Synthesis of novel multifunctional carbazole-based molecules and their thermal, electrochemical and optical properties.

Two novel carbazole-based compounds 7a and 7b were synthesised as potential candidates for application in organic electronics. The materials were fully characterised by NMR spectroscopy, mass spectrometry, FTIR, thermogravimetric analysis, differential scanning calorimetry, cyclic voltammetry, and absorption and emission spectroscopy. Compounds 7a and 7b, both of which were amorphous solids, were stable up to 291 °C and 307 °C, respectively. Compounds 7a and 7b show three distinctive absorption bands: high and mid energy bands due to locally excited (LE) transitions and low energy bands due to intramolecular charge transfer (ICT) transitions. In dichloromethane solutions compounds 7a and 7b gave emission maxima at 561 nm and 482 nm with quantum efficiencies of 5.4% and 97.4% ± 10%, respectively. At positive potential, compounds 7a and 7b gave two different oxidation peaks, respectively: quasi-reversible at 0.55 V and 0.71 V, and reversible at 0.84 V and 0.99 V. At negative potentials, compounds 7a and 7b only exhibited an irreversible reduction peak at -1.86 V and -1.93 V, respectively.

Explosive detonation causes an increase in soil porosity leading to increased TNT transformation.

Explosives are a common soil contaminant at a range of sites, including explosives manufacturing plants and areas associated with landmine detonations. As many explosives are toxic and may cause adverse environmental effects, a large body of research has targeted the remediation of explosives residues in soil. Studies in this area have largely involved spiking 'pristine' soils using explosives solutions. Here we investigate the fate of explosives present in soils following an actual detonation process and compare this to the fate of explosives spiked into 'pristine' undetonated soils. We also assess the effects of the detonations on the physical properties of the soils. Our scanning electron microscopy analyses reveal that detonations result in newly-fractured planes within the soil aggregates, and novel micro Computed Tomography analyses of the soils reveal, for the first time, the effect of the detonations on the internal architecture of the soils. We demonstrate that detonations cause an increase in soil porosity, and this correlates to an increased rate of TNT transformation and loss within the detonated soils, compared to spiked pristine soils. We propose that this increased TNT transformation is due to an increased bioavailability of the TNT within the now more porous post-detonation soils, making the TNT more easily accessible by soil-borne bacteria for potential biodegradation. This new discovery potentially exposes novel remediation methods for explosive contaminated soils where actual detonation of the soil significantly promotes subsequent TNT degradation. This work also suggests previously unexplored ramifications associated with high energy soil disruption.

Detection of 2,4,6-Trinitrotoluene Using a Miniaturized, Disposable Electrochemical Sensor with an Ionic Liquid Gel-Polymer Electrolyte Film.

A new electrochemical method to detect and quantify the explosive compound 2,4,6-trinitrotoluene (TNT) in aqueous solutions is demonstrated. A disposable thin-film electrode modified with a droplet of a gel-polymer electrolyte (GPE) was immersed directly into samples of TNT at concentrations of 1-10 µg/mL. The GPE contained the hydrophobic room-temperature ionic liquid (RTIL) trihexyltetradecylphosphonium bis(trifluoromethylsulfonyl)imide ([P14,6,6,6][NTf2]) and the polymer poly(hexyl methacrylate). The RTIL acted to preconcentrate TNT into the GPE and provided ionic conductivity. The polymer provided both (i) sufficient viscosity to ensure mechanical stability of the GPE and (ii) strong hydrophobicity to minimize leaching of the RTIL. Square wave voltammetry was performed on the first reduction peak of TNT-preconcentrated samples (15 min soaking with mechanical stirring), with linear plots of peak current vs cumulative concentration of TNT, giving an averaged limit of detection of 0.37 µg/mL (aqueous phase concentration). Additionally, the voltammetry of the first reduction peak of TNT in [P14,6,6,6][NTf2] was unaffected by the presence of oxygen-in contrast to that observed in an imidazolium-based RTIL-providing excellent selectivity over oxygen in real environments. The sensor device was able to quickly and easily quantify TNT concentrations at typical ground water contamination levels. The low-cost and portability of the sensor device, along with the minimal amounts of GPE materials required, make this a viable platform for the onsite monitoring of explosives, which is currently a significant operational challenge.

Investigating TNT loss between sample collection and analysis.

Explosives residues are often collected from explosion scenes, and from surfaces suspected of being in contact with explosives, by swabbing with solvent-wetted cotton swabs. It is vital that any explosives traces present on the swabs are successfully extracted and detected when received in a laboratory. However, a 2007 proficiency test initiated by the European Network of Forensic Science Institutes (ENFSI) Expert Working Group on Explosives involving TNT-spiked cotton swabs highlighted that explosives may not always be detected from such samples. This paper outlines work performed to determine potential reasons for this finding. Cotton swabs were spiked using a solution of TNT and stored in nylon bags and glass vials for periods of 1, 2 and 4weeks. Simulated swab extracts were also prepared and investigated. The samples were stored in a freezer, or at room temperature either in the dark or exposed to daylight. Overall, the cotton swabs stored at room temperature and exposed to daylight showed a very rapid loss of TNT over time, whereas cotton swabs stored in the freezer, and all simulated swab extracts, gave high recoveries over time. These results will be of benefit for practicing forensic explosives laboratories and for persons undertaking cold-case reviews involving explosive-based samples.

Assessing a novel contact heater as a new method of recovering explosives traces from porous surfaces.

It can be very challenging to recover explosives traces from porous surfaces, such as clothing and car seats, compared to non-porous surfaces. The contact heater has been developed as a novel instrument designed to recover explosives traces from porous surfaces. Samples are taken by heating and drawing air across a surface, with the air flowing through a sampling cartridge containing adsorbent polymer beads, which act to trap any recovered explosive material. Any collected explosive can then be eluted from this cartridge using a solvent, prior to analysis. This paper outlines work performed to evaluate the usefulness of the contact heater with regards to the recovery of explosives traces from porous materials. Ethylene glycol dinitrate (EGDN) and triacetone triperoxide (TATP) were chosen as two representative explosives for this study. Quantification was performed using GC-MS for EGDN and LC-MS/MS for TATP. Different sampling temperatures, sampling times and elution solvents were investigated. Recovery was trialled from leather, carpet and denim. Recoveries of up to 71% were obtained following optimisation. It was also possible to recover TATP from fabrics exposed to TATP vapour in a vapour-laden jar up to two hours after exposure. The contact heater therefore appears to be a very useful tool for the recovery of explosives traces from porous materials.