Analysis of supersonic flow in Oswatitsch inlet configuration

The aim of this work is a study of the flow parameters relevant for the Oswatitsch intake configuration. Geometry of the cone and inlet are equivalent to those on MiG-21bis fighter aircraft. Supersonic flow parameters for a channeled cone were studied at two different operational Mach numbers. Center body cone is movable along longitudinal axis and analysis is focused on specific positions for supersonic flight regimes. To study the problem, numerical model of axisymmetric two-dimensional Euler flow is applied. (© 2011 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim)     

Structure-based computational database screening, in vitro assay, and NMR assessment of compounds that target TAR RNA

There has been little prior effort to discover new drugs on the basis of a unique RNA structure. Binding of the viral transactivator Tat to the 5' bulge of the transactivation response (TAR) element is necessary for HIV-1 replication, so TAR RNA is a superb target. A computational approach was developed to screen a large chemical library for binding to a three-dimensional RNA structure. Scoring function development, flexible ligand docking, and limited target flexibility were essential. From the ranked list of compounds predicted to bind TAR, 43 were assayed for inhibition of the Tat-TAR interaction via electrophoretic mobility shift assays. Eleven compounds (between 0.1 and 1 microM) inhibited the Tat-TAR interaction, and some inhibited Tat transactivation in cells. NMR spectra verified specific binding to the 5' bulge and no interaction with other regions of TAR.     

Sensitivity enhancement using chemically reactive gas cluster ion beams in secondary ion mass spectrometry (SIMS)

We report for the first time on significant molecular secondary ion yield increases by modifying the chemistry of a water cluster primary ion beam. This was demonstrated using 70-keV ion beams of 0.15 eV/amu. For the neutral drug Bezafibrate, secondary ion yield enhancements ×5–10 were observed when replacing the Ar carrier gas in a water gas cluster ion beam (GCIB) source with a mixture containing 12% CO₂ and 2% O₂ in Ar. For the cationic drug Ranitidine, the ion yield enhancements using the CO₂-containing carrier gas were up to ×20–50 in positive mode and ×2–4 in negative mode. The extent of molecular fragmentation was very similar from both cluster beams. We conclude that additional chemically reactive species are present in the impact zone using the (H₂O/CO₂)_n projectile, which promote the formation of secondary ions of both polarity through projectile impact-induced chemical reactions. This methodology can be applied to further extend the capabilities of high-resolution 3-dimensional mass spectral imaging using reactive GCIB-SIMS.     

Optimisation and on-line acoustic monitoring of laser cleaning of soiled paper

Laser cleaning is an attractive and advanced technique of cleaning cultural heritage materials. However, in the case of paper-based substrates, it may lead to surface discoloration and long-term destabilisation of the cellulosic component. The origin of discoloration during pulsed laser removal (Nd:YAG laser, 532 and 1064 nm) of carbonaceous soiling was studied using UV resonance Raman spectroscopy and X-ray photoelectron spectroscopy. It was concluded that macromolecular conjugated systems are the most probable cause of discoloration, formed as a consequence of thermolytic reactions. With chemiluminometry, we analysed the processes following irradiation. Using photo-ageing and thermally accelerated ageing, it was indicated that, even at fluences lower than the ablation threshold of cellulose, long-term destabilisation of the material should be taken into account. By using much lower laser shot repetition rates than usual, i.e. 1 s^-1, we can allow the substrate to cool between consecutive laser shots, thus minimising the adverse effects of laser treatment. Acoustic monitoring was shown to be an affordable possibility for on-line process control. The amplitude of shock waves was shown not to be wavelength dependent (532 or 1064 nm); however, the parameter can be used to monitor the progress of cleaning. PACS 42.62.-b; 61.80.Ba; 83.80.Mc; 78.20.Hp; 68.37.Xy     

