Epileptic rat brain tissue analyzed by 2D correlation Raman spectroscopy.

Absence epilepsy is the neurological disorder characterized by the pathological spike-and wave discharges present in the electroencephalogram, accompanying a sudden loss of consciousness. Experiments were performed on brain slices obtained from young male WAG/Rij rats (2-3weeks old), so that they were sampled before the appearance of brain-damaging seizures symptoms. Two differing brain areas of the rats' brain tissue were studied: the somatosensory cortex (Sc) and the dorsal lateral geniculate nucleus of the thalamus (DLG). The Raman spectra of the fresh brain scraps, kept during measurements in artificial cerebrospinal fluid, were collected using as an excitation source 442nm, 514.5nm, 785nm and 1064nm laser line. The average spectra were analyzed by 2D correlation method regarding laser line as an external perturbation. In 2D synchronous spectra positive auto-peaks corresponding to the CC stretching and amide I band vibrations show maxima at 1660cm-1 and 1662cm-1 for Sc and DLG, respectively. The prominent auto-peak at 2937cm-1, originated from the CH3 mode in DLG brain area, seems to indicate the importance of methylation, considered to be significant in epileptogenesis. Synchronous and asynchronous correlations peaks, glutamic acid and gamma-aminobutyric acid (GABA), appear in Sc and DLG, respectively. In the 1730-1600cm-1 range occur cross-peaks which appearance might be triggered by glial fibrillary acidic protein (GFAP) activation.

Comparison of pigment content of paint samples using spectrometric methods.

The aim of the paper was to evaluate the influence of pigment concentration and its distribution in polymer binder on the possibility of colour identification and paint sample comparison. Two sets of paint samples: one containing red and another one green pigment were prepared. Each set consisted of 13 samples differing gradually in the concentration of pigment. To obtain the sets of various colour shades white paint was mixed with the appropriate pigment in the form of a concentrated suspension. After solvents evaporation the samples were examined using spectrometric methods. The resin and main filler were identified by IR method. Colour and white pigments were identified on the base of Raman spectra. Colour of samples were compared based on Vis spectrometry according to colour theory. It was found that samples are homogenous (parameter measuring colour similarity ΔE<3). The values of ΔE between the neighbouring samples in the set revealed decreasing linear function and between the first and following one--a logarithmic function.

Characterization of blue pigments used in automotive paints by Raman spectroscopy.

Micro-Raman spectroscopy was applied to forensic identification of pigments in paint chips and provided differentiation between paint samples. Sixty-six blue automotive paint samples, 26 solid and 40 metallic were examined. It was found that the majority of the collected Raman spectra provided information about the pigments present. However, in some cases, fluorescence precluded pigment identification. Using laser excitation at longer wavelengths or pretreatment to effect photobleaching often resulted in reduced fluorescence, particularly for solid color samples, and allowed pigment identification. The examined samples were compared pairwise taking into account number, location, and intensity of absorption bands in their infrared spectra. The estimated discrimination power ranged from 97% for solid paint samples to 99% for metallic paint samples.

Chemical analysis of post explosion samples obtained as a result of model field experiments.

Five different explosives were detonated in a series of field experiments. Each experiment (detonation of the charge of each specific explosive) was repeated three times. The experiments were conducted under controlled conditions, exceeding those of research published so far. Detonated charges were uniform in size and, as far as possible, in shape. The explosives used originated from the same batch. Additionally, the same kind of electric detonators were used. Witness plates (sheets of galvanised steel 100 cm × 90 cm × 0.5 mm) were used to collect post-blast residues in a reproducible way. They were placed relatively close to the charge to minimise the influence of the wind. Samples were collected by systematic swabbing of the surface of the plate by acetone moistened cotton swabs. Samples were packed tight, transferred to the laboratory, and extracted with methanol. Extracts were concentrated by solvent evaporation, cleaned by centrifugation, and analysed using HPLC-DAD. Each extract was analysed three times and the mean value of the amount of the given explosive within the extract was calculated. For each of the explosive materials used the results of the repetition of the experiments proved them to be irreproducible. After each detonation of a specific charge different amounts of given explosives were found in post-blast samples. Also, the intuitively expected relationship between the distance from the charge and amount of post-blast residues were not observed. These results are consistent with previously published results of field experiments. The lack of reproducibility may be explained by differences in efficiency of detonation. The efficiency of a detonation may be influenced even by small differences in the shape of the charge as well as by the position and properties of the detonator. The lack of dependency between the amount of the explosive in the post-blast samples and the distance from the charge may be explained by the fact that during detonation, particles of unreacted explosives are not uniformly dispersed in all directions.

