Showcasing water-based delivery of an amino acid targeting fingermark developer in a hydrogel.

Most recommended methods for visualising fingermarks on paper rely on chemical developers that target and react with amino acids. Traditionally, these developers are sprayed onto paper substrates in solutions of per- and polyfluoroalkyl substances (PFAS), but now those same PFAS chemicals are undergoing phaseout or phasedown, which threatens to undermine forensic capabilities. This situation provides an opportunity to pivot towards greener approaches to fingermark visualisation. The ideal methodology would be a water-based treatment, as these provide superior safety for practitioners, combined with environmental sustainability. A major hurdle to implementing a water-based fingermark developer targeting amino acids is that water, as a universal solvent, can dissolve the eccrine components in fingermarks, as well as any optical or luminescent dyes that are created, causing the ridge detail to run or dissolve. This work circumvents this problem by delivering the amino acid developer alloxan in a hydrogel, which enables sharp fingermark ridge details to be observed despite it being a water-based treatment. Alloxan dissolved in a viscous hydrogel is shown here to react with the amino acids in fingerprint residues to form the coloured dye murexide, supported by optimisation and characterisation studies.

Profiling ephedrine/pseudoephedrine and methamphetamine synthesised from benzaldehyde, nitroethane and dimethyl carbonate.

In previous work, a novel pathway for the synthesis of ephedrine/pseudoephedrine and methamphetamine using the precursors benzaldehyde, nitroethane and dimethyl carbonate was investigated, and an impurity profile presented. This paper presents chiral and stable isotope ratios of ephedrine/pseudoephedrine and methamphetamine synthesised by this pathway. Based on the chiral profile and the more negative δ13C (avg. -33.2‰) and more positive δ2H values, it is possible to distinguish ephedrine/pseudoephedrine and methamphetamine prepared from this pathway from those of "fully synthetic", "semi-synthetic" or "natural" origin. The more positive δ2H values of methamphetamine from this pathway allowed for differentiation from methamphetamine produced from phenyl-2-propanone. It was noted, however, that the use of stable isotope profiling would likely be limited when a benzaldehyde source having a negative δ2H value was used as a precursor. Furthermore, the stable isotope values alone could not be used to differentiate from methamphetamine prepared by the Akabori-Momotani reaction, highlighting the need for combination with impurity profiling.

Once upon a twine: The Donna Steele murder investigation and an improved methodology for the comparison of synthetic twine.

In 2017 Cooktown resident Donna Steele was murdered and the case remained unsolved for more than a year. The forensic evidence from the investigation included two lengths of synthetic twine and a new protocol for the comparison of twine was developed to enhance the potential value of any evidence. The method was developed using 23 samples of similar twine collected across Australia. Traditional methods of physical and microscopic comparisons and polymer analysis by infrared spectroscopy were retained. Micro-spectrophotometry was used as an objective assessment of colour and was able to identify five groupings within the background samples. Measurements of hydrogen and carbon stable isotopic composition provided further delineation of the background samples. Combining traditional methods with micro-spectrophotometry and stable isotope measurements, the two case samples were found to be distinct from the background population and were indistinguishable when compared to each other.

Solvent-free strategies for developing latent fingermarks on paper: a review.

With growing environmental concern and supply chain uncertainty, now is a fitting time to re-evaluate solvent-free methodologies in forensic chemistry processes. Here, this paper reviews solvent-free approaches for fingermark visualisation, including chemical fuming and vapour phase treatments, dry-transfer treatments, application of heat, and thermal paper specific treatments. After providing historical context, three objectives have been emphasised: identify feasible scenarios for implementing solvent-free methods; showcase the effectiveness of solvent-free methods relative to their nearest solution-based equivalent; and estimate the technological readiness level of each method discussed. Having reviewed the literature, dry-transfer methods of developing latent fingermarks on paper were found to be the most promising and feasible solvent-free approaches for near-term implementation. Such methods make use of standard materials and equipment commonly found in forensic laboratories, are effective at fingermark visualisation, and mitigate most of the pressing issues pertaining to environmental concern and solvent scarcity.

Stable isotope characterisation of 3,4-methylenedioxyphenyl-2-propanone and 3,4-methylenedioxyamphetamine prepared from piperonal.

RATIONALE: Stable isotopic ratios can provide information for illicit drug profiling. The research presented here investigated the variations in stable isotopic ratios of hydrogen (δ2 H), carbon (δ13 C), nitrogen (δ15 N) and oxygen (δ18 O) during the synthesis of MDP2P (3,4-methylenedioxyphenyl-2-propanone) and MDA (3,4-methylenedioxyamphetamine) prepared via the 'nitrostyrene' route. METHODS: Samples of MDA and MDP2P were synthesised from two isotopically characterised starting materials, piperonal and nitroethane. The isotopic compositions of the nitrostyrene intermediate (3,4-methylenedioxyphenyl-2-nitropropene, MDP2NP) and products MDP2P and MDA were also measured by isotope ratio mass spectrometry. RESULTS: A significantly negative change occurred to δ2 H values during the production of MDP2NP, MDP2P and MDA, indicating a mechanism that favours inclusion or retention of 1 H over 2 H. This suggests that the δ2 H compositions of MDA/MDP2P prepared from piperonal will not provide information on the synthetic history. Minimal changes were observed in δ13 C composition during the synthesis of MDP2NP, MDP2P and MDA, and minimal δ15 N compositional changes occurred in MDP2NP and MDA. Progressing from piperonal to MDP2NP, a minimal change occurred to δ18 O composition. A variable change to δ18 O was observed from MDP2NP with one sample becoming more positive in δ18 O composition and two samples becoming more negative. Progressing from MDP2NP to MDA, a significant negative change occurred to δ18 O composition. CONCLUSIONS: The changes to stable isotopic ratios observed during the preparation of MDA and MDP2P from piperonal may prove useful when attempting to compare batch-to-batch variations between seizures and provide information with tactical intelligence applications.

