The author discusses the benefits for forensic science from greater engagement with basic and other applied areas of chemistry and gives examples of how his organization, the Australian Federal Police, have partnered with academia and others to promote the use of chemistry in areas of trace evidence, illicit drugs, fingerprint detection, and explosives.
The application of a wide range of chemical techniques and methods to issues relating to judicial matters is not a new phenomena. However with increasing sensitivity of instrumentation and the use of robust mathematical systems in the interpretation of results, attention should be refocused onto the interpretation of those results within a specific case context and emphasizes the urgent need for clear communication between scientist, police and lawyer. This paper explores some of the emerging applications of techniques such as isotope ratio mass spectrometry (IRMS) within a forensic science context and the issues this raises.
This review paper updates the previous literature in relation to the continued and developing use of Stable Isotope Ratio analysis in samples which are relevant to forensic science. Recent advances in the analysis of drug samples, explosive materials and samples derived from human and animal samples are discussed. The paper also aims to put the use of IRMS into a forensic context and discuss its evidential potential.
The plant Ricinus communis (castor bean plant) contains the toxic protein ricin, a chemical warfare agent. The ability to determine specimen and provenance of R. communis extracts would aid forensic and law enforcement agencies. The metabolome of R. communis has been subjected to chemical and multivariate statistical analysis, which allowed some specimen determinations to be made.
The HI/Pred synthesis of methamphetamine from ephedrine is one of the most prevalent methods used for the illicit manufacture of methamphetamine in Australasia. The synthetic determinants of the products isotopic composition have been evaluated by isotope ratio mass spectrometry and 2H NMR spectroscopy.
Gas chromatography-mass spectrometry analysis of the organic peroxide explosives triacetone triperoxide and hexamethylene triperoxide diamine (HMTD), prepared from domestically available off-the-shelf precursors, showed that compounds originating from such precursors could be detected. Furthermore, some compounds could also be detected in the residues of samples that had been subjected to thermal initiation.
Assessment of the impact of radiological emergencies requires rapid, robust methods of measurement and analysis. This paper describes the development and validation of a method to estimate the excretion rate of 210Po in urine. This allows the determination of the 210Po intake, which is required to estimate the resulting radiation dose.
The title ligand, 2-(o-anilinyl)-4,4-dimethyl-2-oxazoline (l), represents a relatively unexplored metal-binding framework. The treatment of cobalt(II) metal salts with l leads to the isolation and characterization of five novel (κ2-N,N′-bonded) complexes having either distorted tetrahedral or octahedral bonding motifs around the metal centre. This work represents the first systematic investigation of the binding properties of l with a first-row metal in formally the 2+ oxidation state.
Different chemical modifications, such as the bioisosteric replacement of the naphthalene moiety by nitrogen-containing aromatic heterocycles is carried out in a series of 4-arylpiperazine-ethyl-naphthalene carboxamides. Although the presence of a quinoxaline or quinoline moiety leads to reduced lipophilicity, the affinity and/or selectivity for 5-HT1A receptors is conserved or increased. A 4-phenyl-1,2,3,6-tetrahydropyridine in place of the corresponding 4-phenyl-piperazine side chain is also favourable.
Parathion, an organophosphorous pesticide, is always associated to hydrophobic bilayers. It is located near the interface, and oriented with the nitro group pointing toward the charged headgroups and the ethoxy chains to the hydrophobic core.
The octahedral complexes, [Ni(β-diketonate)2(ppaX)], have been synthesized. The electrochemical behaviour of the complexes reveals quasi-reversible or irreversible one-electron oxidation to Ni(III) depending on the type of β-diketonate ligand present.
Mesoporous layered materials consisting of positively charged metal hydroxide layers with nitrate as counterions show promise as adsorbing media for ink-jet printing. We have prepared materials with varying Mg:Al molar ratios and examined their dye adsorption properties. The adsorption of common ink-jet printing dyes was found to correlate with the Mg:Al molar ratio and textural properties of these materials.
