A definitive RNAA method for determination of selenium in biological samples: uncertainty evaluation and assessment of degree of accuracy

This article describes work on the development of a highly accurate RNAA method for determination of selenium in biological samples. The analytical post-irradiation procedure is based on a combination of cation-exchange and extraction chromatography with final selective and quantitative fixation of selenium on a column packed with 3,3′-diaminobenzidine (DAB) supported on Amberlite XAD4, followed by gamma-ray spectrometric measurement. The suitability and accuracy of the method was demonstrated by analysing CRMs with certified selenium content. The uncertainty budget for Se determination in standard reference material Peach Leaves NBS 1547 was estimated; the combined standard uncertainty was calculated as 1.7%. The described method fulfils all the criteria for definitive methods. It was subsequently used for determination of selenium in biological materials intended as new CRMs and proficiency test samples.     

The effect of UV-irradiation on composting of polyethylene modified by cellulose

LDPE and its blend with cellulose, obtained by extrusion, were UV-irradiated with different doses or biodegraded in soil up to 1 year. Simultaneously, the same samples were 1 year biodegraded after 20 h UV pre-irradiation in the same conditions. The course of photo- and biodegradation was monitored by estimation of average molecular weights and polydispersity, gel amount, changes of PE crystallinity and mechanical properties. Moreover, the biodegradation degree was calculated on the basis of carbon dioxide evolved and surface morphological changes were observed by SEM. It was found that biodegradation of PE + cellulose is hampered by intermolecular crosslinking of both components. Although, the rate of decomposition of PE + cellulose blends is low it is enough for disintegration of such materials in the natural environment.     

An Efficient Microwave-Assisted Synthesis of Structurally Diverse Styrylquinolines

Summary. Aromatic aldehydes undergo condensation with quinaldines under microwave irradiation to afford structurally diverse styrylquinolines in high yields under solvent-free conditions. A comparison with the conventional method clearly indicates the advantages of the new protocol.     

H-bonded complexes of aniline with HF/F- and anilide with HF in terms of symmetry-adapted perturbation, atoms in molecules, and natural bond orbitals theories

The hydrogen-bonded isoelectronic complexes of aniline with HF/F- and an ionic form of aniline with HF were investigated by use of computational methods: Symmetry-Adapted Perturbation Theory (SAPT), Atoms in Molecules (AIM), and Natural Bond Orbitals (NBO) approaches. All computations were based on structural models previously generated at the B3LYP/6-311+(d,p) level. The differences between neutral (Ph-NH2...HF)and anionic (Ph-NH2...F- and Ph-NH-...HF) complexes were clearly outlined. The discussed charged complexes serve as Lewis acids and base, HF and F-, respectively. It was found that electrostatic and induction energy terms, obtained as a result of the SAPT method, are most dependent on the type of H-bonding (i.e.,charged or neutral). The electrostatic term is the most distinctive between the neutral and charge-assisted hydrogen bonds in the investigated two-body systems, whereas the latter is more significant in the case of weaker interactions (larger H...B distances). Application of Principal Component Analysis (PCA) to energy components obtained from the SAPT procedure indicated that all of them are relatively well intercorrelated.The above-mentioned terms together with the exchange energy terms are the most important contributions ofthe main principal component, which describes 95% of the total variance. Comparison of AIM parameters in bond critical points for modeled H-bond systems shows a good agreement with those from equilibrium complexes, both experimental and calculated ones. It was found that charged H-bonded complexes exhibit larger fluctuation of electron density and its Laplacian in bond critical points, in line with SAPT analysis. NBO results confirmed the effect of the strength of interaction on property changes both in the region of H-bonding and outside of it. The latter, more distant consequences follow the Bent-Walsh rule for all studied complexes.     

Three-dimensional effects on line-of-sight visualization measurements of supersonic and hypersonic flow over cylinders

Flow visualization experiments were performed for supersonic and hypersonic nitrogen test gas flows over a cylinder. The results were used to quantify the influence of three-dimensional effects on optical line-of-sight visualization measurements. Images of cylindrical models of varying aspect ratios (length to diameter) were taken. Shock stand-off distance measurements for the models were compared with a two-dimensional approximation and numerical simulations. For aspect ratios of two and above, the two-dimensional approximation was acceptable within experimental uncertainty. The measured shock stand-off decreased by less than 5% from an asymptotic value for an infinite length cylinder. For smaller aspect ratios, a correction factor for the shock stand-off needs to be applied if comparisons between the two-dimensional approximation and experimental measurements are to be drawn. An estimate of this correction factor has been derived from an empirical fit to the available data.      

Supersonic velocimetry in a shock tube using laser enhanced ionisation and planar laser induced fluorescence

 A novel flow-tagging technique is presented which was employed to measure gas velocities in the free stream of a shock tube. This method is based on the laser spectroscopic techniques of Laser-Enhanced Ionisation (LEI) and Laser-Induced Fluorescence (LIF). The flow in the shock tube is seeded with small amounts of sodium, and LEI is used to produce a substantial depletion of neutral sodium atom concentration in a well-defined region of the flow, by using two wavelength-resonance excitation and subsequent collisional ionisation. At a specific time delay, single-laser-pulse planar LIF is utilised to produce a two-dimensional (2-D) inverse image of the depleted tagged region downstream of the flow. By measuring the displacement of the tagged region, free stream velocities in a shock tube were determined. Large variations in the concentration of sodium seeded into the flow were observed and even in the presence of these large variations accurate free-stream velocity measurements were obtained. The experimentally determined value for velocity compares very well with the predicted velocity. Received: 25 March 1996/Revised version: 8 July 1996