Application of infrared and Raman spectroscopy in paint trace examination.

Raman spectroscopy has proved to be a promising technique in forensic examinations, where optical microscopy, micro-infrared spectroscopy, and microspectrophotometry in the visible and UV range are used for identification and differentiation between paint traces. Often no organic pigments are detected using Fourier transform infrared spectroscopy, because their content in a trace is usually undetectable. Application of a micro-Raman spectrometer equipped with several excitation lasers helps forensic experts in paint analysis enabling identification of main pigments. Three cases concerning comparative examination of car paint are discussed in detail. The comparison of Raman spectra of paint chips found on clothing of a victim or smears found on body of a damaged car to these of paint chips originated from the suspected car enabled us to identify the car involved in the accident. When no comparative material is available, the method can be useful in establishing the color and make of the car.

Establishing of chemical composition of printing ink.

The subject of the examinations was primarily court tax marks of 50 and 200 PLN, which were suspected not to be genuine. Both inks on the questioned marks as well as comparative genuine marks and inks sent by the manufacturer were analyzed. No information about their chemical composition was available from manufacturer. In the examinations, infrared (IR), visible, X-ray fluorescence, and Raman spectrometry were used. The examinations showed that inks and glue on the marks of both values were the same as samples of those sent by the manufacturer. Discrepancies in some results were observed probably due to contamination, that is, an accidental presence of the foreign substance on the surface (e.g., sweat, saliva while sticking the marks to the surface or physical handling of the documents). It was concluded that there are original (genuine) court tax marks.

Black painted pottery, Kildehuse II, Odense County, Denmark.

This work aimed at characterization of a black layer covering a Bronze Age (period VI) pot surface. To solve research problems plane polarized light microscopy (PLM), scanning microscopy with X-ray microanalyser (SEM/EDS), Raman and FTIR microspectroscopies were applied. Observation of the black layer under the PLM suggests that we deal with an opaque, isotropic layer, purposely put on leather-hard, burnished surface of a pot. No traces of organic substances that might have modified a pot surface before painting were detected. The black layer coats the pot with a continuous 0.2-0.4 µm thick layer. The black layer must have been applied while warm or hot. It is recognized that the black layer is a true painting layer. Spectroscopic analyses (Raman and FTIR) point that birch tar or a birch-pine tar had been applied. Carbon black should be definitely excluded. The analyzed organic substance is structurally ordered in various degrees, due to varying temperature influence. Some Raman spectra reveal, in second-order region of the spectrum (>2000 cm(-1)), the graphite presence. Scarce points reveal the presence of inorganic admixtures: clay minerals, feldspars and quartz. The next question is: Is it an organic paint or a carbon-based, "mixed" paint? Inorganic admixtures are only casual. Relatively high concentration of alumina is expected to have appeared due to aluminum mobility in acidic environment and this was provided by organic tar/pitch substances. Phosphorus (usually with calcium) mostly concentrates together with clay minerals. Thus, hypothesis on bone powder or ash addition to tar/pitch should be excluded. Some elements may originate not only from inorganic substances but also from wood ashes.

Pyrolysis-gas chromatography/mass spectrometry analysis as a useful tool in forensic examination of automotive paint traces.

Pyrolysis (Py)-GC/MS was applied in comparative analysis of polymer binder of 150 automobile clearcoat samples. It was found that binders of identical type and similar infrared spectra can be, in most cases, effectively differentiated, sometimes based only on the presence of peaks of very low intensity originating from minor paint components. The qualitative procedure of pyrograms comparison was developed. The results obtained, enable one to draw the conclusion that Py-GC/MS appears as valuable, very informative analytical technique of car paint samples examination. Providing identification of paint pyrolysis products, it enables discrimination of samples on the basis of their composition. However, in some cases, paint samples were still indistinguishable on the basis of their pyrograms.

Differentiation and evaluation of evidence value of styrene acrylic urethane topcoat car paints analysed by pyrolysis-gas chromatography.