The addition of (chlorocarbonyl)phenyl ketene (2) to 5-alkylpyrazol-3(4H)-ones 1 led to the formation of hydroxypyrazolo[1,2-a ]pyrazole-dione/pyrazolo[1,2-a ]pyrazole-trione derivatives 3. This is ascribed to hydrogen exchange in initially formed unstable, mesoionic pyrazolo[1,2-a]pyrazol-4-ium-5-olates. In contrast, condensation of the same ketene with 3-alkyl-1-phenyl-2-pyrazolin-5-ones 4 afforded 4-hydroxy-3-alkyl-1,5-diphenylpyrano[2,3-c]pyrazol-6-one derivatives 5. The latter reaction provides a new and rapid route to 4-hydroxy-2-pyrones fused to pyrazole rings, in good to excellent yields.
Reactions of hexavacant polyoxotungstate [H2P2W12O48]12– with various transition metal cations lead to the isolation of three double Dawson-type polyoxotungstates. All the compounds are further connected into supramolecular structures via H-bonding interactions. The {P2W12} building block undergo structural transformation from {P2W12} to {P2W17} or {P2W14} in the synthesis of these three compounds.
A new class of luminescent organometallic/inorganic nanohybrid LB films based on a π-conjugated digold(I) bis(acetylide) complex and inorganic polyoxometalates (POMs) were prepared and characterized by π–isotherms, AFM, STM and SPS. These hybrid LB composites display strong photovoltaic effect with the performance dependent of the nature of POMs.
A series of nickel complexes bearing 2-(1H-2-benzimidazolyl)-6-(1-(arylimino)ethyl)pyridines was synthesized and characterized. Upon activation with Et2AlCl, good catalytic activities up to 106 g mol–1 (Ni) h–1 for ethylene oligomerization with major dimerization were exhibited. These complexes with a N–H group on the benzimidazole exhibit a higher activity than their analogues containing alkylated benzimidazoles.
This paper describes the synthesis and pharmacological evaluation of a series of novel substituted 4′-phenoxypropyl analogues of clozapine, for the potential treatment of schizophrenia. The synthesized compounds exhibited a favourable receptor binding affinity profile compared with clozapine for the target receptors of interest. From the ensuing behavioural evaluation, two analogues have emerged as potential lead compounds for further evaluation as prospective antipsychotic agents.
Doubly ortho-linked cis-4,4′-bis(diarylamino)stilbene/fluorene hybrids have potential application in organic light emitting diodes (OLEDs). Here we study the structural, electronic, and optical properties of these molecules. The results presented in this work suggest that these doubly ortho-linked cis-4,4′-bis(diarylamino)stilbene/fluorene hybrids show great potential as efficient hole transport, sky-blue fluorescent OLED materials.
The feasibility of granulated Pt/carbon nanotubes (CNTs) for further industrial application was tested in a hydrogenation process. They exhibited a better catalytic performance than Pt/activated carbon. We evinced that larger dominant pores of Pt/CNT catalyst allow the easy mass transfer of H2 to convert nitrobenzene and intermediates into aniline quickly.
A simple and efficient chemoselective thioacetalization of carbonyl compounds has been achieved using Ce(OTf)3 (10 mol-%) as a catalyst under solvent-free conditions. Advantages of the methodology include short reaction times, excellent yields, catalytic use of a water tolerant Lewis acid, and recovery and reuse of the catalyst.
Supramolecular structures are of considerable complexity, with several ligand and metal ions forming a unit that is often helical. Very little is known about the mechanism of their formation from the building blocks. Using combined kinetic and equilibrium investigations, we have determined two pathways for Cu(II) (blue) and Ni(II) (green) as indicated in the graph.
The publication rate on RAFT polymerization continues to increase with the latest publication of a third update. Freely access the three reviews previously written by CSIRO scientists Moad, Rizzardo, and Thang on this subject in Australian Journal of Chemistry.