Chemometric study on the forensic discrimination of soil types using their infrared spectral characteristics

Soil has been utilized in criminal investigations for some time because of its prevalence and transferability. It is usually the physical characteristics that are studied, however the research carried out here aims to make use of the chemical profile of soil samples. The research we are presenting in this work used sieved (2mm) soil samples taken from the top soil layer (about 10cm) that were then analysed using mid infrared spectroscopy. The spectra obtained were pre-treated and then input into two chemometric classification tools: Nonlinear iterative partial least squares followed by linear discriminant analysis (NIPALS-LDA) and partial least squares discriminant analysis (PLS-DA). The models produced show that it is possible to discriminate between soil samples from different land use types and both approaches are comparable in performance. NIPALS-LDA performs much better than PLS-DA in classifying samples to locatio

The forensic analysis of soil by FTIR with multivariate analysis

Over the past few years more and more studies have been carried out in an attempt to utilize chemical profiles of soil using a wide variety of analytical methods. The value of soil as evidence rests with its prevalence at crime scenes and its transferability between the scene and the criminal. This can be of value for comparison if the scene of crime is known, but could also be so in the identification of a scene. The main basis for the comparison of sites to determine provenance is that soils vary from one place to another. The aim of this work is to find simple methods to identify soil provenance based on FTIR and multivariate analysi

The effect of household corrosive substances on latent fingermark development in the context of deliberate corrosive substance attacks

Corrosive substance attacks (CSA) are a prevalent issue in the UK with 525 offenses involving a corrosive substance reported to the police in the year ending March 2022. Easy availability, low cost, and concealability in public are common reasons for choosing a corrosive substance as a weapon. The Metropolitan Police revealed that 68% of 1849 CSA cases resulted in no suspect identified or evidential difficulties. There is limited research into the effect of corrosive substances on latent fingermarks. This study aimed to determine the potential for fingermarks to be recovered from surfaces exposed to a household corrosive substance within the context of a deliberate CSA. Natural and sebaceous-loaded fingermarks were exposed to Domestos bleach, Harpic limescale remover (hydrochloric acid-based) and lemon juice. Harpic limescale remover had the most detrimental effect, with only 7.1% of fingermarks (n = 378) exposed being identifiable (defined as sufficient clear ridge detail for identification) after enhancement, followed by bleach with only 10.3% of fingermarks (n = 378) identifiable. Lemon juice had the least detrimental effect on fingermarks, with 40.5% fingermarks (n = 378) identifiable compared to 53.4% for the controls (not exposed to any substance; n = 378). Throughout the study, fewer natural fingermarks were identifiable after exposure to corrosive substances compared to sebaceous fingermarks which was as expected. Overall, this study demonstrated that there is potential to recover latent fingermarks, depending on their composition, following exposure to a household corrosive substance. This area warrants further research to establish best practice to maximize the potential to recover identifiable fingermarks

Microcrystalline identification of selected designer drugs

A microcrystalline test for the detection of 4-methylmethcathinone (mephedrone), benzylpiperazine (BZP) and 5,6-methylenedioxy-2-aminoindane (MDAI) using aqueous solutions of mercury chloride is described. Each of the compounds investigated formed specific drug–reagent crystals within minutes. The uniqueness of the test was confirmed by comparison of the microcrystalline response to that of other psychoactive stimulants and a common cutting agent. The limit of detection and cut-off levels for reference standards were established to 3 g/L and 5 g/L for mephedrone, 0.5 g/L for MDAI and 0.2 g/L and 0.3 g/L for BZP, respectively. Various mixtures of standards of either mephedrone, BZP or MDAI combined with caffeine were investigated for their microcrystalline response. Results showed that simultaneous detection of drug and cutting agent was possible with the concentrations tested but were dependant on the ratio of drug to cutting agent. BZP could be detected alongside caffeine from as low as 20% (v/v), MDAI from 40% (v/v) and mephedrone from 50% (v/v) and higher. Finally, seven samples of online purchased ‘legal highs’ were analysed using the developed test and the findings were compared to FTIR and GC–MS results. It was shown that 6 out of 7 samples did not contain the advertised active ingredient. Five samples consisted of BZP, caffeine and 1-[3-(trifluoromethyl)phenyl]piperazine (3-TFMPP). The microcrystalline tests carried out on these samples showed positive results for both BZP and caffeine without interference from other substances present

An investigation of digoxin by cyclic voltammetry using gold and silver solid electrodes and chemometric analysis

Digoxin, one of the main cardiac glycosides medication, has shown to have a strong analytical response under investigation by voltammetric analysis using mercury electrodes, achieving nanomole sensitivity. In this study we investigated the suitability of solid electrodes as gold and silver electrodes in voltammetric analysis of this active pharmaceutical ingredient. The scope of the investigation was to evaluate if the use of these solid electrodes, more practical and especially less dangerous, under an operative and environmental aspects could represent a valid further possibility to add to the use of the mercury ones. Both of the solid electrodes have been tested at different pH of 5, 7.4, 10, and 11. PCA analysis has been performed and specific responses achieved. Micromole sensitivity has been achieved for both of the electrodes, showing that the use of these sensors could represent a preliminary analytical approach when the more accurate alternative choice is not necessary, being more practical and less environmental impacting than using mercury

Reversing microcrystalline tests: an analytical approach to recycling of microcrystals from drugs of abuse

