Etude de la composition initiale et du vieillissement des traces digitales: vers le développement d'une méthode de datation?

«Quel est l'âge de cette trace digitale?» Cette question est relativement souvent soulevée au tribunal ou lors d'investigations, lorsque la personne suspectée admet avoir laissé ses empreintes digitales sur une scène de crime mais prétend l'avoir fait à un autre moment que celui du crime et pour une raison innocente. Toutefois, aucune réponse ne peut actuellement être donnée à cette question, puisqu'aucune méthodologie n'est pour l'heure validée et acceptée par l'ensemble de la communauté forensique. Néanmoins, l'inventaire de cas américains conduit dans cette recherche a montré que les experts fournissent tout de même des témoignages au tribunal concernant l'âge de traces digitales, même si ceux-­‐ci sont majoritairement basés sur des paramètres subjectifs et mal documentés. Il a été relativement aisé d'accéder à des cas américains détaillés, ce qui explique le choix de l'exemple. Toutefois, la problématique de la datation des traces digitales est rencontrée dans le monde entier, et le manque de consensus actuel dans les réponses données souligne la nécessité d'effectuer des études sur le sujet. Le but de la présente recherche est donc d'évaluer la possibilité de développer une méthode de datation objective des traces digitales. Comme les questions entourant la mise au point d'une telle procédure ne sont pas nouvelles, différentes tentatives ont déjà été décrites dans la littérature. Cette recherche les a étudiées de manière critique, et souligne que la plupart des méthodologies reportées souffrent de limitations prévenant leur utilisation pratique. Néanmoins, certaines approches basées sur l'évolution dans le temps de composés intrinsèques aux résidus papillaires se sont montrées prometteuses. Ainsi, un recensement détaillé de la littérature a été conduit afin d'identifier les composés présents dans les traces digitales et les techniques analytiques capables de les détecter. Le choix a été fait de se concentrer sur les composés sébacés détectés par chromatographie gazeuse couplée à la spectrométrie de masse (GC/MS) ou par spectroscopie infrarouge à transformée de Fourier. Des analyses GC/MS ont été menées afin de caractériser la variabilité initiale de lipides cibles au sein des traces digitales d'un même donneur (intra-­‐variabilité) et entre les traces digitales de donneurs différents (inter-­‐variabilité). Ainsi, plusieurs molécules ont été identifiées et quantifiées pour la première fois dans les résidus papillaires. De plus, il a été déterminé que l'intra-­‐variabilité des résidus était significativement plus basse que l'inter-­‐variabilité, mais que ces deux types de variabilité pouvaient être réduits en utilisant différents pré-­‐ traitements statistiques s'inspirant du domaine du profilage de produits stupéfiants. Il a également été possible de proposer un modèle objectif de classification des donneurs permettant de les regrouper dans deux classes principales en se basant sur la composition initiale de leurs traces digitales. Ces classes correspondent à ce qui est actuellement appelé de manière relativement subjective des « bons » ou « mauvais » donneurs. Le potentiel d'un tel modèle est élevé dans le domaine de la recherche en traces digitales, puisqu'il permet de sélectionner des donneurs représentatifs selon les composés d'intérêt. En utilisant la GC/MS et la FTIR, une étude détaillée a été conduite sur les effets de différents facteurs d'influence sur la composition initiale et le vieillissement de molécules lipidiques au sein des traces digitales. Il a ainsi été déterminé que des modèles univariés et multivariés pouvaient être construits pour décrire le vieillissement des composés cibles (transformés en paramètres de vieillissement par pré-­‐traitement), mais que certains facteurs d'influence affectaient ces modèles plus sérieusement que d'autres. En effet, le donneur, le substrat et l'application de techniques de révélation semblent empêcher la construction de modèles reproductibles. Les autres facteurs testés (moment de déposition, pression, température et illumination) influencent également les résidus et leur vieillissement, mais des modèles combinant différentes valeurs de ces facteurs ont tout de même prouvé leur robustesse dans des situations bien définies. De plus, des traces digitales-­‐tests ont été analysées par GC/MS afin d'être datées en utilisant certains des modèles construits. Il s'est avéré que des estimations correctes étaient obtenues pour plus de 60 % des traces-­‐tests datées, et jusqu'à 100% lorsque les conditions de stockage étaient connues. Ces résultats sont intéressants mais il est impératif de conduire des recherches supplémentaires afin d'évaluer les possibilités d'application de ces modèles dans des cas réels. Dans une perspective plus fondamentale, une étude pilote a également été effectuée sur l'utilisation de la spectroscopie infrarouge combinée à l'imagerie chimique (FTIR-­‐CI) afin d'obtenir des informations quant à la composition et au vieillissement des traces digitales. Plus précisément, la capacité de cette technique à mettre en évidence le vieillissement et l'effet de certains facteurs d'influence sur de larges zones de traces digitales a été investiguée. Cette information a ensuite été comparée avec celle obtenue par les spectres FTIR simples. Il en a ainsi résulté que la FTIR-­‐CI était un outil puissant, mais que son utilisation dans l'étude des résidus papillaires à des buts forensiques avait des limites. En effet, dans cette recherche, cette technique n'a pas permis d'obtenir des informations supplémentaires par rapport aux spectres FTIR traditionnels et a également montré des désavantages majeurs, à savoir de longs temps d'analyse et de traitement, particulièrement lorsque de larges zones de traces digitales doivent être couvertes. Finalement, les résultats obtenus dans ce travail ont permis la proposition et discussion d'une approche pragmatique