Constituents of "teabacco": A forensic analysis of cigarettes made from diverted nicotine replacement therapy lozenges in smoke-free prisons.

Following the implementation of prison smoke-free policies, there have been reports of prisoners creating substitute cigarettes made from nicotine replacement therapy patches or lozenges infused with tea leaves ("teabacco"). No studies have analyzed the chemical constituents of teabacco made from nicotine lozenges, so as to document any potential related health hazards. Teabacco samples were made by a participant who reported creating teabacco while incarcerated in a smoke-free prison in Queensland, Australia, and the process was video-recorded for replication in a laboratory. A simple linear smoking system captured the teabacco smoke for analysis. Inductively coupled plasma optical emission spectroscopy (ICP-OES) was used to analyze elemental composition and gas chromatography coupled with a mass spectrometer (GC-MS) analyzed the captured smoke using the National Institute of Standards and Technology mass spectral library. Analyses determined that quantities of copper, aluminum, and lead concentrations, and levels of inhaled total particulate matter, were above recommended guidelines for safe ingestion. Analysis of teabacco smoke using GC-MS identified potentially toxic compounds catechol and nicotine. However, our findings show that smoking this form of teabacco is less harmful than smoking teabacco made from nicotine patches, or smoking traditional tobacco cigarettes. Considering the limited potential health harm of smoking teabacco made from lozenges, and that nicotine lozenges represent the only form of smoking cessation support for individuals entering smoke-free prisons, we caution against the removal of nicotine lozenges from Queensland's prisons, at least until further research directly establishes health harms associated with this form of teabacco.

'Teabacco': Smoking of nicotine-infused tea as an unintended consequence of prison smoking bans.

INTRODUCTION AND AIMS: Following the introduction of smoke-free policies in prisons in several countries, there have been anecdotal reports of prisoners creating cigarettes by mixing nicotine patches or lozenges with tea leaves ('teabacco'). Among a sample of people recently released from smoke-free prisons in Queensland, Australia, the aims of this study were to explore the perceived popularity of teabacco use, motivations for its use and describe the process of creating teabacco to identify potential associated health risks. DESIGN AND METHODS: This study used a mixed-methods design. Eighty-two people recently released from prison in Queensland, Australia completed surveys at parole offices measuring teabacco use while incarcerated. Twenty-one teabacco smokers took part in follow-up, qualitative interviews to explore survey responses in greater depth. RESULTS: The majority of survey participants (57%) reported smoking teabacco while incarcerated, with 37% smoking teabacco frequently (> once per week). Teabacco use was primarily motivated by cigarette cravings. Participants described the perceived inevitability of prisoners finding substitutes for tobacco. Multivariate analyses found that self-rated poor physical health, having been incarcerated five or more times, experiencing cigarette cravings while incarcerated, and use of illicit drugs while incarcerated were positively associated with frequent teabacco use in prison. DISCUSSION AND CONCLUSIONS: Our findings suggest that teabacco use has become common practice in Queensland's smoke-free prisons. Correctional smoking bans are an important public health initiative but should be complemented with demand and harm reduction measures cognisant of the risk environment.

A comparison of plastic cable ties based on physical, chemical and stable isotopic measurements.

Plastic cable ties can be utilised in a range of serious criminal activities and a comparison of cable ties, or fragments, may form part of the physical evidence presented to a Court of law. This research assessed the potential value of evidence based on the analysis of plastic cable ties. Twenty packets of black coloured plastic cable ties (nominally 200mm×4.8mm) were purchased in pack sizes ranging from 25 to 100 individual cable ties (Brisbane, Australia, March 2015). Representative samples from each packet were visually examined, compared and tested to determine their physical dimensions, chemical compositions and stable isotopic compositions (δ2H, δ13C and δ15N). All of the individual cable ties from a given packet were found to be indistinguishable with respect to appearance, physical, chemical and isotopic measurements (within-batch variability). Individual cable ties were also found to be isotopically homogeneous with respect to hydrogen, carbon and nitrogen. All of the cable ties analysed were found to have very similar chemical compositions and to be manufactured predominantly from nylon 6,6. The elemental compositions of composite samples, prepared from each packet, were found to be highly variable and, as such, were of very limited value. Cable ties from ten of the twenty packets were uniquely characterised by physical appearance (between-batch variability). Physical measurements such as the width, thickness and tooth-count of the grip section did not provide additional discrimination. Cable ties from nineteen of the twenty packets were uniquely characterised by isotopic composition, based on δ2H and δ15N measurements. Samples from two packets of Crescent brand cable ties were found to be indistinguishable with respect to all of the tests applied in this study. These two packets were inadvertently purchased from the same retailer and had the same barcode and batch number. It was considered a reasonable assumption that these two packets originated from the same manufacturing batch. The authors reason that a likelihood ratio (that might be presented to a Court of law) can be derived from this type of discrete data based on a calculation of the possible combinations of distinguishable objects (unordered sampling with replacement) in a convenience sample collected from the background population. In this example, a database of 19 distinguishable objects can yield a likelihood ratio as high as 210, with a verbal equivalent of "moderately strong support" for a proposition that two cable ties have the same isotopic composition because they originate from the same batch rather than by random chance.

