Forensic analysis of automotive paints by Raman spectroscopy

In this work, the possible contribution of Raman spectroscopy in forensic science is evaluated, more specifically for the analysis of automotive paint samples. Spectra from paint flakes as well as from cross sections were examined, in order to identify not only the pigments but also binders and extenders in all paint layers. Moreover, the possibility of distinguishing paint samples from different cars was evaluated to assess the use of vibrational spectroscopic techniques in the investigation of a hit-and-run accident. The presence of rutile and extenders, such as calcite and barium sulphate, could be demonstrated by their characteristic Raman bands. However, the identification of the binder by Raman spectroscopy was hampered: only with additional information from IR analysis could most of the bands in the spectrum be assigned to molecular vibrations of the binders. In contrast, organic pigments, having very distinctive and well-resolved characteristic bands, could easily be identified by comparing the spectra from the basecoat of the sample with spectra from a reference database. Because of these characteristic bands, the basecoat seems to provide the best spectra to distinguish paint samples. Moreover, some paints can also be distinguished by the absence or presence of the bands from calcium carbonate and barium sulphate in the primer surfacer. When recording spectra from paint flakes, Raman bands from the spectra of the clearcoat as well as from the basecoat are obtained. Copyright © 2005 John Wiley & Sons, Ltd.     

Natural and Synthetic Xanthones as Monoamine Oxidase Inhibitors: Biological Assay and 3D‐QSAR

Fifty‐nine xanthones (=9H‐xanthen‐9‐ones) of natural or synthetic origin were investigated for their inhibitory activity toward monoamine‐oxidase A (MAO‐A) and MAO‐B. The compounds demonstrated reversible, time‐independent activities, with selectivity toward MAO‐A. The most active inhibitor had an IC₅₀ of 40 nM . Electron absorption spectroscopy revealed the formation of a 1 : 1 charge‐transfer complex between lumiflavine and xanthones. 3D‐QSAR Studies according to the CoMFA/GOLPE procedure provided information on the relationship between steric and electrostatic fields and MAO‐A inhibition. The ALMOND procedure yielded additional topographical information on structural factors favoring activity.     

Surface organization of hyperbranched polymer molecules,as studied by atomic force microscopy

The recent emergence of hyperbranched polymers has opened the door for the design of a large variety of novel, well‐controlled chain architectures. For instance, «comb‐like» and “dendritic‐like” polymers can be obtained from hyperbranched poly(chloroethyl vinyl ether)‐g‐polystyrene (PCEVE‐g‐PS) copolymers, with excellent control over the dimensions of the polystyrene lateral branches and the PCEVE backbone. In this work, the nanometer scale organization of these materials is studied by means of Tapping Mode Atomic Force Microscopy. We focus on the influence of the intrinsic molecular architecture of the hyperbranched PCEVE‐g‐PS on the organization of the material. In the case of thin deposits, we observe a layer‐by‐layer organization. On the free surface, it is possible to image single polymer molecules and to analyze their size in terms of polymer molecular weight. In most cases, the molecules are found to adopt an extended conformation and to form lamellar arrangements. We observe that the degree of lateral ordering of these molecules strongly depends on their intrinsic architecture.     

Three-dimensional centrifugal instabilities development inside a parallelepipedic open cavity of various shape

This experimental study reports flow developments inside a parallelepipedic cavity of variable shape and dimensions. That flow is generated by the interaction between a laminar boundary layer and the cavity, which creates shear-layer oscillations. The aim is to understand the three-dimensional flow morphology varying the Reynolds number and the cavity shape. Flow visualizations are obtained in a plane situated inside the cavity in order to get the dynamical structures. Dimensional analysis of the cavity flow teaches that three dimensionless numbers are necessary for the flow reduction. This is confirmed by experimental results pointing thresholds of appearance of instabilities identified for some combinations of Reynolds number and geometric parameters. The key mechanisms for their existence are centrifugal effects induced by a vortex of spanwise axis with sufficient intensity, and viscous effects due to the wall confinement of the cavity. Their destruction is linked to flow transition to turbulence above a limiting convective velocity generated by the vortex of spanwise axis. These instabilities are generally present in a spanwise row of counter-rotating pairs of vortices, but for some cases, isolated pairs are also identified. Secondary modulations of primary instabilities are also present for particular parameters. Results permit to discriminate the relevant scales associated with the shear layer and the inner cavity flow.     

