A Study on Auto-Catalysis and Product Inhibition: A Nucleophilic Aromatic Substitution Reaction Catalysed within the Cavity of an Octanuclear Coordination Cage.

The ability of an octanuclear cubic coordination cage to catalyse a nucleophilic aromatic substitution reaction on a cavity-bound guest was studied with 2,4-dinitrofluorobenzene (DNFB) as the guest/substrate. It was found that DNFB undergoes a catalysed reaction with hydroxide ions within the cavity of the cubic cage (in aqueous buffer solution, pH 8.6). The rate enhancement of kcat/kuncat was determined to be 22, with cavity binding of the guest being required for catalysis to occur. The product, 2,4-dinitrophenolate (DNP), remained bound within the cavity due to electrostatic stabilisation and exerts two apparently contradictory effects: it initially auto-catalyses the reaction when present at low concentrations, but at higher concentrations inhibits catalysis when a pair of DNP guests block the cavity. When encapsulated, the UV/Vis absorption spectrum of DNP is red-shifted when compared to the spectrum of free DNP in aqueous solution. Further investigations using other aromatic guests determined that a similar red-shift on cavity binding also occurred for 4-nitrophenolate (4NP) at pH 8.6. The red-shift was used to determine the stoichiometry of guest binding of DNP and 4NP within the cage cavity, which was confirmed by structural analysis with X-ray crystallography; and was also used to perform catalytic kinetic studies in the solution-state.

Differentiating Between V- and G-Series Nerve Agent and Simulant Vapours Using Fluorescent Film Responses.

In-field rapid and reliable identification of nerve agents is critical for the protection of Defence and National Security personnel as well as communities. Fluorescence-based detectors can be portable and provide rapid detection of chemical threats. However, most current approaches cannot differentiate between dilute vapors of nerve agent classes and are susceptible to false positives due to the presence of common acids. Here a fluorescence-based method is shown for rapid differentiation between the V-series and phosphonofluoridate G-series nerve agents and avoids false positives due to common acids. Differentiation is achieved through harnessing two different mechanisms. Detection of the V-series is achieved using photoinduced hole transfer whereby the fluorescence of the sensing material is quenched in the presence of the V-series agent. The G-series is detected using a turn-on mechanism in which a silylated excited state intramolecular proton transfer sensing molecule is selectively deprotected by hydrogen fluoride, which is typically found as a contaminant and/or breakdown product in G-series agents such as sarin. The strategy provided discrimination between classes, as the sensor for the G-series agent class is insensitive to the V-series agent, and vice versa, and neither responded to common acids.

Detection of aqueous and gaseous hydrogen sulfide with lanthanide-macrocycle binary complexes.

Two novel, discrete lanthanide-macrocycle binary complexes for the detection of hydrogen sulfide are reported. The hydrogen sulfide sensing mechanism utilises the copper sequestration at a secondary binding site, with resulting bimetallic lanthanide(III)/copper(II) complexes (Ln = Eu3+ and Tb3+) exhibiting high selectivity, good sensitivity and excellent reversibility for aqueous hydrogen sulfide. The inclusion of the DO2A macrocycle and 4-(2-pyridyl)-1,2,3-triazole dipicolinic acid ligand, results in a complex with good solubility and stability. The europium(III) complex also displayed a low limit of detection (665 ppb) with a response time of 30 seconds with gaseous hydrogen sulfide. The improved water solubility and stability over a previous complex results in these sensors having the potential for use in environmental monitoring and biological studies for various functional settings.

The preservation of sarin and O,O'-diisopropyl fluorophosphate inside coordination cage hosts.