afin d'aborder les questions de datation des traces digitales. Cette approche permet ainsi d'identifier quel type d'information le scientifique serait capable d'apporter aux enquêteurs et/ou au tribunal à l'heure actuelle. De plus, le canevas proposé décrit également les différentes étapes itératives de développement qui devraient être suivies par la recherche afin de parvenir à la validation d'une méthodologie de datation des traces digitales objective, dont les capacités et limites sont connues et documentées. -- "How old is this fingermark?" This question is relatively often raised in trials when suspects admit that they have left their fingermarks on a crime scene but allege that the contact occurred at a time different to that of the crime and for legitimate reasons. However, no answer can be given to this question so far, because no fingermark dating methodology has been validated and accepted by the whole forensic community. Nevertheless, the review of past American cases highlighted that experts actually gave/give testimonies in courts about the age of fingermarks, even if mostly based on subjective and badly documented parameters. It was relatively easy to access fully described American cases, thus explaining the origin of the given examples. However, fingermark dating issues are encountered worldwide, and the lack of consensus among the given answers highlights the necessity to conduct research on the subject. The present work thus aims at studying the possibility to develop an objective fingermark dating method. As the questions surrounding the development of dating procedures are not new, different attempts were already described in the literature. This research proposes a critical review of these attempts and highlights that most of the reported methodologies still suffer from limitations preventing their use in actual practice. Nevertheless, some approaches based on the evolution of intrinsic compounds detected in fingermark residue over time appear to be promising. Thus, an exhaustive review of the literature was conducted in order to identify the compounds available in the fingermark residue and the analytical techniques capable of analysing them. It was chosen to concentrate on sebaceous compounds analysed using gas chromatography coupled with mass spectrometry (GC/MS) or Fourier transform infrared spectroscopy (FTIR). GC/MS analyses were conducted in order to characterize the initial variability of target lipids among fresh fingermarks of the same donor (intra-­‐variability) and between fingermarks of different donors (inter-­‐variability). As a result, many molecules were identified and quantified for the first time in fingermark residue. Furthermore, it was determined that the intra-­‐variability of the fingermark residue was significantly lower than the inter-­‐variability, but that it was possible to reduce both kind of variability using different statistical pre-­‐ treatments inspired from the drug profiling area. It was also possible to propose an objective donor classification model allowing the grouping of donors in two main classes based on their initial lipid composition. These classes correspond to what is relatively subjectively called "good" or "bad" donors. The potential of such a model is high for the fingermark research field, as it allows the selection of representative donors based on compounds of interest. Using GC/MS and FTIR, an in-­‐depth study of the effects of different influence factors on the initial composition and aging of target lipid molecules found in fingermark residue was conducted. It was determined that univariate and multivariate models could be build to describe the aging of target compounds (transformed in aging parameters through pre-­‐ processing techniques), but that some influence factors were affecting these models more than others. In fact, the donor, the substrate and the application of enhancement techniques seemed to hinder the construction of reproducible models. The other tested factors (deposition moment, pressure, temperature and illumination) also affected the residue and their aging, but models combining different values of these factors still proved to be robust. Furthermore, test-­‐fingermarks were analysed with GC/MS in order to be dated using some of the generated models. It turned out that correct estimations were obtained for 60% of the dated test-­‐fingermarks and until 100% when the storage conditions were known. These results are interesting but further research should be conducted to evaluate if these models could be used in uncontrolled casework conditions. In a more fundamental perspective, a pilot study was also conducted on the use of infrared spectroscopy combined with chemical imaging in order to gain information about the fingermark composition and aging. More precisely, its ability to highlight influence factors and aging effects over large areas of fingermarks was investigated. This information was then compared with that given by individual FTIR spectra. It was concluded that while FTIR-­‐ CI is a powerful tool, its use to study natural fingermark residue for forensic purposes has to be carefully considered. In fact, in this study, this technique does not yield more information on residue distribution than traditional FTIR spectra and also suffers from major drawbacks, such as long analysis and processing time, particularly when large fingermark areas need to be covered. Finally, the results obtained in this research allowed the proposition and discussion of a formal and pragmatic framework to approach the fingermark dating questions. It allows identifying which type of information the scientist would be able to bring so far to investigators and/or Justice. Furthermore, this proposed framework also describes the different iterative development steps that the research should follow in order to achieve the validation of an objective fingermark dating methodology, whose capacities and limits are well known and properly documented.