2,2,5,5,8,8‐Hexa­methyl‐2,3,5,6,7,8‐hexa­hydro­imidazo­[1,2‐a]­pyrazine‐3,6‐dione,a bicyclic product of α‐amino­isobutyric acid condensation

The title compound, C₁₂H₁₉N₃O₂, is an unusual product of silica‐catalyzed intermolecular condensation of α‐amino­isobutyric acid. The mol­ecule has three types of C—N bonds: a double bond, a cis‐amide bond and single bonds, two of which are typical and two having intermediate lengths due to π‐electron delocalization between C=N and C=O groups. The cis‐amide moieties interact to form dimers via hydrogen bonds which stack in parallel layers.     

Affine translation surfaces with constant sectional curvature

In this paper we characterize affine translation surfaces with constant Gaussian curvature. We show that such surfaces must be flat and that one of the defining curves must be planar.     

Recent trends in trace element determination and speciation using inductively coupled plasma mass spectrometry

During the past decade, inductively coupled plasma mass spectrometry (ICPMS) has evolved from a delicate research tool, intended for the well-trained scientist only, into a more robust and well-established analytical technique for trace and ultra-trace element determination, with a few thousand of instruments used worldwide. Despite this immense success, it should be realized that in its ’standard configuration’– i.e. equipped with a pneumatic nebulizer for sample introduction and with a quadrupole filter – ICPMS also shows a number of important limitations and disadvantages: (i) the occurrence of spectral interferences may hamper accurate trace element determination, (ii) solid samples have to be taken into solution prior to analysis and (iii) no information on the ‘chemical form’ in which an element appears can be obtained. Self-evidently, efforts have been and still are made to overcome the aforementioned limitations to the largest possible extent. The application of a double focusing sector field mass spectrometer in ICPMS instrumentation offers a higher mass resolution, such that spectral overlap can be avoided to an important extent. Additionally, in a sector field instrument, photons are efficiently eliminated from the ion beam, resulting in very low background intensities, making it also very well-suited for extreme trace analysis. Also the combination of the ICP as an ion source and a quadrupole filter operated in a so-called ‘alternate’ stability region, an ion trap or a Fourier transform ion cyclotron resonance mass spectrometer allows high(er) mass resolution to be obtained. With modern quadrupole-based instruments, important types of spectral interferences can be avoided by working under ‘cool plasma’ conditions or by applying a collision cell. The use of electrothermal vaporization (ETV) or especially laser ablation (LA) for sample introduction permits direct analysis of solid samples with sufficient accuracy for many purposes. The application range of LA-ICPMS has become very wide and the introduction of UV lasers has led to an improved spatial resolution. Solid sampling ETV-ICPMS on the other hand can be used for some specific applications only, but accurate calibration is more straightforward than with LA-ICPMS. Limited multi-element capabilities, resulting from the transient signals observed with ETV or single shot LA, can be avoided by the use of a time-of-flight (TOF) ICPMS instrument. Finally, when combined with a powerful chromatographic separation technique, an ICP-mass spectrometer can be used as a highly sensitive, element-specific multi-element detector in elemental speciation studies. Especially liquid (HPLC-ICPMS) and – to a lesser extent – gas (GC-ICPMS) chromatography have already been widely used in combination with ICPMS. In speciation work, sample preparation is often observed to be troublesome and this aspect is presently receiving considerable attention. For GC-ICPMS, new sample pretreatment approaches, such as headspace solid phase microextraction (headspace SPME) and the purge-and-trap technique have been introduced. Also supercritical fluid chromatography (SFC) and capillary electrophoresis (CE) show potential to be of use in combination with ICPMS, but so far the application ranges of SFC-ICPMS and CE-ICPMS are rather limited. It is the aim of the present paper to concisely discuss the aforementioned recent ’trends’ in ICPMS, using selected real-life applications reported in the literature.     

Three Dimensional Affine Hyperspheres Generated by Two Dimensional Partial Differential Equations

It is well‐known that locally strongly convex affine hyperspheres can be determinedas solutions of differential equations of Monge‐Ampère type. In this paper we study in particular the 3‐dimensional case and we assume that the hypersphere admits a Killing vector field (with respect to the affine metric) whose integral curves are geodesics with respect to both the induced affine connection and the Levi‐Civita connection of the affine metric. We show that besides the already known examples, such hyperspheres can be constructed starting from the 2‐dimensional Poisson equation, the 2‐dimensional sine‐Gordon equation or the 2‐dimensional cosh‐Gordon equation.