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.     

Preparation and self-assembly of chiral porphyrin diads on the gold electrodes of quartz crystal microbalances: a novel potential approach to the development of enantioselective chemical sensors

Porphyrin diad 1 was synthesized by reaction of the acyl chloride of porphyrin 2 and trans-1,2-dithiane-4,5-diol. The Co complex of this diad was studied as a potential enantioselective receptor for chiral recognition in solution and in the solid state. In solution both enantiomers of limonene induce significant changes in the visible and circular dichroism (CD) spectra of [Co2(1)], while a different behavior is observed in the case of the enantiomeric pair of trans-1,2-diaminocyclohexane. A different efficiency of [Co2(1)] chiral recognition is obtained for these compounds, with a remarkable degree of enantiodiscrimination observed in the case of limonene. Self-assembled monolayers of [Co2(1)] were deposited onto the gold electrodes of quartz crystal microbalances to be used as sensing materials of nanogravimetric sensors operating in the gas phase. The enantiodiscrimination properties of these sensors towards the enantiomeric pairs of chiral analytes have been studied. While in the case of analytes bearing donor ligand atoms we did not observe a remarkable enantioselectivity, a significant degree of chiral discrimination was observed in the case of limonene; this result is particularly encouraging for the potential development of enantioselective chemical sensors for use in an array configuration.     

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.     

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.     

Use of highly efficient Draper-Lin small composite designs in the formal optimisation of both operational and chemical crucial variables affecting a FIA-chemiluminescence detection system

A new formal strategy in the multidimensional optimisation of the experimental variables affecting the chemiluminescence (CL) detection in flow injection analysis (FIA) is proposed here. The strategy implies several steps, being the most significant: selection of the variables to be studied and their experimental domain; use of a screening design to detect significant variables and interactions into the experimental region; study of the main effect of variables and second-order interactions; and finally application of a Draper-Lin small composite design (orthogonal) to obtain the optimum values of the significant variables. The methodology is applied to the determination of methylamine by FIA based on the use of the peroxyoxalate CL (PO-CL) reaction. Considering the high number of experiments required due to the different chemical and instrumental variables to be taken account and their adequate compatibility to obtain maximum sensitivity, the methodology offers a rigorous study of the main effects and interactions, achieving a reduction of experimental work.     

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.     

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.     

Investigation of drift gas selectivity in high resolution ion mobility spectrometry with mass spectrometry detection

Recent studies in electrospray ionization (ESI)/ion mobility spectrometry (IMS) have focussed on employing different drift gases to alter separation efficiency for some molecules. This study investigates four structurally similar classes of molecules (cocaine and metabolites, amphetamines, benzodiazepines, and small peptides) to determine the effect of structure on relative mobility changes in four drift gases (helium, nitrogen, argon, carbon dioxide). Collision cross sections were plotted against drift gas polarizability and a linear relationship was found for the nineteen compounds evaluated in the study. Based on the reduced mobility database, all nineteen compounds could be separated in one of the four drift gases, however, the drift gas that provided optimal separation was specific for the two compounds.