Mobile phase versus stationary phase approaches to the direct injection of biological fluids in liquid chromatography

The liquid chromatographic analysis of drugs in urine through direct injection without any sample pretreatment was extended to micellar chromatography with nonionic surfactants, the Pinkerton ISRP column and the shielded hydrophobic phase (Hisep) column. The feasibility of using each was demonstrated through the determination of the diuretic, hydrochlorothiazide, in urine. Good separation, recovery, precision and linearity, and adequate limits of detection were obtained for this analysis with all three techniques. The advantages and limitations of the mobile phase approach of micellar chromatography and the two stationary phase approaches are discussed for the direct injection of urine as well as other biological fluids.     

Method development for the determination of iron in milligram amounts of rice plants (Oryza sativa L.) from cultivation experiments using graphite furnace atomic absorption spectrometry

The amount of sample that is available for analysis in laboratory plant cultivation experiments is usually very limited. Highly sensitive analytical techniques are therefore required, even for elements that are present in the plants at mg g^–1 concentrations, and graphite furnace atomic absorption spectrometry (GFAAS) was chosen in this work because of its micro-sampling capability, and its relatively simple operation. Four micro-methods were investigated for the determination of iron in roots and leaves of rice plants: i) a micro-digestion with nitric and hydrochloric acids, ii) a slurry procedure using tetramethylammonium hydroxide (TMAH) tissue solubilizer, iii) a slurry prepared in 1.4 mol L^–1 nitric acid, and treated in an ultrasonic bath, and iv) the direct analysis of solid samples. The micro-digestion was suffering from high blank values and contamination problems, so that it could not be recommended for routine purposes. The TMAH method exhibited poor precision and occasional low recoveries, particularly for real samples. Direct solid sampling analysis gave results similar to those obtained with the slurry technique with ultrasonic agitation for the determination of iron in certified reference materials with iron content up to about 100 g g^–1, but was too sensitive for the investigated rice plants, which had an iron content up to several mg g^–1. The slurry technique with ultrasonic treatment of the samples, suspended in dilute nitric acid, was finally adopted as the method of choice.The method was then applied for the determination of iron in the leaves and in different compartments of the roots of two rice cultivars, one sensitive to iron toxicity, an important nutritional disorder, and the other one resistant to iron toxicity. The results suggest that the higher resistance to iron toxicity of the second cultivar is due to a smaller uptake of iron from the soil, resulting in lower iron levels in all compartments of the plant.     

Solution Properties of the Exopolysaccharide Produced by Pseudomonas Marginalis Strain HT041B 1

Abstract

The solution properties of the exopolysaccharide marginalan produced by Pseudomonas marginalis HT041B were investigated by means of low-angle laser light-scattering, capillary viscometry, and rheology. Potentiometric and viscosimetric data indicated the absence of a cooperative transition of the disorder-to-order type. The experimental findings obtained in dilute solution (Mark-Houwink coefficients, rigidity coefficient, characteristic ratio) suggested that the polymer behaves like a semiflexible chain which adopts a disordered conformation. The rheological behaviour of more concentrated marginalan solutions, as determined by means of both steady shear and oscillatory measurements, further confirmed the disordered conformational state of the polymer in solution.

     

Influence of narrow starter notches on the initial crack growth resistance curve of ceramics

In experimental R-curve investigations crack development usually starts from notches. The validity of R-curves depends on the size of the notch root radius. This influence is completely ignored in most cases. In this theoretical study it is shown how the notch radius affects the formally computed crack resistance curve. First, the influence of the notch radius on the starting point of the R-curve, the so-called crack-tip toughness K _I0, will be addressed. Then, the effect of the notch on the shielding stress intensity factor will be discussed, and, finally, the influence on T-stress and the consequences on local path stability will be shown.     

A weight function for the single edge crack based on approximative displacement fields

Weight functions for the calculation of stress intensity factors can simply be determined by using an extension of the Petroski-Achenbach method. The procedure is demonstrated for an edge crack in a strip of finite width. The resulting weight function is compared with solutions available in the literature.     

A direct comparison of non-destructive techniques for determining bridging stress distributions

Crack bridging is an important source of crack propagation resistance in many materials and the bridging stress distribution as a function of crack opening displacement is widely believed to represent a true material property uninfluenced by sample geometry, loading conditions, and other extrinsic factors. Accordingly, accurate measurement of the bridging stress distribution is needed and many non-destructive methods have been developed. However, there are many challenges to accurately determining bridging stresses. A comparison of bridging stresses measured using R-curve, crack opening displacement (COD), and spectroscopy methods has been made using two bridging ceramics, Y₂O₃ and MgO doped Si₃N₄ and 99.5% pure Al₂O₃. The COD method is surface sensitive and gives a lower peak bridging stress compared to the R-curve technique which samples through the entire material thickness. This is attributed to a more compliant near surface bridging zone. Conversely, when R-curves rise steeply over the first few micrometers of growth from a notch, an effect of negative T-stress is expected to raise the R-curve determined peak bridging stress. Spectroscopy methods were only found to yield reliable bridging stress results if a reasonable through thickness volume of material is sampled. It was found that 2.5% of the specimen thickness achieved using fluorescence spectroscopy appears adequate for Al₂O₃ while 0.1–0.2% of the sample thickness achieved using Raman spectroscopy for Si₃N₄ appears inadequate. Overall, it is concluded that in the absence of T-stresses a bridging distribution can be determined that is a true material property. Also, a new method is proposed for determining the bridging stresses of fatigue cracks from (1) the bridging stress distribution for monotonically loaded cracks and (2) experimental fatigue data.     

Evaluation of intramolecular energy transfer process in the lanthanide(III) bis- and tris-(TTA) complexes: Photoluminescent and triboluminescent behavior

This work reports the energy transfer mechanism process of [Eu(TTA)₂(NO₃)(TPPO)₂] (bis-TTA complex) and [Eu(TTA)₃(TPPO)₂] (tris-TTA complex) based on experimental and theoretical spectroscopic properties, where TTA=2-thienoyltrifluoroacetone and TPPO=triphenylphosphine oxide. These complexes were synthesized and characterized by elemental analyses, infrared spectroscopy and thermogravimetric analysis. The theoretical complexes geometry data by using Sparkle model for the calculation of lanthanide complexes (SMLC) is in agreement with the crystalline structure determined by single-crystal X-ray diffraction analysis. The emission spectra for [Gd(TTA)₃(TPPO)₂] and [Gd(TTA)₂(NO₃)(TPPO)₂] complexes are associated to T→S₀ transitions centered on coordinated TTA ligands. Experimental luminescent properties of the bis-TTA complex have been quantified through emission intensity parameters Ω_λ (λ=2 and 4), spontaneous emission rates (A_rad), luminescence lifetime (τ), emission quantum efficiency (η) and emission quantum yield (q), which were compared with those for tris-TTA complex. The experimental data showed that the intensity parameter value for bis-TTA complex is twice smaller than the one for tris-TTA complex, indicating the less polarizable chemical environment in the system containing nitrate ion. A good agreement between the theoretical and experimental quantum yields for both Eu(III) complexes was obtained. The triboluminescence (TL) of the [Eu(TTA)₂(NO₃)(TPPO)₂] complexes are discussed in terms of ligand-to-metal energy transfer.