The host-guest chemistry of O,O'-diisopropyl fluorophosphate (DFP), a phosphonofluoridate G-series chemical warfare agent simulant, was investigated in the presence of a number of octanuclear cubic coordination cage hosts. The aim was to demonstrate cage-catalysed hydrolysis of DFP at near neutral pH: however, two octanuclear coordination cages, HPEG (containing water-solubilising PEG groups) and HW (containing water-solubilising hydroxymethyl groups), were actually found to increase the lifetime of DFP in aqueous buffer solution (pH 8.7). Crystallographic analysis of DFP with a structurally related host cage revealed that DFP binds to windows in the cage surface, not in the internal cavity. The phosphorus-fluorine bond is directed into the cavity rather than towards the external environment, with the cage/DFP association protecting DFP from hydrolysis. Initial studies with the chemical warfare agent (CWA) sarin (GB) with HPEG cage in a buffered solution also showed a drastically reduced rate of hydrolysis for sarin when bound in the host cage. The ability of these cages to inhibit hydrolysis of these P-F bond containing organophosphorus guests, by encapsulation, may have applications in forensic sample preservation and analysis.

Chemical forensic profiling and attribution signature determination of sarin nerve agent using GC-MS, LC-MS and NMR.

Sarin is a highly toxic nerve agent classified by the Chemical Weapon Convention as a Schedule 1 chemical with no use other than to kill or injure. Moreover, in recent times, chemical warfare agents have been deployed against both military and civilian populations. Chemical warfare agents always contain minor impurities that can provide important chemical attribution signatures (CAS) that can aid in forensic investigations. In order to understand the trace molecular composition of sarin, various analytical approaches including GC-MS, LC-MS and NMR were used to determine the chemical markers of a set of sarin samples. Precursor materials were studied and the full characterisation of a synthetic process was undertaken in order to provide new insights into potential chemical attribution signatures for this agent. Several compounds that were identified in the precursor were also found in the sarin samples linking it to its method of preparation. The identification of these CAS contributes critical information about a synthetic route to sarin, and has potential for translation to related nerve agents.

Acid is a potential interferent in fluorescent sensing of chemical warfare agent vapors.

A common feature of fluorescent sensing materials for detecting chemical warfare agents (CWAs) and simulants is the presence of nitrogen-based groups designed to nucleophilically displace a phosphorus atom substituent, with the reaction causing a measurable fluorescence change. However, such groups are also basic and so sensitive to acid. In this study we show it is critical to disentangle the response of a candidate sensing material to acid and CWA simulant. We report that pyridyl-containing sensing materials designed to react with a CWA gave a strong and rapid increase in fluorescence when exposed to Sarin, which is known to contain hydrofluoric acid. However, when tested against acid-free diethylchlorophosphate and di-iso-propylfluorophosphate, simulants typically used for evaluating novel G-series CWA sensors, there was no change in the fluorescence. In contrast, simulants that had been stored or tested under a standard laboratory conditions all led to strong changes in fluorescence, due to acid impurities. Thus the results provide strong evidence that care needs to be taken when interpreting the results of fluorescence-based solid-state sensing studies of G-series CWAs and their simulants. There are also implications for the application of these pyridyl-based fluorescence and other nucleophilic/basic sensing systems to real-world CWA detection.

A highly efficient red-emitting luminescent paper-based chemosensor for hydrogen sulfide.

The first discrete bimetallic europium(iii)/copper(ii) complex for the fast, sensitive and selective luminescent detection of both aqueous and gaseous hydrogen sulfide has been developed. The chemosensor displayed an impressive response time of 30 seconds and a low theoretical limit of detection (100 ppb) for gaseous hydrogen sulfide.

Challenges in Fluorescence Detection of Chemical Warfare Agent Vapors Using Solid-State Films.