Development of techniques for determination of primary components of dental medicament paste mixtures for root canal treatment.

AIMS: The purpose of the present study was to develop techniques to evaluate and quantify the primary components of dental medicament paste mixtures for root canal treatment, and to evaluate if degradation of the primary components occurred during storage. METHODS: The first part of the study developed a mass spectrometry (MS) method for determination of best recovery process. For this process, analytical grades of triamcinolone acetonide, clindamycin HCl, and doxycycline hyclate were sourced and analyzed. This was followed by solid-phase extraction (SPE) and an analysis of active components in dental pastes. RESULTS: By utilizing the targeted analytical properties of multiple reaction monitoring MS methods, coupled with SPE technique, the active components of endodontic dental pastes could be quantified and compared. The developed methods showed consistency over multiple runs, with a high level of reproducibility. None of the active components of the tested pastes degraded over the periods of product life tested. CONCLUSION: The inactivation or destruction of any of the primary components of endodontic medicaments in storage, or when mixed with other pastes, could affect treatment outcomes. The present study provides a reliable technique for the analysis of the active components of root canal medicaments.

Isotopic profiling of seized benzylpiperazine and trifluoromethylphenylpiperazine tablets using δ13C and δ15N stable isotopes.

This paper demonstrates the use of isotopic analysis of 23 benzylpiperazine (BZP) and trifluoromethylphenylpiperazine (TFMPP) containing tablets seized on two independent occasions by the Northern Territory (NT) Police, Australia. Isolation (High Performance Liquid Chromatography (HPLC)) of BZP and TFMPP followed by Isotope Ratio Mass Spectrometry (IRMS) (carbon and nitrogen stable isotopes) analysis was performed. Results are presented for δ13C and δ15N values of the respective piperazine analogues. The isotopic data and statistical analysis suggest a common source of manufacture for the BZP samples but suggest different sources for the TFMPP isolated from the corresponding BZP containing tablets investigated. The use of IRMS in this case study demonstrated the ability to obtain information regarding the BZP/TFMPP sources unattainable via conventional chemical analysis.

Precursor discrimination of designer drug benzylpiperazine using δ13C and δ15N stable isotopes.

Advances in analytical technology and emerging techniques have resulted in the increased exploitation of chemical and isotopic profiling for source linkage/discrimination of illicit drugs for forensic purposes. Although not routinely used for illicit drug investigations, such information has been obtained and its application demonstrated through the use of isotope ratio mass spectrometry (IRMS). There is a solid platform of research available relating to the isotopic analysis of methylenedioxymethamphetamine (MDMA) and methamphetamine (MA), however with the recently flourishing designer drug market it was of interest to examine the isotopic profiles of the popular 'party drug' benzylpiperazine hydrochloride (BZP·HCl). A preliminary analysis of δ13C and δ15N isotopic ratios in BZP·HCl products and corresponding synthetic intermediates (piperazine·HCl) synthesized in-house from three different precursor suppliers was conducted using IRMS. Analysis of the δ13C and δ15N isotopic data indicated that discrimination and correct grouping of all the intermediates and some of the product samples examined in this study were achievable.

Investigation of the l-phenylacetylcarbinol process to substituted benzaldehydes of interest.

The large scale industrial manufacture of the nasal decongestant pseudoephedrine is typically carried out by the reductive amination of l-phenylacetylcarbinol (l-PAC), which in turn is produced via the biotransformation of benzaldehyde using yeast. In recent years there has been increasing legislative control of the supply of pseudoephedrine due to it being diverted for the clandestine production of methylamphetamine and there is some evidence that a number of clandestine drug laboratory chemists have considered the application of the l-PAC process to manufacture their own pseudoephedrine. This work examined the use of a number of substituted benzaldehydes for the manufacture of the corresponding substituted l-PAC analogue followed by reductive amination to the corresponding substituted pseudoephedrine/ephedrine analogues. These substituted pseudoephedrine/ephedrine analogues were either reduced or oxidised to determine the feasibility of producing the corresponding methylamphetamine or methcathinone analogues. As a result, the l-PAC process was identified as a viable route for synthesis of substituted methylamphetamines and methcathinones.