Infrared spectroscopy of Mg-doped SrRuO3 thin films /

The reflectance of thin films of magnesium doped SrRu03(Mg-SR0) produced by pulsed laser deposition on SrTiOa (100) substrates has been measured at room temperature between 100 and 7500 cm~^. The films were chosen to have wide range of thickness, stoichiometry and electrical properties. As the films were very thin (less than 300 nm), and some were insulating the reflectance data shows structures due to both the film and the substrate. Hence, the data was analyzed using Kramers-Kronig constrained variational fitting (VDF) method to extract the real optical conductivity of the Mg-SRO films. Although the VDF technique is flexible enough to fit all features of the reflectance spectra, it seems that VDF could not eliminate the substrate's contribution from fllm conductivity results. Also the comparison of the two different programs implementing VDF fltting shows that this technique has a uniqueness problem. The optical properties are discussed in light of the measured structural and transport properties of the fllms which vary with preparation conditions and can be correlated with differences in stoichiometry. This investigation was aimed at checking the VDF technique and also getting answer to the question whether Mg^"*" substitutes in to Ru or Sr site. Analysis of our data suggests that Mg^+ goes to Ru site.

The vibrational spectra and the normal coordinate analysis of thiocarbonye halides /|nby C. R. Subramaniam. -- 260 St. Catharines, Ont. : [s. n.],

The infrared and the Raman spectra of eSelF has been obtained for the first time and has been analysed to give the in-plane normal vibrational frequencies of the molecule, in the ground state. A normal co-ordinate analysis has been carried out for the molecules CSF2, CSClF and eSel 2 using a Urey-Bradley type of potential function and the elements of the [L] matrix elements, the distribution of the potential energy in Urey-Bradley space, and the displacement vector diagrams for the normal modes of vibration for these molecules, have been obtained. The bond for~e constants obtained through the normal co-ordinate analysis, have given some interesting results. The stretching force constant, Kes ' varies markedly with halogen substitution and the force constants KeF and Keel also vary with substitution.

Laser induced thermal lens and near infrared absorption studies of ch overtones in some organic compounds

Vibrational overtone spectroscopy of X-H (X=C,N,O) containing molecules is an area of recent interest. The spectroscopic studies of higher vibrational levels yield valuable informations, regarding,the molecular structure, intra- and inter-molecular interactions, radiationless transitions, intra-molecular vibrational relaxations, multiphoton excitations and chemical reactivities, which cannot be z obtained by other spectroscopic methods. This thesis presents the results of experimental investigations on the overtone spectra of some organic compounds in the liquid phase for the characterization of CH bonds. The spectra in the fifth overtone region (1fiV=6) are recorded using a dual beam thermal lens setup and the lower overtones (.AV=2-5) are recorded spectrophotometrically.The thesis is presented in six chapters.

