Efficient sensing of explosives by using fluorescent nonporous films of oligophenyleneethynylene derivatives thanks to optimal structure orientation and exciton migration.

The fluorescence of thin films of a diimine-substituted phenyleneethynylene compound can be efficiently quenched by nitroaromatic vapors, which is not the case for the unsubstituted parent compound. Thin-film porosity is usually considered to be an essential factor for efficient quenching, but in the present case the origin of the quenching is completely different, as both films are nonporous and hermetic to 2,4-dinitrotoluene (DNT) molecules. The molecular organization in the two crystallized thin films offers a low level of π stacking for both compounds, but the orientation of the phenylenethynylene fluorophore differs markedly with respect to the surface of the films. For the substituted compound, the fluorophore is almost parallel to the surface, thus making it readily available to molecules of a nitroaromatic quencher. This rationale is also observed in the case of a related compound bearing methoxy side chains instead of the long octyloxy moieties. Fluorescence-lifetime experiments show that the efficient quenching process in the nonporous crystallized films of the substituted compound is due to a fast (<70 ps) diffusion of excitons from the bulk of the film toward the surface where they are quenched, thus providing evidence of antenna effects.

Elaboration, activity and stability of silica-based nitroaromatic sensors.

Functionalized silica-based thin films, modified with hydrophobic groups, were synthesized and used as sensors for nitroaromatic compound (NAC) specific detection. Their performance and behavior, in terms of stability, ageing and regeneration, have been fully characterized by combining chemical characterization techniques and electron microscopy. NAC was efficiently and specifically detected using these silica-based sensors, but showed a great degradation in the presence of humidity. Moreover, the sensor sensitivity seriously decreases with storage time. Methyl- and phenyl-functionalization helped to overcome this humidity sensitivity. Surface characterization enabled us to establish a direct correlation between the appearance, and increasing amount, of adsorbed carbonyl-containing species, and sensor efficiency. This contamination, appearing after only one month, was particularly important when sensors were stored in plastic containers. Rinsing with cyclohexane enables us to recover part of the sensor performance but does not yield a complete regeneration of the sensors. This work led us to the definition of optimized elaboration and storage conditions for nitroaromatic sensors.

Ability of various materials to detect explosive vapors by fluorescent technologies: a comparative study.

For the development of fluorescent sensors, one of the key points is choosing the sensitive material. In this article, we aim at evaluating, under strictly identical experimental conditions, the performance of three materials for the detection of dinitrotoluene (a volatile marker of trinitrotoluene) through different parameters: response time, fluorescence intensity, sensitivity, reversibility, reaction after successive exposures and long-term stability. The results are discussed according to the nature of the sensitive materials. This first study rendered it possible to select a conjugated molecule as the best sensitive material for the development of a lab-made prototype. In a second part, the selectivity of this particular sensitive material was studied and its ability to detect TNT could be demonstrated.

Comparison of fluorescence and QCM technologies: example of explosives detection with a pi-conjugated thin film.

A pi-conjugated compound was synthesized as a sensitive material for explosives detection. The detection of vapors of 2,4-dinitrotoluene was demonstrated with quartz crystal microbalance (QCM) and fluorescence transduction methods. The fluorescence intensity monitoring shows a higher sensitivity and selectivity than the monitoring of the QCM frequency. Both methods appear to be synergic when used simultaneously as the sensor helps to discriminate interferent vapors from nitroaromatics.

Ultra trace detection of explosives in air: development of a portable fluorescent detector.

This paper describes a system for the detection of nitroaromatic explosives consisting of a portable detector based on a specific fluorescent material. The developed sensor was able to perform an ultra trace detection of explosives, such as trinitrotoluene (TNT) or its derivate 2,4-dinitrotoluene (DNT), in ambient air or on objects tainted with explosives. In the presence of nitroaromatic vapors, the fluorescence of the material was found to decrease due to the adsorption of nitroaromatic molecules on its specific adsorption sites. The sensor exhibited a large sensitivity to TNT or DNT at their vapor pressures (respectively 6 and 148 ppbv) and the detection threshold was evaluated on a laboratory test setup and was found to be 0.75 ppbv for TNT. Moreover, the detector demonstrated no loss of performance in the presence of humidity or interfering compounds. All the tests led to the conclusion that the sensor fulfills the main requirements for the identification of suspect luggage, forensic analyses or battlefields clearing.