Immobilization of nanostructured lipid particles in polysaccharide films

Lipid-based equilibrium self-assemblies and their hierarchically ordered forms have been known since the last few decades. Related progress in colloids and interface science led the development of oil-in-water type internally self-assembled lipid particles, known as Isasomes, which have aroused great interest in biotechnological applications. These submicrometer-sized lipid particles are internally nanostructured in a form of various liquid-crystalline or microemulsion phases, which facilitate their loading with hydrophilic, hydrophobic, and amphiphilic molecules. Their internal nanostructure can also be finely tuned. Recently, it has been shown that Isasomes can be entrapped in thermoreversible polysaccharide hydrogels. Herein, we report on the immobilization of Isasomes in solid polysaccharide films prepared by drying particle-loaded κ-carrageenan and methyl cellulose-based hydrogels. These rather simple but elegant media facilitate the storage of these functional particles and their subsequent release by simple resolubilization in water and/or thermal transitions. Systematic rehydration studies of such Isasome-loaded films have shown that the Isasomes can be remobilized and/or recovered after resolubilization of loaded films, even after several months.     

Interactions of salicylic acid derivatives with calcite crystals

Investigation of basic interactions between the active pharmaceutical compounds and calcium carbonates is of great importance because of the possibility to use the carbonates as a mineral carrier in drug delivery systems. In this study the mode and extent of interactions of salicylic acid and its amino acid derivates, chosen as pharmaceutically relevant model compounds, with calcite crystals are described. Therefore, the crystal growth kinetics of well defined rhombohedral calcite seed crystals in the systems containing salicylic acid (SA), 5-amino salicylic acid (5-ASA), N-salicyloil-l-aspartic acid (N-Sal-Asp) or N-salicyloil-l-glutamic acid (N-Sal-Glu), were investigated. The precipitation systems were of relatively low initial supersaturation and of apparently neutral pH. The data on the crystal growth rate reductions in the presence of the applied salicylate molecules were analyzed by means of Cabrera & Vermileya's, and Kubota & Mullin's models of interactions of the dissolved additives and crystal surfaces. The crystal growth kinetic experiments were additionally supported with the appropriate electrokinetic, spectroscopic and adsorption measurements. The Langmuir adsorption constants were determined and they were found to be in a good correlation with values obtained from crystal growth kinetic analyses. The results indicated that salicylate molecules preferentially adsorb along the steps on the growing calcite surfaces. The values of average spacing between the adjacent salicylate adsorption active sites and the average distance between the neighboring adsorbed salicylate molecules were also estimated.     

Use of genetic algorithms with multivariate regression for determination of gelatine in historic papers based on FT-IR and NIR spectral data

Quantitative non-destructive analysis of individual constituents of historic rag paper is crucial for its effective preservation. In this work, we examine the potentials of mid- and near-infrared spectroscopy, however, in order to fully utilise the selectivity inherent to spectroscopic multivariate measurements, genetic algorithms were used to select spectral data derived from information-rich FT-IR or UV-vis-NIR measurements to build multivariate calibration models based on partial least squares regression, relating spectra to gelatine content in paper. A selective but laborious chromatographic method for the quantification of hydroxyproline (HYP) has been developed to provide the reference data on gelatine content. We used 9-fluorenylmethyl chloroformate (FMOC) to derivatise HYP, which was subsequently determined using reverse-phase liquid chromatographic separation and fluorimetric detection. In this process, the sample is consumed, which is why the method can only be used as a reference method.The sampling flexibility afforded by small-size field-portable spectroscopic instrumentation combined with chemometric data analysis, represents an attractive addition to existing analytical techniques for cultural heritage materials.     

A chemiluminescence study of madder lakes on paper

The photo degradation of watercolour drawings prepared with madder lake pigments on gelatine-sized paper was studied by chemiluminometry, viscometry, and colorimetry. A method of recto irradiation and verso measurement was developed to overcome absorption of the emitted photons by the paint layer. A complex relationship between paper substrate, applied chromophores and associated transition metals was observed with strong correlations between the presence of transition metals associated with the madder lakes and the degradation of the paper substrate and the applied paint layer as well as evidence of pro-oxidative activity by the chromophores in the applied paint layers. The pro-oxidant behaviour appears to be dependent on the type of transition metal present. This is the first in-depth research into the photodegradation of madder lake-based watercolours which attempts to understand the chemistry of the processes.