlo-Rechnungen wurden ausgeführt, um die Modifizierung der isotropen Abstrahlung der Quelle durch deren Schutzabdeckung zu studieren und um den mittleren Energieverlust zu erhalten. Eine Li-Bestimmung in einigen Mineralen wurde durchgeführt.

     

Analytical utility of coupled transport across a supported liquid membrane Selective preconcentration of zinc

A liquid membrane comprising 5-10% bis(2,4,4-trimethylpentyl)phosphinic acid in dodecane that is supported between an aqueous sample at pH 4.7-6.0 and a 0.1M HCl receiver results in uphill transport of Zn(II) from the sample into the receiver. With 2 ml of receiver, a 5 cm(2) membrane and 60 min dialysis time, Zn(II) is preconcentrated by a factor of ca. 13 when the initial concentration in the sample is in the range 1.5 x 10(-7)-1.5 x 10(-4)M. The enrichment factor is directly proportional to time up to 30 min since the transport rate of Zn(II) across the membrane is constant over this period. At longer times the flux is slowed as the system begins to approach equilibrium. The presence of other metals such as Cu(II), Co(II), Ni(II), Cd(II), Pb(II) and Fe(II) does not change the enrichment factor for Zn(II), even when the interferent is at a concentration high enough for the rate of transport (nmole/min) of the interferent and Zn(II) to be about the same. The flux of Zn(II) was about 40 times that of Cu(II) and 100 times that of Co(II) when their concentrations in the sample were equal. The other metal ions examined are not significantly transported.     

Analytical applications of membrane extraction in chromatography and electrophoresis

An overview of the analytical applications of membrane-based systems for sample enrichment in chromatography and capillary electrophoresis is presented. A brief introduction to the different types of membranes and the main forces related to the transport through them is also given.     

Molecularly imprinted sol-gel nanotubes membrane for biochemical separations

In this study, we report a simple procedure for applying molecular imprinting functional groups to the inner surfaces of the template-synthesized sol-gel nanotubes for chemical separation of estrone. The silica nanotubes were synthesized within the pores of nanopore alumina template membranes using a sol-gel method by simultaneous hydrolysis of a silica monomer-imprinted molecule complex and tetraethoxysilane (TEOS). A covalent imprinting strategy was employed by generating a sacrificial spacer through the reaction of the isocyanate group of 3-(triethoxysilyl)propyl isocyanate and a phenol moiety of estrone to form a thermally cleavable urethane bond. This allowed us to remove the imprinted estrone by simple thermal reaction and to simultaneously introduce functional groups into the cavity formed by the silica nanotubes. Experiments indicated that estrone could be bound selectively by such an approach and have a binding affinity of 864 +/- 137 (n = 3).     

Analytical possibilities of microelectrode use for stripping voltammetry

The analytical utility of microelectrodes for stripping voltammetry is discussed from several points of view. The application of microelectrodes for microanalysis is demonstrated using a novel capillary flow injection system. Heavy metals at g l^–1 concentrations have been determined in l-samples. The influence of electrode size and convection during the deposition period of anodic stripping voltammetry on the reproducibility of trace metal determination was studied for various types of electrodes. In the case of mercury film microelectrodes, the precision can be improved if the accumulation of the analyte is performed under quiescent conditions. Practical examples of stripping voltammetry with microelectrodes such as copper determination in whisky and trace metal measurements in drinking water are given.     

Capillary electrophoresis of platinum-group elements. Analytical, speciation and biochemical studies

A great deal of research has been carried out in recent years on developing high-efficiency capillary electrophoresis (CE) techniques that are able to separate rapidly and selectively ionic platinum metal species in a wide variety of their complexed forms. Using a range of illustrative examples, this review examines the potential and utilization of various CE separation approaches and detection modes in this expanding area. Also covered are CE procedures suitable for solving practical analytical problems and for platinum metal speciation purposes. Presenting a comprehensive treatise on the evolving practices of CE concerning platinum anticancer drugs--in particular, the examination of the stability of intact drugs, the separation and identification of products of their metabolism and interactions with biomolecules (including kinetic studies of the binding behavior)--this paper witnesses a welcome shift of the main research activities to those performed under physiological conditions.     

