A way of establishing quality of measurements in gas analysis—national and international aspects

Standardising quality of measurements at both the national and international level results in a unity in measurement that may be regarded a synonym of traceability. In gas analysis, the key issue in achieving this aim is production of gaseous reference materials. Establishing a network of secondary measurement standards at gaseous CRM producers’ sites in Ukraine might be interesting for those involved in gas analysis activities. Inevitably, problems concerning the recognition of measuring capabilities of both national metrological institutes and local CRM producers are now an international issue. Thus, the problems of national adoption of international standards, as well as harmonisation between different international documents are currently relevant, and Ukrainian experience may be useful to others in this field. Presented at the 3rd International Conference on Metrology, November 2006, Tel Aviv, Israel.     

New In-situ Sampling and Analysis of the Production of CeO<Subscript>2</Subscript> Powders from Liquid Precursors using a Novel Wet Collection System in a rf Inductively Coupled Thermal Plasma Reactor. Part 1: Reactor System and Sampling Probe

A new reactor and a novel in-situ sampling technique were developed for the study of the synthesis of CeO₂ powders produced from dissolved cerium nitrate salts. The conical reactor minimized particle recirculation and provided a highly symmetrical and undisturbed plasma flow suitable for the analysis of the phenomena affecting the formation of CeO₂ powders. Both a calorimetric study of the reactor and a thermodynamic analysis of CeO₂ formation were conducted. The sampling probe is described and near-isokinetic sampling was achieved. The sampled particles were collected using a miniature wet collection system, i.e. a mist atomizer and a custom-made spray chamber. A numerical simulation of the velocity and temperature fields of the plasma gas in the reactor was done using Fluent. A comprehensive droplet-to-particle formation mechanism presented elsewhere is revisited and expanded based on calorimetry, thermodynamics of CeO₂ formation, numerical simulations and collected particles. No traces of other oxidation states other than CeO₂ were found.     

Preconcentration of Cadmium and Zinc on a Chelating Sorbent and Their Determination by Flame Atomic Absorption Spectrometry

A method is developed for cadmium and zinc preconcentration on a minicolumn packed with a new chelating polymer sorbent. The effects of the test solution pH and volume, the sample matrix composition, the eluent volume, and the sample and eluent flow rates are studied. Zinc and cadmium in the eluate are determined by flame atomic absorption spectrometry. Under optimal conditions, the determined ion recovery is more than 95%. The detection limits (3σ, n = 20) are found to be 15.0 (Cd) and 17.2 (Zn) ng/mL. The developed method is employed for cadmium and zinc determination in samples of seawater and water obtained after oil pumping.     

Flow-injection analysis with a small cylindrical wire type electrode

An amperometric detector with a small thin mercury film electrode is described. The device demonstrates advantageous operational characteristics such as small dispersion (D<2) and “memory effect” (me<0.6%), extensive maximum sample frequency (msf −200 samples/h), and high sensitivity. It has been proven useful in flow-injection analysis at a constant potential under hydrodynamic conditions.     

Chemical and thermal stability of alkanethiol and sulfur passivated InP(100)

InP(100) surfaces treated with Na2Sx9H20 and CnH(2n+1)SH are examined by contact angle measurement, X-ray photoelectron spectroscopy, and atomic force microscopy to determine the chemical and thermal behavior of these passivated surfaces. The surfaces coated by octadecanethiol (n = 18) self-assembled monolayers (SAMs) are found to be more stable toward oxidation than the S-passivated surface. The chemical stability of octadecanethiol SAMs in various environments is examined. The thiol monolayer is found to be stable in 0.1 M HCl but degrades in 0.1 M NaOH, boiling chloroform, and water. The behavior of these surfaces at elevated temperatures under a vacuum is also investigated. The octadecanethiol-coated InP(100) is stable up to 473 K, above which the films begin to degrade. Unlike other substrates on which the entire molecule including the sulfur headgroup desorbs together, on InP, the sulfur headgroup remains on the surface even after annealing to 673 K. These observations suggest that the desorption occurs by S-C bond cleavage as well as In-S bond cleavage. The sulfur of S-passivated InP is found to be more thermally stable than that of the octadecanethiol monolayer, perhaps due to their different bonding geometries and hence energies.     