Vibration-rotation spectra of CH3F

Rotational structure has been resolved and analyzed in the 1049-cm−1 parallel fundamental and the 1182 cm−1 perpendicular fundamental bands in the infrared spectrum of the CH3F molecule. Combination bands at 2223 cm−1 and around 2650 cm−1 have also been studied. The effective resolving power of the spectrometer was 0.25 cm−1 for all these bands. The two long-wavelength fundamentals have been analyzed in much greater detail than in previous work, and a complete analysis of the perpendicular band has been made, including the J-structure in the P and R branches of the sub-bands. Rotational constants of CH3F determined in this work and elsewhere are summarized in Table XIII of the text. Some anomalous intensity perturbations in the rotation lines of the 1182-cm−1 fundamental have been observed, and are discussed.

The vibrational spectra of natural and perdeuterated monochlorogallane, H2Ga([mu]-Cl)2GaH2, and an empirical harmonic potential function

The infrared and Raman spectra of monochlorogallane and its fully deuterated isotopomer are recorded and assigned on the basis of the dimeric structures. H2Ga(μ-Cl)2GaH2 and D2Ga(μ-Cl)2GaD2, conforming to D2 symmetry. The observed frequencies are corrected for anharmonicity and fitted to a potential function in which 19 of the 33 independent force constants are refined.

Understanding spectra of highly excited vibrational states

Some of the characteristics of high overtone spectra observed in the near infrared are discussed, particularly in relation to local mode effects, the increasing density of states, and the effect of inter-state resonances and intramolecular vibrational redistribution.

The infrared spectrum of the ν2 and ν3 bands of H16OF, H18OF, and D16OF

Fourier transform IR spectra in the ν2 and ν3 regions between 800 and 1500 cm−1 have been measured of H16OF with a resolution of 0.007 cm−1 and of H18OF and DOF with a resolution of 0.040 cm−1. Ground state constants have been improved for H16OF and have been obtained for the first time for H18OF. Parameters of the v2 = 1 and v3 = 1 excited states have been determined from rovibrational analyses of ca. 1000 ν2/ν3 lines which were fitted with σ 0.36, 4.5, and 7.6 × 10−3 cm−1 for H16OF, H18OF, and D16OF, respectively. Band centers of ν2/ν3 are 1353.40466(5)/889.07974(6), 1350.3976(5)/862.2967(7), and 1002.0083(9)/891.0014(15) cm−1, respectively, for the three isotopic species. While ν2 and ν3 are sufficiently separated in HOF to be treated independently, a Coriolis resonance is evident in DOF, the interaction constant ξ23c = 0.19073(16) cm−1 being in agreement with the prediction from the harmonic force field.

Developments in near infrared spectroscopy

Vibrational spectroscopy at high excitation is an important research frontier for two reasons. Firstly, the near infrared is proving to be an important area for the analytical applications of spectroscopy, and we would therefore like to understand how the spectra we observe relate to the molecular structure of the absorbing species. Secondly, there is a fundamental interest in understanding molecular dynamics and energy flow within a polyatomic molecule at high excitation, because this is the boundary between spectroscopy and chemistry through which we try to understand the details of a chemical reaction. In this presentation I shall survey recent progress in this field.

Whole crop cereals 2. Prediction of apparent digestibility and energy value from in vitro digestion techniques and near infrared reflectance spectroscopy and of chemical composition by near infrared reflectance spectroscopy

Samples of whole crop wheat (WCW, n = 134) and whole crop barley (WCB, n = 16) were collected from commercial farms in the UK over a 2-year period (2003/2004 and 2004/2005). Near infrared reflectance spectroscopy (NIRS) was compared with laboratory and in vitro digestibility measures to predict digestible organic matter in the dry matter (DOMD) and metabolisable energy (ME) contents measured in vivo using sheep. Spectral models using the mean spectra of two scans were compared with those using individual spectra (duplicate spectra). Overall NIRS accurately predicted the concentration of chemical components in whole crop cereals apart from crude protein. ammonia-nitrogen, water-soluble carbohydrates, fermentation acids and solubility values. In addition. the spectral models had higher prediction power for in vivo DOMD and ME than chemical components or in vitro digestion methods. Overall there Was a benefit from the use of duplicate spectra rather than mean spectra and this was especially so for predicting in vivo DOMD and ME where the sample population size was smaller. The spectral models derived deal equally well with WCW and WCB and Would he of considerable practical value allowing rapid determination of nutritive value of these forages before their use in diets of productive animals. (C) 2008 Elsevier B.V. All rights reserved.

