Revealing the spatial distribution of chemical species within latent fingermarks using vibrational spectroscopy.

Latent fingermarks are an important form of crime-scene trace evidence and their usefulness may be increased by a greater understanding of the effect of chemical distribution within fingermarks on the sensitivity and robustness of fingermark detection methods. Specifically, the relative abundance and micro-distribution of sebaceous (lipophilic) and eccrine (hydrophilic) material in fingermarks have long been debated in the field, yet direct visualisation of relative abundance and micro-distribution was rarely achieved. Such a visualisation is nonetheless essential to provide explanations for the variation in reproducibility or robustness of latent fingermark detection with existing methods, and to identify new strategies to increase detection capabilities. In this investigation, we have used SR-ATR-FTIR and confocal Raman microscopy to probe the spatial micro-distribution of the sebaceous and eccrine chemical components within latent fingermarks, deposited on non-porous surfaces. It was determined that fingermarks exhibit a complex spatial distribution, influenced by the ratio of lipophilic to aqueous components, and to a first approximation resemble a water-in-oil or oil-in-water emulsion. Detection of a substantial lipid component in "eccrine enriched fingermarks" (wherein hands are washed to remove lipids) is noteworthy, as it provides a potential explanation for several scenarios of unexpected fingermark detection using methods previously thought unsuitable for "eccrine deposits". Furthermore, the pronounced distribution of lipids observed in natural fingermark deposits was intriguing and agrees with recent discussion in this research field that natural fingermarks contain a much higher lipid content than previously thought.

Deuterated polymers for probing phase separation using infrared microspectroscopy.

Infrared (IR) microspectroscopy has the capacity to determine the extent of phase separation in polymer blends. However, a major limitation in the use of this technique has been its reliance on overlapping peaks in the IR spectra to differentiate between polymers of similar chemical compositions in blends. The objective of this study was to evaluate the suitability of deuteration of one mixture component to separate infrared (IR) absorption bands and provide image contrast in phase separated materials. Deuteration of poly(3-hydroxyoctanoate) (PHO) was achieved via microbial biosynthesis using deuterated substrates, and the characteristic C-D stretching vibrations provided distinct signals completely separated from the C-H signals of protonated poly(3-hydroxybutyrate) (PHB). Phase separation was observed in 50:50 (% w/w) blends as domains up to 100 µm through the film cross sections, consistent with earlier reports of phase separation observed by scanning electron microscopy (SEM) of freeze-fractured protonated polymer blends. The presence of deuterated phases throughout the film suggests there is some miscibility at smaller length scales, which increased with increasing PHB content. These investigations indicate that biodeuteration combined with IR microspectroscopy represents a useful tool for mapping the phase behavior of polymer blends.

A spectroscopic study of nicotine analogue 2-phenylpyrrolidine (PPD) using resonant two-photon ionization (R2PI), microwave, and 2D NMR techniques.

Conformational preferences of the nicotine analogue 2-phenylpyrrolidine (PPD) have been studied in both gaseous and solution phases. Theoretical calculations at the MP2 and B3LYP levels point to 5-6 stable conformers which differ in three degrees of conformational freedom; torsion between the two rings, inversion at the pyrrolidine (PY) amine, and PY ring puckering, characterized using the Cremer-Pople definition for pseudorotation. Only one conformer has a trans arrangement between the amino hydrogen and the phenyl substituent. It is 6-8 kJ mol(-1) more stable than the cis conformers, has a perpendicular ring arrangement, and puckers at the nitrogen atom--similar to structures reported for nicotine. Resonant two-photon ionization (R2PI) data, including hole burn spectra, indicate only one conformer is present in the free jet expansion, and band contour analysis suggests assignment to the trans conformer. Confirmation was provided by microwave spectroscopy. Fifty-seven lines measured in the 48-72 GHz region were assigned to 206 b-type transitions and fitted to yield rotational constants within 2 MHz of MP2 values predicted for the trans conformer. The solution-phase conformers of PPD were studied using 1D and 2D (1)H NMR spectroscopy and solvent-based theoretical calculations. In marked contrast to the gas phase, NMR data reveals only cis conformers present in solution. Calculations confirm increased stability for these conformers when placed in simulated chloroform or water environments. Solvent molecules are believed to disrupt a crucial N...H(ortho) stabilizing interaction present within the trans conformer.