Pyrolysis (Py)-GC/MS was applied to differentiate between automobile paint samples. The method was used for analysis of 36 samples of styrene acrylic urethane clearcoats that were indistinguishable on the basis of their infrared spectra and elemental composition. Differences observed in the obtained pyrograms of the compared paint samples were relatively small. Therefore, statistical analysis of the obtained results was performed. The likelihood ratio test suitable for multivariate data analysis supported by analysis of data structure by graphical model was used. This approach allowed not only distinguishing the samples compared, but also allowed the evaluation of the evidential value of such observations, which is very important from a forensic point of view.

PRAXIS--combined mu-Raman and mu-XRF spectrometers in the examination of forensic samples.

Recently, two analytical techniques--Raman and XRF spectroscopy--have been often applied in criminalistic examinations of different kinds of trace evidences. In this paper, the application of the new combined mu-Raman and mu-XRF spectrometer in analysis of multilayer paint chips, modern inks, plastics and fibres was evaluated. It was ascertained that the apparatus possesses real advantages and could be helpful in the identification of examined materials after some modifications, i.e. by adding an extra laser and decreasing the spot size of the X-ray beam.

The use of rigid, fibrillar Congo red nanostructures for scaffolding protein assemblies and inducing the formation of amyloid-like arrangement of molecules.

The ordered amyloid-like organization of protein aggregates was obtained using for their formation the rigid fibrillar nanostructures of Congo red as the scaffolding. The higher rigidity of used dye nanoparticles resulted from the stronger stacking of molecules at low pH (near the pK of the dye amino group) because of the decreased charge repulsion. The polylysine, human globin, and immunoglobulin L chain were arranged in this way to form deposits of amyloid properties. The scaffolding was introduced simply by mixing the dye and proteins at a low pH or the dye was used in the preorganized form by maintaining it in the electric field before and during protein addition. The polarization and electron microscopy studies confirmed the unidirectional organization of the complex. The precipitate of the complex was used for studies directly or after the partial or complete removal of the dye. The results suggest that the process of formation of amyloid-like deposits may bypass the nucleation step. It is possible if the protein aggregation occurs in unidirectionally organized (because of scaffolding) assembly of molecules, arranged prior to self-association. The recognition of the structure of amphoteric Congo red nanoparticles used for the scaffolding was based on the molecular dynamics simulation.

Comparison of the effectiveness of Tenax TA and Carbotrap 300 in concentration of flammable liquids compounds.

The aim of research was to compare two adsorbents, Tenax TA and Carbotrap 300, to evaluate their usefulness as passive adsorbents of flammable liquids compounds. It was also to determine whether Carbotrap 300 could be used in a passive adsorption mode, contrary to manufacturer recommendations. To compare the adsorption properties and the thermal desorption efficiency for Tenax TA and Carbotrap, the components of test mixture were adsorbed and then chromatographically analyzed. The analysis was conducted by means of an automated thermal desorber coupled with a gas chromatograph and a mass spectrometer. This research established that although these adsorbents significantly differ from each other in adsorption properties, each of them can be successfully used for passive adsorption of ignitable liquids compounds. Tenax TA turned out to be more effective for the adsorption of nonpolar, high-boiling compounds, whereas Carbotrap is more effective for polar and volatile compounds. The examined adsorbents differ in their susceptibility to thermal desorption. For Carbotrap 300, after the analysis an additional treatment is required to remove the remnants of adsorbed compounds. With Tenax TA, this additional step is not necessary because the thermal desorption is sufficiently effective that this product is immediately ready for re-use.

Application of the micro-FTIR spectroscopy, Raman spectroscopy and XRF method examination of inks.

In routine examination of inks on questioned documents non-destructive analytical methods, such as microscopic and optical techniques are applied first. However, they are often insufficient to identify the inks used for the preparation of the document. In such cases, it is necessary to apply chemical methods that normally cause partial destruction of the examined material. The aim of this work was to evaluate the possibility of discrimination between inks by the use of spectrometric methods, i.e. micro-FTIR spectroscopy, Raman spectroscopy and XRF. About 70 samples of blue and black ballpoint pen and gel inks were examined. It was found that about 90% of the samples of the same type and colour could be distinguished using these methods.