Ultrafast charge separation in a photoreactive rhenium-appended porphyrin assembly monitored by picosecond transient infrared spectroscopy

Rhenium(bipyridine)(tricarbonyl)(picoline) units have been linked covalently to tetraphenylmetalloporphyrins of magnesium and zinc via an amide bond between the bipyridine and one phenyl substituent of the porphyrin. The resulting complexes, abbreviated as [Re(CO)(3)(Pic)Bpy-MgTPP][OTf] and [Re(CO)(3)(Pic)Bpy-ZnTPP][OTf], exhibit no signs of electronic interaction between the Re(CO)(3)(bpy) units and the metalloporphyrin units in their ground states. However, emission spectroscopy reveals solvent-dependent quenching of porphyrin emission on irradiation into the long-wavelength absorption bands localized on the porphyrin. The characteristics of the excited states have been probed by picosecond time-resolved absorption (TRVIS) spectroscopy and time-resolved infrared (TRIR) spectroscopy in nitrile solvents. The presence of the charge-separated state involving electron transfer from MgTPP or ZnTPP to Re(bpy) is signaled in the TRIR spectra by a low-frequency shift in the nu(CO) bands of the Re(CO)(3) moiety similar to that observed by spectroelectrochemical reduction. Long-wavelength excitation of [Re(CO)(3)(Pic)Bpy-MTPP][OTf] results in characteristic TRVIS spectra of the S-1 state of the porphyrin that decay with a time constant of 17 ps (M = Mg) or 24 ps (M = Zn). The IR bands of the CS state appear on a time scale of less than 1 ps (Mg) or ca. 5 ps (Zn) and decay giving way to a vibrationally excited (i.e., hot) ground state via back electron transfer. The IR bands of the precursors recover with a time constant of 35 ps (Mg) or 55 ps (Zn). The short lifetimes of the charge-transfer states carry implications for the mechanism of reaction in the presence of triethylamine.

Space exposure of infrared filters and materials on the NASA Long Duration Exposure Facility (LDEF)

Infrared optical-multilayer filters and materials were exposed to the space environment of low Earth for a period of nearly six years on the NASA Long Duration Exposure Facility (LDEF) mission. This report describes the effects of that environment on the physical and optical properties of filters and materials used in an experiment designed by the University of reading Infrared multilayer Laboratory. Results of the experiment comprise IR processed spectra both before (1983), and after (1990) exposure, in conjunction with unexposed control samples.

Infrared linear dichroism spectroscopy on amyloid fibrils aligned by molecular combing

We report the use of molecular combing as an alignment method to obtain macroscopically oriented amyloid fibrils on planar surfaces. The aligned fibrils are studied by polarized infrared spectroscopy. This gives structural information that cannot be definitively obtained from standard infrared experiments on isotropic samples, for example, confirmation of the characteristic cross-beta amyloid core structure, the side-chain orientation from specific amino acids, and the arrangement of the strands within the fibrils, as we demonstrate here. We employed amyloid fibrils from hen egg white lysozyme (HEWL) and from a model octapeptide. Our results demonstrate molecular combing as a straightforward method to align amyloid fibrils, producing highly anisotropic infrared linear dichroism (IRLD) spectra.

Water vapour continuum absorption in near-infrared windows derived from laboratory measurements

In most near-infrared atmospheric windows, absorption of solar radiation is dominated by the water vapor self-continuum and yet there is a paucity of measurements in these windows. We report new laboratory measurements of the self-continuum absorption at temperatures between 293 and 472 K and pressures from 0.015 to 5 atm in four near-infrared windows between 1 and 4 m (10000-2500 cm-1); the measurements are made over a wider range of wavenumber, temperatures and pressures than any previous measurements. They show that the self-continuum in these windows is typically one order of magnitude stronger than given in representations of the continuum widely used in climate and weather prediction models. These results are also not consistent with current theories attributing the self continuum within windows to the far-wings of strong spectral lines in the nearby water vapor absorption bands; we suggest that they are more consistent with water dimers being the major contributor to the continuum. The calculated global-average clear-sky atmospheric absorption of solar radiation is increased by 0.75 W/m2 (which is about 1% of the total clear-sky absorption) by using these new measurements as compared to calculations with the MT_CKD-2.5 self-continuum model.