Chemical characterisation and classification of forensic trace evidence

Automotive paint, in the form of paint chips and/or smears, is one of the most commonly encountered forms of forensic trace evidence located at automotive related incidents. There is an increasing demand for more scientifically rigorous approaches to the interpretation of such evidence. This dissertation presents studies examining the use of a suite of spectroscopic techniques in conjunction with multivariate statistics, in order to develop analytical and interpretational protocols for automotive paint evidence

Synchrotron FTIR characterisation of automotive primer surfacer paint coatings for forensic purposes

Synchrotron FTIR microspectroscopy was used to characterise and assess the chemical diversity of electrocoat primer, primer surfacer and basecoats of automotive paint samples from 75 vehicles representing a range of international car manufacturers. Significant diversity was found in the synchrotron FTIR data from the primer surfacer coats. Classification using principal component analysis revealed 14 discrete groups, which could be associated with the country of manufacture, the specific manufacturer and manufacturing plant, the year of manufacture of the vehicle and in some instances the number of layers in the paint system. The model generated from the primer surfacer was significantly more discriminating than a previous model generated from FTIR analysis of clear coats of the same vehicles. Analysis of the primer surfacer also avoids issues of possible environmental degradation and component migration seen with FTIR analysis of automotive clear coats. Providing such information concerning vehicle origin would aid in the development of investigative leads from the analysis of questioned automotive paint samples located at the scene of a crime or on the body/clothing of a hit and run victim

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

Structure elucidation and characterization of patulin synthase, insights into the formation of a fungal mycotoxin

Patulin synthase (PatE) from Penicillium expansum is a flavin-dependent enzyme that catalyses the last step in the biosynthesis of the mycotoxin patulin. This secondary metabolite is often present in fruit and fruit-derived products, causing postharvest losses. The patE gene was expressed in Aspergillus niger allowing purification and characterization of PatE. This confirmed that PatE is active not only on the proposed patulin precursor ascladiol but also on several aromatic alcohols including 5-hydroxymethylfurfural. By elucidating its crystal structure, details on its catalytic mechanism were revealed. Several aspects of the active site architecture are reminiscent of that of fungal aryl-alcohol oxidases. Yet, PatE is most efficient with ascladiol as substrate confirming its dedicated role in biosynthesis of patulin.</p

Classification of polyethylene cling films by attenuated total reflectance-Fourier transform infrared spectroscopy and chemometrics

Attenuated total reflectance-Fourier transform infrared spectroscopy (ATR-FTIR) was utilised to analyse nine differently branded cling films. Principal component analysis (PCA) was used to assess the intra-sample variability, i.e. the variation within individual cling film rolls; as well as the inter-sample variability, which explores the variability between different rolls of cling film. Linear discriminant analysis (LDA) was then employed to develop a predictive classification model which gave 100% correct differentiation between three brand groupings of cling film, and accurately classified all of the validation samples obtained from different rolls from the same manufacturers

Endogenous antigen processing drives the primary CD4+ T cell response to influenza.

By convention, CD4+ T lymphocytes recognize foreign and self peptides derived from internalized antigens in combination with major histocompatibility complex class II molecules. Alternative pathways of epitope production have been identified, but their contributions to host defense have not been established. We show here in a mouse infection model that the CD4+ T cell response to influenza, critical for durable protection from the virus, is driven principally by unconventional processing of antigen synthesized within the infected antigen-presenting cell, not by classical processing of endocytosed virions or material from infected cells. Investigation of the cellular components involved, including the H2-M molecular chaperone, the proteasome and γ-interferon-inducible lysosomal thiol reductase revealed considerable heterogeneity in the generation of individual epitopes, an arrangement that ensures peptide diversity and broad CD4+ T cell engagement. These results could fundamentally revise strategies for rational vaccine design and may lead to key insights into the induction of autoimmune and anti-tumor responses

MRI Indices of Cortical Development in Young People With Psychotic Experiences: Influence of Genetic Risk and Persistence of Symptoms

Background Psychotic experiences (PEs) are considered part of an extended psychosis phenotype and are associated with an elevated risk of developing a psychotic disorder. Risk of transition increases with persistence of PEs, and this is thought to be modulated by genetic and environmental factors. However, it is unclear if persistence is associated with progressive schizophrenia-like changes in neuroanatomy. Methods We examined cortical morphometry using MRI in 247 young adults, from a population-based cohort, assessed for the presence of PEs at ages 18 and 20. We then incorporated a polygenic risk score for schizophrenia (PRS) to elucidate the effects of high genetic risk. Finally, we used atlas-based tractography data to examine the underlying white matter. Results Individuals with persisting PEs showed reductions in gyrification (local gyrification index: lGI) in the left temporal gyrus as well as atypical associations with brain volume (TBV) in the left occipital and right prefrontal gyri. No main effect was found for the PRS, but interaction effects with PEs were identified in the orbitofrontal, parietal, and temporal regions. Examination of underlying white matter did not provide strong evidence of further disturbances. Conclusions Disturbances in lGI were similar to schizophrenia but findings were mostly limited to those with persistent PEs. These could reflect subtle changes that worsen with impending psychosis or reflect an early vulnerability associated with the persistence of PEs. The lack of clear differences in underlying white matter suggests our findings reflect early disturbances in cortical expansion rather than progressive changes in brain structure