Organophosphorus (OP)-based nerve agents are extremely toxic and potent acetylcholinesterase inhibitors and recent attacks involving nerve agents highlight the need for fast detection and intervention. Fluorescence-based detection, where the sensing material undergoes a chemical reaction with the agent causing a measurable change in the luminescence, is one method for sensing and identifying nerve agents. Most studies use the simulants diethylchlorophosphate and di-iso-propylfluorophosphate to evaluate the performance of sensors due to their reduced toxicity relative to OP nerve agents. While detection of nerve agent simulants in solution is relatively widely reported, there are fewer reports on vapor detection using solid-state sensors. Herein, progress in organic semiconductor sensing materials developed for solid-state detection of OP-based nerve agent vapors is reviewed. The effect of acid impurities arising from the hydrolysis of simulants and nerve agents on the efficacy and selectivity of the reported sensing materials is also discussed. Indeed, in some cases it is unclear whether it is the simulant that is detected or the acid hydrolysis products. Finally, it is highlighted that while analyte diffusion into the sensing film is critical in the design of fast, responsive sensing systems, it is an area that is currently not well studied.

Qualitative colorimetric analysis of a Ir(iii)/Eu(iii) dyad in the presence of chemical warfare agents and simulants on a paper matrix.

The addition of G- and V-series organophosphorus chemical warfare agents and simulants to a paper-based assay of a dual-luminescent Ir(iii)/Eu(iii) dyad generated different emissive responses between the classes and compound types. The emission responses are complex and based not only on altering the balance between red Eu(iii)-based and blue Ir(iii)-based luminescent components, but also incorporate other factors such as analyte volatility, concentration and UV absorption. The extent of this emission colour change was analysed colorimetrically and related to the change in RGB output over time.

An investigation into artefacts formed during gas chromatography/mass spectrometry analysis of firearms propellant that contains diphenylamine as the stabiliser.

In the course of providing assistance to legal counsel in a matter that involved the analysis of firearms propellant by gas chromatography/mass spectrometry it was noticed that phenoxazine was reported as a component of 0.22 calibre propellant that contained diphenylamine as the stabiliser. The research was conducted to find how phenoxazine was formed. The results showed that the compound was not phenoxazine but a diphenylamine derivative 4-(phenylimino) cyclohexa-2,5-dien-1-one that formed in the injection port of the gas chromatograph. In addition a second artefact was found to form in the ion source of the mass spectrometer. While the presence of the artefacts does not affect the ability to identify particles as propellant they may impact on comparison with source ammunition.

Mechanistic insights into the luminescent sensing of organophosphorus chemical warfare agents and simulants using trivalent lanthanide complexes.

Organophosphorus chemical warfare agents (OP CWAs) are potent acetylcholinesterase inhibitors that can cause incapacitation and death within minutes of exposure, and furthermore are largely undetectable by the human senses. Fast, efficient, sensitive and selective detection of these compounds is therefore critical to minimise exposure. Traditional molecular-based sensing approaches have exploited the chemical reactivity of the OP CWAs, whereas more recently supramolecular-based approaches using non-covalent interactions have gained momentum. This is due, in part, to the potential development of sensors with second-generation properties, such as reversibility and multifunction capabilities. Supramolecular sensors also offer opportunities for incorporation of metal ions allowing for the exploitation of their unique properties. In particular, trivalent lanthanide ions are being increasingly used in the OP CWA sensing event and their use in supramolecular sensors is discussed in this Minireview. We focus on the fundamental interactions of simple lanthanide systems with OP CWAs and simulants, along with the development of more elaborate and complex systems including those containing nanotubes, polymers and gold nanoparticles. Whilst literature investigations into lanthanide-based OP CWA detection systems are relatively scarce, their unique and versatile properties provide a promising platform for the development of more efficient and complex sensing systems into the future.

VX and VG chemical warfare agents bidentate complexation with lanthanide ions.

Investigations into V-agent interaction with 1,10-phenanthroline nitrate Ln(III) complexes (Eu and Tb) were carried out using luminescence and UV-Vis spectroscopy. Addition of several equivalents of agent resulted in the loss of luminescence intensity and the observation of free 1,10-phenanthroline by UV-Vis. We propose a displacement mechanism in which the V-agent acts as a bidentate ligand to the lanthanide ion. Association constants were determined by luminescence titrations and found to be 10(5) mol(-1) dm(3).