Several polymers have been used to detect nitroaromatic explosives by a variety of transduction schemes. Detection relies on both electronic and structural interactions between the sensing material and the analyte. Quenching of luminescent polymers by electron deficient nitroaromatic explosives, such as trinitrotoluene, may be monitored to detect explosives. Resistive sensing using carbon black particles that have been coated with different organic polymers and deposited across metallic leads can also be used to detect nitroaromatic vapors in an electronic nose approach. Frequency changes in surface acoustic wave devices may be monitored to detect nitroaromatics after their adsorption into polymer coatings. Luminescent polymetalloles have recently been investigated for sensing explosives in aqueous-based solutions and for improved visual detection of trace particulates on surfaces.

http://nathan.instras.com/ResearchProposalDB/doc-151.pdf

Polymer sensors for nitroaromatic explosives detection

The synthesis, spectroscopic characterization, and fluorescence quenching efficiency of polymers and copolymers containing tetraphenylsilole or tetraphenylgermole with Si-Si, Ge-Ge, and Si-Ge backbones are reported. Poly(tetraphenyl)germole, 2, was synthesized from the reduction of dichloro(tetraphenyl)germole with 2 equivs of Li. Silole-germole alternating copolymer 3 was synthesized by coupling dilithium salts of tetraphenylsilole dianion with dichloro(tetraphenyl)germole. Other tetraphenylmetallole-silane copolymers, 4-12, were synthesized through the Wurtz-type coupling of the dilithium salts of the tetraphenylmetallole dianion and corresponding dichloro(dialkyl)silanes. The molecular weights (M(w)) of these metallole-silane copolymers are in the range of 4000 approximately 6000. Detection of nitroaromatic molecules, such as nitrobenzene (NB), 2,4-dinitrotoluene (DNT), 2,4,6-trinitrotoluene (TNT), and picric acid (PA), has been explored. A linear Stern-Volmer relationship was observed for the first three analytes, but not for picric acid. Fluorescence spectra of polymetalloles or metallole-silane copolymers obtained in either toluene solutions or thin polymer films displayed no shift in the maximum of the emission wavelength. This suggests that the polymetalloles or metallole-silanes exhibit neither pi-stacking of polymer chains nor excimer formation. Fluorescence lifetimes of polymetalloles and metallole-silanes were measured both in the presence and absence of TNT, and tau(o)/tau is invariant. This requires that photoluminescence quenching occurs by a static mechanism.

Detection of nitroaromatic explosives based on photoluminescent polymers containing metalloles.

Three new electron-rich metal-organic frameworks (MOF-1-MOF-3) have been synthesized by employing ligands bearing aromatic tags. The key role of the chosen aromatic tags is to enhance the -electron density of the luminescent MOFs. Single-crystal X-ray structures have revealed that these MOFs form three-dimensional porous networks with the aromatic tags projecting inwardly into the pores. These highly luminescent electron-rich MOFs have been successfully utilized for the detection of explosive nitroaromatic compounds (NACs) on the basis of fluorescence quenching. Although all of the prepared MOFs can serve as sensors for NACs, MOF-1 and MOF-2 exhibit superior sensitivity towards 4-nitrotoluene (4-NT) and 2,4-dinitrotoluene (DNT) compared to 2,4,6-trinitrotoluene (TNT) and 1,3,5-trinitrobenzene (TNB). MOF-3, on the other hand, shows an order of sensitivity in accordance with the electron deficiencies of the substrates. To understand such anomalous behavior, we have thoroughly analyzed both the steady-state and time-resolved fluorescence quenching associated with these interactions. Determination of static Stern-Volmer constants (K-S) as well as collisional constants (K-C) has revealed that MOF-1 and MOF-2 have higher K-S values with 4-NT than with TNT, whereas for MOF-3 the reverse order is observed. This apparently anomalous phenomenon was well corroborated by theoretical calculations. Moreover, recyclability and sensitivity studies have revealed that these MOFs can be reused several times and that their sensitivities towards TNT solution are at the parts per billion (ppb) level.

Modification of Extended Open Frameworks with Fluorescent Tags for Sensing Explosives: Competition between Size Selectivity and Electron Deficiency

Metal–organic frameworks (MOFs), composed of organic ligands and metal nodes, are well known for their high and permanent porosity, crystalline nature and versatile potential applications, which promoted them to be one of the most rapidly developing research focuses in chemical and materials science. During the various applications of MOFs, the photoluminescence properties of MOFs have received growing attention, especially for nitroaromatics (NACs) sensing, due to the consideration of homeland security, environmental cleaning and military issues. In this highlight, we summarize the progress in recent research in NACs sensing based on LMOFs cataloged by sensing techniques in the past three years, and then we describe the sensing applications for nano-MOF type materials and MOF film, together with MOF film applications.

Metal–organic frameworks based luminescent materials for nitroaromatics sensing

Several π-electron rich fluorescent aromatic compounds containing trimethylsilylethynyl functionality have been synthesized by employing Sonogashira coupling reaction and they were characterized fully by NMR (1H, 13C)/IR spectroscopy. Incorporation of bulky trimethylsilylethynyl groups on the peripheral of the fluorophores prevents self-quenching of the initial intensity through π–π interaction and thereby maintains the spectroscopic stability in solution. These compounds showed fluorescence behavior in chloroform solution and were used as selective fluorescence sensors for the detection of electron deficient nitroaromatics. All these fluorophores showed the largest quenching response with high selectivity for nitroaromatics among the various electron deficient aromatic compounds tested. Quantitative analysis of the fluorescence titration profile of 9,10-bis(trimethylsilylethynyl)anthracene with picric acid provided evidence that this particular fluorophore detects picric acid even at ppb level. A sharp visual detection of 2,4,6-trinitrotoluene was observed upon subjecting 1,3,6,8-tetrakis(trimethylsilylethynyl)pyrene fluorophore to increasing quantities of 2,4,6-trinitrotoluene in chloroform. Furthermore, thin film of the fluorophores was made by spin coating of a solution of 1.0 × 10−3 M in chloroform or dichloromethane on a quartz plate and was used for the detection of vapors of nitroaromatics at room temperature. The vapor-phase sensing experiments suggested that the sensing process is reproducible and quite selective for nitroaromatic compounds. Selective fluorescence quenching response including a sharp visual color change for nitroaromatics makes these fluorophores as promising fluorescence sensory materials for nitroaromatic compounds (NAC) with a detection limit of even ppb level as judged with picric acid.

Fluorescence and visual sensing of nitroaromatic explosives using electron rich discrete fluorophores

We describe a pulsed spectrometer for detection of nuclear quadrupole resonance on the nuclei of nitrogen N-14 with fast Fourier transform. The use of a multipulse sequence, four channel system for data registration and processing permits detection of the nuclear quadrupole resonance (NQR) signal in the presence of strong interference and the piezo effect. Using this spectrometer we registered the NQR signal from an explosive sample of 150 g (92% RDX) at a distance of 22 cm, and the time of detection was 81 s.

R. Fisher

Papers

Pulsed spectrometer for nuclear quadrupole resonance for remote detection of nitrogen in explosives