Differentiating individuals through the chemical composition of their fingermarks.

Fingermark patterns are one of the oldest means of biometric identification. During this last decade, the molecules that constitute the fingermark residue have gained interest among the forensic research community to gain additional intelligence regarding its donor profile including its gender, age, lifestyle or even its pathological state. In this work, the molecular composition of fingermarks have been studied to monitor the variability between donors and to explore its capacity to differentiate individuals using supervised multi-class classification models. Over one year, fingermarks from thirteen donors have been analysed by Matrix-Assisted Laser Desorption/Ionisation Mass Spectrometry Imaging (n = 716) and mined by different machine learning approaches. We demonstrate the potential of the fingermark chemical composition to help differentiating individuals with an accuracy between 80% and 96% depending on the period of sample collection for each donor and size of the pool of donors. It would be premature at this stage to transpose the results of this research to real cases, however the conclusions of this study can provide a better understanding of the variations of the chemical composition of the fingermark residue in between individuals over long periods and help clarifying the notion of donorship.

Chemical composition of the fingermark residue: Assessment of the intravariability over one year using MALDI-MSI.

These past years, the chemical composition of fingermarks have attracted interest of researchers to meet multiple objectives like the determination of an individual's age, gender or lifestyle or the impact of some fingermark detection processes, to cite a few. These studies have highlighted the need to investigate the consistency of the fingermark composition over time. This research explores the evolution of the secretion residue composition of thirteen donors over one year, focusing on the intravariability. The dual use of Matrix-Assisted Laser Desorption/Ionisation Mass Spectrometry Imaging (MALDI-MSI) and chemometrics provided valuable data regarding the evolution of composition over time as well as the consistency of presence of hundreds of compounds.

Influence of the printing process on the traces produced by the discharge of 3D-printed Liberators.

Since its introduction in 1986, 3D printing technology is in constant development. 3D printers are becoming more and more performant and accessible. In 2013, the Liberator blueprints are released online. This single-shot pistol can be entirely manufactured using a 3D printer, except for the firing pin and the ammunition. First, this research aims at establishing an overview of all the elements and traces potentially present when a 3D-printed firearm is involved, whether it is fired or not. In the second part, we study these elements for exploitability to obtain information about the manufacture of the firearm (printing processes, 3D printers and polymers). For this purpose, a total of 36 Liberators were manufactured using different printing conditions (i.e., printing processes, printers, polymers and parameters). The tested printing processes were based on the principles of Material Extrusion (ME), Vat Photopolymerization (VP) and Powder Bed Fusion (PBF). All 3D-printed firearms manufactured via ME and PBF were able to fire whereas Liberators manufactured by VP printing could not be fired. This could be explained by the lack of precision of the prints making it impossible to assemble some of the Liberators, or by the fact that the polymer was not suitable to produce the springs. All the barrels were broken by the discharge, projecting polymer pieces or fragments into the environment. These polymer pieces or fragments were examined to determine which printing process was used as well as other elements related to printing parameters and conditions (e.g., layer height, filling pattern and infill density). This information is useful to determine whether a certain command file, slicer or 3D printer could be at the source of a questioned 3D-printed firearm. Melted polymer or polymer particles on elements of ammunition may also be present after the firing process. However, the examination of these particles does not allow inferring other information, except the possible use of a 3D-printed polymer firearm.

Development of a printed quality control test strip for the analysis and imaging of fingermark composition.

In the last decade, there have been many scientific developments regarding the use of mass spectrometry to analyse the composition of fingermarks. In this context, the development of a dedicated quality control test strip would benefit the forensic community by providing a way to assess the reproducibility of the measures as well as to perform inter-laboratory comparisons. To accomplish this goal, the use of a chemical printer offers the possibility of combining a visual template with artificial fingerprint secretions. The design of the quality control test strip as well as the preliminary assessment of its performance with fingermark detection reagents and matrix-assisted laser desorption-ionisation combined with mass spectrometry imaging (MALDI-MSI) are presented in this paper. The chosen template combines two geometric patterns intended to help assess the chemical analysis (full square) and imaging (lined square) capabilities of the instrument. The artificial secretion is composed of two distinct solutions: artificial sweat and artificial sebum. The printing reproducibility and chemical homogeneity of the quality control test strips were assessed in two ways: (1) using MALDI-MSI, the printed pattern was analysed and the m/z values compared to the reference list based on the artificial secretion composition, and (2) using two common fingermark detection techniques, the printed pattern was processed using an amino acid reagent (ninhydrin) and a lipid stain (Oil Red O). Overall, the results highlight the potential of a printed quality control test strip for the assessment of the quality of fingermark detection techniques as well as the possibility of performing quality monitoring of mass-spectrometry-based techniques over time.

Detecting early myocardial ischemia in rat heart by MALDI imaging mass spectrometry.

Diagnostics of myocardial infarction in human post-mortem hearts can be achieved only if ischemia persisted for at least 6-12 h when certain morphological changes appear in myocardium. The initial 4 h of ischemia is difficult to diagnose due to lack of a standardized method. Developing a panel of molecular tissue markers is a promising approach and can be accelerated by characterization of molecular changes. This study is the first untargeted metabolomic profiling of ischemic myocardium during the initial 4 h directly from tissue section. Ischemic hearts from an ex-vivo Langendorff model were analysed using matrix assisted laser desorption/ionization imaging mass spectrometry (MALDI IMS) at 15 min, 30 min, 1 h, 2 h, and 4 h. Region-specific molecular changes were identified even in absence of evident histological lesions and were segregated by unsupervised cluster analysis. Significantly differentially expressed features were detected by multivariate analysis starting at 15 min while their number increased with prolonged ischemia. The biggest significant increase at 15 min was observed for m/z 682.1294 (likely corresponding to S-NADHX-a damage product of nicotinamide adenine dinucleotide (NADH)). Based on the previously reported role of NAD+/NADH ratio in regulating localization of the sodium channel (Nav1.5) at the plasma membrane, Nav1.5 was evaluated by immunofluorescence. As expected, a fainter signal was observed at the plasma membrane in the predicted ischemic region starting 30 min of ischemia and the change became the most pronounced by 4 h. Metabolomic changes occur early during ischemia, can assist in identifying markers for post-mortem diagnostics and improve understanding of molecular mechanisms.