Case Study: Doping Substances in Equestrian Food Supplements

In the course of investigations on equestrian supplemental products for the presence of doping substances, two products were found to contain forbidden substances. As reported earlier a plant extract (Mexican cactus extract) named “Energy 5” contained the anabolic androgenic steroids (AAS) stanozolol, 17β-hydroxy-17α-methyl-5α-androstane-3β-ol (3β,5α-THMT) as well as mestanolone not declared on the label. In the present study, a product called “Super Kalm Paste” was tested. Analysis by gas chromatography - mass spectrometry (GC-MS) revealed that the preparation contained the class I anti-arrhythmics quinine (trade names Kinidin^TM, Durules) and cinchonine. The samples were prepared according to a sample preparation procedure established for anabolic steroids in nutritional supplements for humans. The sample treatment comprised the extraction and purification of the analytes as well as the chemical conversion with N-methyl-N-trimethylsilyl-trifluoracetamide (MSTFA) to yield the trimethylsilyl (TMS)-derivatives. To verify whether the administration of such products could lead to positive doping tests, a pilot excretion study on “Energy 5” was conducted with two geldings, and urine samples were collected. Gas chromatography - high resolution mass spectrometry (GC-HRMS) after solid phase extraction and mixed derivatisation has demonstrated the presence of the stanozolol metabolite 16β-hydroxy-stanozolol in urine samples after “Energy 5” application.     

Some applications of silica aerogels

Silica aerogels are very highly divided materials which are synthesised through the association of a chemical step, the so-called sol–gel chemistry, with a physical step which is a particular way of drying the wet gel, namely under supercritical conditions with respect to the liquid phase filling its porosity. This drying process preserves the texture of the dry material: in practice it strongly reduces the pore collapse. The resulting hyperporous solids that have bulk densities of the same magnitude as air develop new and very interesting physical and even chemical properties. Owing to their poor chemical reactivity, very large surface areas (of the order of 1,000 m ²/g), unusual porous volumes (greater than 95%), morphologies (monoliths or powders), optical properties (transparent, opaque or translucent), and very low thermal conductivity, they find high added-value applications in the physics of high-energy particles (Cherenkov emitters), transparent and superinsulating double windows, life and space science as well.     

Thermal analysis and X-ray studies of chiral ferroelectric liquid crystalline materials and their binary mixtures

Summary Thermal properties of a homologous series of ferroelectric liquid crystals S-(-)-[4-(2-n-alkoxy-propionyloxy)]biphenyl-4'-[n-alkoxy-(3,5-dimethyl)]benzoate have been investigated by polarizing optical microscopy and differential scanning calorimetry. The mesophases were identified and confirmed by X-ray too. Three binary mixtures were prepared from the individual homologues. In one of the mixtures (Mix1), the ferroelectric SmC* phase has broadened and became enantiotropic. This mesophase remained monotropic in the other two mixtures (Mix2, Mix3). The chiral nematic N* phase did not appear in Mix1, but remained monotropic for the other two mixtures. Two molecular parameters, the layer spacing and the average intermolecular distance have been calculated from the X-ray results for the homologues and their mixtures. An intercalated tail-to-tail packing of molecules was found both in the single compounds and their mixtures resulting in the layer spacing about half of the molecular length of the single compounds.     

Posets isomorphic to their extensions

A standard extension for a poset P is a system Q of lower ends (descending subsets) of P containing all principal ideals of P. An isomorphism between P and Q is called recycling if [Y]Q for all YQ. The existence of such an isomorphism has rather restrictive consequences for the system Q in question. For example, if Q contains all lower ends generated by chains then a recycling isomorphism between P and Q forces Q to be precisely the system of all principal ideals. For certain standard extensions Q, it turns out that every isomorphism between P and Q (if there is any) must be recycling. Our results include the well-known fact that a poset cannot be isomorphic to the system of all lower ends, as well as the fact that a poset is isomorphic to the system of all ideals (i.e., directed lower ends) only if every ideal is principal.     

Analytical Detectors Based on Microplasma Spectrometry

Miniaturizing all dimensions of apparatus, such as electronics and computers, is the current trend followed by scientists in various fields. The idea of Lab-on-a-Chip has significantly expanded and found its broad applications in analytical chemistry. Microplasmas can act as a sample excitation source and are the miniaturized versions of full-sized plasmas. These can be created in various forms, such as direct current, microwave induced, capacitively coupled and inductively coupled plasmas. Scaling down the size would reduce the amount of gases, liquids and consumables required, as well as the sample analysis time, which in turn would decrease the operating costs. Therefore, several research groups are involved in the development of microplasmas for utilisation in analytical instruments.