Repeated use of a hydrophobic ligand-containing porous membrane for protein recovery

A porous hollow-fiber membrane containing a phenyl group as a hydrophobic ligand was prepared by radiation-induced graft polymerization of glycidyl methacrylate, followed by successive ring-opening reactions with phenol and water. Bovine serum albumin (BSA) was bound to the ligand during permeation of a BSA solution in phosphate buffer containing 2M (NH₄)₂SO₄ through the pores of the hollow fiber. Subsequent elution with an (NH₄)₂SO₄-free buffer exhibited an elution percentage of 82%. Repeated cycles of adsorption and elution caused the accumulation of BSA on the pore surface, resulting in a decrease in the binding capacity of BSA with increasing number of cycles. In contrast, by permeating 1 M NaOH after each elution, the binding capacity of BSA was maintained even after ten cycles. This alkaline regeneration was found to be effective in ensuring repeated use of the phenyl-group-containing porous membrane for recovery of proteins.     

Determination of phosphatidylcitoline in serum with use of a choline-sensitive membrane electrode

A choline-sensitive membrane electrode made with potassium tetrakis(p-chlorophenyl) borate as the exchanger and o-nitrophenyl phenyl ether as membrane solvent in poly (vinyl chloride) was almost insensitive to the surfactant sodium deoxycholate. By using this electrode, choline ( 10^?5 M) formed by the enzymatic hydrolysis of phosphatidylcholine with phospholipase D in the presence of sodium deoxycholate as activator was successfully measured. The method was applied to the determination of phosphatidylcholine in serum.     

Analytical use of the selective extraction of copper as its phenylacetate

Chloroform solution of phenylacetic add has been found very suitable for extraction and colorimetric determination of copper. Iron and uranium are the main interferences, which can be overcome by masking with ammonium fluoridc. Under these conditions, only gold(III), platinum(IV) and palladium(II) are co-extracted, but their colour does not interfere with measurement of the green copper extract at 700 nm. The method has been applied to the determination of copper in iron, steels, uranium, lead concentrates and alloys containing nickel, cobalt, etc. The extraction procedure can also be used to remove interference of iron, copper and uranium in the determination of manganese with formaldoxime.     

Arsenic compounds in marine and terrestrial organisms: Analytical,chemical and biochemical aspects

Arsenic has a reputation as a poison, because arsenic trioxide was used during medieval times as an agent for murder. Lingering memories of these events make any arsenic-containing material suspect. Toxicity is a property of a specific compound and varies with the composition and structure of compounds. Developments in analytical methodology made it possible not only to determine total arsenic in a variety of matrices but also arsenic compounds. Knowledge about the arsenic cycle in marine systems has expanded considerably during the past decade. The marine arsenic cycle appears to be more complex than the cycle in the terrestrial environment. More attention must be given to the minor arsenic-containing compounds detected in organisms and experiments should be undertaken that provide information about the biochemical pathways used for the transformation of arsenic compounds.     

Analytical assessment of the oscillating chemical reactions by use chemiluminescence detection

This paper introduces the chemiluminescence (CL) detection in oscillating reaction-based determinations using the analyte pulse perturbation technique, a straightforward and expeditious approach to deriving quantitative analytical information from oscillating chemical reactions. The behavior of the H(2)O(2)-KSCN-CuSO(4)-NaOH oscillating system in the presence of luminol was examined by using the proposed detection method and the classical potentiometric technique. Some analytical and practical aspects of both detection systems are discussed. A new analytical method for the determination of vitamin B(6) based on the sequential perturbation produced by different amounts of this substance on the oscillating chemical system was also developed in order to assess the potential of CL detection for routine analyses. The calibration curve thus obtained was linear over the range 0.5-2.0 mumol of vitamin B(6), and the precision and throughput were also quite good (3.04% as RSD and nine samples h(-1), respectively). The proposed method was validated by determining the vitamin in pharmaceutical preparations.     

Manipulation of cell-sized phospholipid-coated microdroplets and their use as biochemical microreactors

Cell-sized water droplets coated by a phospholipid layer mimicking the inner surface of living cells were manipulated by laser tweezers and used as biochemical microreactors. The cell-sized phospholipid-coated microdroplets (CPMDs) consisted of a water droplet in mineral oil with a diameter of 1-100 microm and coated by 1,2-dioleoyl-sn-glycero-3-phosphoethanolamine. We monitored the time development of biochemical reactions in a single CPMD obtained after the controlled fusion of two CPMDs containing a substrate and an enzyme, respectively. We present results on two enzymatic reactions: calcein production in the presence of esterase and green fluorescence protein expression.