A combined analysis of microcrystalline tests followed by LC-MS or GC-MS analysis is described. Microcrystalline tests are shown to be non-destructive as addition products formed were easily dissociated after the application of an appropriate solvent. Subsequent analysis of the sample was done to quantify the recovery of the drug. Examples were performed using the date rape drug γ-hydroxybutyrate (GHB) and the synthetic opioid methadone

IL-10-conditioned dendritic cells, decommissioned for recruitment of adaptive immunity, elicit innate inflammatory gene products in response to danger signals

Dendritic cells (DCs) are the professional APCs of the immune system, enabling T cells to perceive and respond appropriately to potentially dangerous microbes, while also being able to maintain T cell tolerance toward self. In part, such tolerance can be determined by IL-10 released from certain types of regulatory T cells. IL-10 has previously been shown to render DCs unable to activate T cells and it has been assumed that this process represents a general block in maturation. Using serial analysis of gene expression, we show that IL-10 pretreatment of murine bone marrow-derived DCs alone causes significant changes in gene expression. Furthermore, these cells retain the ability to respond to Toll-like receptor agonists, but in a manner skewed toward the selective induction of mediators known to enhance local inflammation and innate immunity, among which we highlight a novel CXCR2 ligand, DC inflammatory protein-1. These data suggest that, while the presence of a protolerogenic and purportedly anti-inflammatory agent such as IL-10 precludes DCs from acquiring their potential as initiators of adaptive immunity, their ability to act as initiators of innate immunity in response to Toll-like receptor signaling is enhanced

An investigation of Digoxin by Cyclic Voltammetry using Gold and Silver Solid Electrodes and Chemometric Analysis

Digoxin, one of the main cardiac glycosides medication, has shown to have a strong analytical response under investigation by voltammetric analysis using mercury electrodes, achieving nanomole sensitivity. In this study we investigated the suitability of solid electrodes as gold and silver electrodes in voltammetric analysis of this active pharmaceutical ingredient. The scope of the investigation was to evaluate if the use of these solid electrodes, more practical and especially less dangerous, under an operative and environmental aspects could represent a valid further possibility to add to the use of the mercury ones. Both of the solid electrodes have been tested at different pH of 5, 7.4, 10, and 11. PCA analysis has been performed and specific responses achieved. Micromole sensitivity has been achieved for both of the electrodes, showing that the use of these sensors could represent a preliminary analytical approach when the more accurate alternative choice is not necessary, being more practical and less environmental impacting than using mercury

A study of in vitro metabolism and cytotoxicity of mephedrone and methoxetamine in human and pig liver models using GC/MS and LC/MS analyses

In the current study, the metabolism of two novel psychoactive substances (NPS), mephedrone and methoxetamine (MXE), was studied in vitro using pig liver microsomes to determine potential metabolites by liquid chromatography mass spectrometry (LC-MS). Later, in vitro studies were performed using HepaRG™ Cells to determine the human metabolites of these drugs using gas-chromatography mass spectrometry (GC-MS). The aim of the study was to be able to detect metabolites from the metabolic mixture in the human cell lines using a GC-MS, since this is a more readily available technique within forensic laboratories Microsomes were prepared through a conventional ultracentrifugation method and incubated under optimised conditions with the drugs for 3 h. Subsequently, the samples were investigated using LC-MS. A similar methodology was then applied for the HepaRG™ Cell and GC-MS conditions were optimised by using N,O-Bis(trimethylsilyl)trifluoroacetamide (BSTFA) as a derivatisation agent. The analysis showed two molecules from a successful in vitro metabolism, namely hydroxytoly-mephedrone and nor-dihydro mephedrone. For Methoxetamine (MXE), two metabolites are presented, produced by the O-demethylation and reduction of the ketone moiety to the corresponding alcohol, respectively. Using the human HepaRG™ cells, only nor-dihydro mephedrone could be identified by GC-MS. Since hydroxytoly-mephedrone and the MXE metabolites are more polar, it is suggested that GC-MS even with derivatisation may not be suitable. In addition, cytotoxicity was studied utilizing HepaRG™ cell lines. The drugs show cytotoxic effects causing in vitro cell death, within the specified range of EC50 0.3211 mM (79 μg/mL) and 0.6297 mM for mephedrone and MXE, respectively. These drugs were able to cause 73-84% cell death

Variation in amino acid and lipid composition of latent fingerprints

The enhancement of latent fingerprints, both at the crime scene and in the laboratory using an array of chemical, physical and optical techniques, permits their use for identification. Despite the plethora of techniques available, there are occasions when latent fingerprints are not successfully enhanced. An understanding of latent fingerprint chemistry and behaviour will aid the improvement of current techniques and the development of novel ones. In this study the amino acid and fatty acid content of ‘real’ latent fingerprints collected on a non-porous surface was analysed by gas chromatography–mass spectrometry. Squalene was also quantified in addition. Hexadecanoic acid, octadecanoic acid and cis-9- octadecenoic acid were the most abundant fatty acids in all samples. There was, however, wide variation in the relative amounts of each fatty acid in each sample. It was clearly demonstrated that touching sebum-rich areas of the face immediately prior to fingerprint deposition resulted in a significant increase in the amount of fatty acids and squalene deposited in the resulting ‘groomed’ fingerprints. Serine was the most abundant amino acid identified followed by glycine, alanine and aspartic acid. The significant quantitative differences between the ‘natural’ and ‘groomed’ fingerprint samples seen for fatty acids were not observed in the case of the amino acids. This study demonstrates the variation in latent fingerprint composition between individuals and the impact of the sampling protocol on the quantitative analysis of fingerprints