Characterisation of chemical component migration in automotive paint by synchrotron infrared imaging.

Synchrotron infrared chemical imaging was employed to examine and assess the extent of interlayer component migration within multilayer automotive paint samples, with a particular emphasis on the cross-linking additive melamine. Two dimensional infrared chemical images revealed that melamine consistently diffuses in select paint samples from the underlying basecoat into the outermost clear coat layer. Pigments from the basecoat were also found to migrate into the adjoining layers. This is significant as the relative abundance of both melamine and pigments will vary greatly depending upon the region of the layer analysed. This component migration will undoubtedly impact the information gleaned from a questioned sample via library searching software or multivariate statistics. As a result, appropriate analytical protocols will need to be utilised to mitigate the effects of interlayer pigment and melamine diffusion, so as to afford a true representation of the composition of the coating for forensic identification purposes.

Resonant 2-photon ionization study of the conformation and the binding of water molecules to 2-phenylethanethiol (PhCH2CH2SH).

The structures of 2-phenylethanethiol (PET, PhCH(2)CH(2)SH) and its 1:1 water clusters have been studied using resonant two-photon ionization spectroscopy including band contour analysis and UV-UV holeburning, combined with extensive ab initio calculations on ground and excited states. The most populated conformer, labeled Ggpi, has a gauche arrangement about the SCCC and HSCC bonds that permits a stabilizing SH...dpi type of hydrogen bond. The other observed conformer, Ag, is anti with respect to the SCCC bond. In the dominant 1:1 water cluster, a water molecule binds to the Ggpi conformer via an OH...S hydrogen bond and two significant CH...O interactions. There is also evidence for water binding to conformer Ag with a similar arrangement, and for a second Ggpi cluster where water inserts between the SH and the aromatic ring. The additional interactions to the water molecules result in net D(e) binding energies approximately double those resulting from a single thiol-water hydrogen bond. The (1)(pi,pi(*)) excited state lifetimes in the bare molecules are very short because of internal conversion to a dissociative (1)(n,pi(*)) state related to the thiol. In the dominant Gw(1) cluster, the lifetime is significantly increased from <1 to approximately 4 ns. Hydrogen bonding to the thiol, which raises the energy of the dissociative (1)(n,pi(*)) state, accounts for this behavior.

Resonant two-photon ionization and ab initio conformational analysis of haloethyl benzenes (PhCH(2)CH(2)X,X=Cl,F).

The S(1) <-- S(0) transitions of the gaseous (2-fluoroethyl)-benzene (FEB) and (2-chloroethyl)-benzene (CEB) have been investigated using a combination of two-color resonant two-photon ionization and UV-UV hole burning spectroscopy. Both anti and gauche conformers have been identified on the basis of rotational band contour analysis supported by ab initio calculations on the ground and electronically excited states. The gauche origin band of FEB at 37,673 cm(-1) is redshifted 50 cm(-1) relative to the corresponding anti origin, while CEB origin bands overlap at 37,646 cm(-1). Relative conformational stability and populations in the jet have been estimated for both molecules, based on the intensity ratio of S(1) <-- S(0) band origin transitions. These are compared with a range of related molecules with the structural motif PhCH(2)CH(2)X (X=CH(3),CH(2)CH(3),NH(2),OH,COOH,CCH,CN). Theory and experimental results for FEB and CEB show repulsive interactions between the halogen substituents and the pi cloud of the phenyl rings destabilizing the gauche conformers, but the preference for the anti conformers is relatively modest. The gauche conformer origins show very different hybrid character: FEB is largely b type, while CEB is an ac hybrid in keeping with theoretically computed TM "rotations" (theta(elec)) of -7 degrees and -56 degrees , respectively. This difference is attributed largely to rotation of the side chain in opposite directions about the C(1)C(alpha) bond. Spectra of FEB(H(2)O) and CEB(H(2)O) single water clusters show evidence of an anti conformation in the host molecule.