Detection Of Nitroaromatic Explosives Research Articles

Fluorescent organic–inorganic hybrid polyphosphazene microspheres for the trace detection of nitroaromatic explosives

Highly cross-linked, intrinsically fluorescent organic–inorganic hybrid polymer microspheres bearing primary amine groups on the surface have been successfully prepared through a one-pot polycondensation of hexachlorocyclotriphosphazene with benzidine. Just by the single-step introduction of plentiful π-conjugated benzidine units in the structure, the resulting microspheres easily obtain both the luminescence and abundant active amino groups, with no need for more modification. Thus further using the microspheres as fluorescence-based nitroaromatic sensor, 2,4,6-trinitrotoluene, 2,4-dinitrotoluene, and picric acid can be effectively and sensitively detected. Because the nitroaromatic analytes can be effectively enriched on the surface of the microspheres by the charge-transfer complexing interaction between electron-deficient aromatic rings and electron-rich amino groups, which facilitates the electron transfer and energy transfer from microspheres to nitroaromatics, and finally leads to a significant and sensitive fluorescence quenching response. Moreover, the microspheres also exhibit remarkable thermal stability, photobleaching stability, and solvent resistance and dispersion ability in various solvents including both aqueous and organic media, owing to the highly cross-linked and organic–inorganic hybrid structure.

A Rational Self‐Sacrificing Template Route to Metal–Organic Framework Nanotubes and Reversible Vapor‐Phase Detection of Nitroaromatic Explosives

Metal-organic framework nanotubes (MOFNTs) are achieved by a strategy in which MOF nanorods formed initially act as a self-sacrificing template for the formation of the final MOFNTs. The fluorescent MOFNTs obtained exhibit high sensitivity, significant selectivity, and a fast response rate for the reversible vapor-phase detection of nitroaromatic explosives.

Rapid detection of nitroaromatic and nitramine explosives on chromatographic paper and their reflectometric sensing on PVC tablets

Rapid and inexpensive sensing of explosive traces in soil and post-blast debris for environmental and criminological purposes with optical sensors has recently gained importance. The developed sensing method for nitro-aromatic and nitramine-based explosives is based on dropping an acetone solution of the analyte to an adsorbent surface, letting the solvent to dry, spraying an analytical reagent to produce a persistent spot, and indirectly measuring its reflectance by means of a miniature spectrometer. This method proved to be useful for on-site determination of nitro-aromatics (trinitrotoluene (TNT), 2,4,6-trinitrophenylmethylnitramine (tetryl) and dinitrotoluene (DNT)) and nitramines (1,3,5-trinitro-1,3,5-triazacyclohexane (RDX) and octahydro-1,3,5,7-tetranitro-1,3,5,7-tetrazocine (HMX)) pre-adsorbed on a poly vinyl chloride (PVC) surface, with the use of different spray reagents for each group of explosives producing different colors. The calibration equations of the tested compounds as reflectance vs. concentration showed excellent linearity (correlation coefficient: 0.998–0.999). The linear quantification interval in terms of absolute quantity of analyte was 0.1–0.5μg. The developed method was successfully tested for the analysis of military explosives Comp B and Octol, and was validated against high performance liquid chromatography (HPLC). The reflectometric sensing method could also be used for qualitative identification of the nitrated explosives on a chromatographic paper. The reagent-impregnated paper could also serve as sensor, enabling semi-quantitative determinations of TNT and tetryl.

Surfactant-assisted synthesis of lanthanide metal-organic framework nanorods and their fluorescence sensing of nitroaromatic explosives

Nanocrystals of [Eu 2(BDC) 3(H 2O) 2] n ( 1), a lanthanide-containing metal-organic framework (MOF) with a two-dimensional layer structure, were synthesized by using a surfactant-assisted hydothermal method. Nanorods with different sizes were prepared in the presence of a cationic surfactant, cetyltrimethyl ammonium bromide, depending on various reaction times. To demonstrate the ability of 1 nanorods for detection of nitroaromatic explosives, the fluorescence quenching and fluorescence titration experiments were carried out. Fluorescence of 1 nanorods was found to be highly sensitive to the nitroaromatics such as 2-nitrotoluene, 4-nitrotoluene, 2,4-dinitrotoluene, and 2,6-dinitrotoluene, suggesting that lanthanide-containing MOF nanocrystals can be excellent candidates for the rapid detection of nitroaromatic explosives.

Wearable electrochemical sensors for in situ analysis in marine environments

The development of wearable screen-printed electrochemical sensors on underwater garments comprised of the synthetic rubber neoprene is reported. These wearable sensors are able to determine the presence of environmental pollutants and security threats in marine environments. Owing to its unique elastic and superhydrophobic morphology, neoprene is an attractive substrate for thick-film electrochemical sensors for aquatic environments and offers high-resolution printing with no apparent defects. The neoprene-based sensor was evaluated for the voltammetric detection of trace heavy metal contaminants and nitroaromatic explosives in seawater samples. We also describe the first example of enzyme (tyrosinase) immobilization on a wearable substrate towards the amperometric biosensing of phenolic contaminants in seawater. Furthermore, the integration of a miniaturized potentiostat directly on the underwater garment is demonstrated. The wearable sensor-potentiostat microsystem provides a visual indication and alert if the levels of harmful contaminants have exceeded a pre-defined threshold. The concept discussed here is well-suited for integration into dry- and wetsuits worn by divers and recreational surfers/swimmers, thereby providing them with the ability to continuously assess their surroundings for environmental contaminants and security hazards.

Fluorescent carbazole dendrimers for the detection of explosives

Three generations of fluorescent carbazole dendrimers with spirobifluorene cores are studied as model chemosensor systems for the detection of nitroaromatic explosives via fluorescence quenching. Stern–Volmer measurements in solution with a series of nitrated analytes including the 2,4,6-trinitrotoluene (TNT) byproduct 2,4-dinitrotoluene (DNT) and the plastic explosives taggant 2,3-dimethyl-2,3-dinitrobutane (DMNB) showed an increase in affinity and hence quenching efficiency between the first and second generation dendrimers. In spite of the differences in the solution Stern–Volmer constants the solid state quenching response to the analytes was found to be independent of generation with the exception of 1,4-dinitrobenzene (DNB), where the quenching decreases with increasing generation. It was found that it was necessary to heat the films to release the analytes with the temperature required dependent on the analyte and/or dendrimer generation. These two results show that a simple solution Stern–Volmer analysis is not always sufficient for qualifying film sensing performance and that the drive to develop sensing materials with high solution Stern–Volmer constants for real applications needs to be reconsidered.

Fluorescent metal–organic framework for selective sensing of nitroaromatic explosives

Highly luminescent micrometre-sized fine particles of a Zn(II) metal-organic framework (MOF) of a new π-electron rich tricarboxylate dispersed in ethanol is demonstrated as a selective sensory material for the detection of nitroaromatic explosives via a fluorescence quenching mechanism.

A facile and sensitive fluorescent sensor using electrospun nanofibrous film for nitroaromatic explosive detection

A newly developed electrospun nanofibrous film sensor based on tetrakis(4-methoxylphenyl)porphyrin (TMOPP) and polystyrene showed favorable fluorescence sensing performance towards four nitroaromatic explosives. The morphology of nanofibers was uniform with diameters of 300–400 nm. The sensing nanofibrous film possessed satisfactory reproducibility amongst three batches, reversibility with loss of sensing signal only ∼10% after six quenching-regeneration cycles, and selectivity to give minimal response to common interferents. Using amine modification as a new approach and by introducing a porogen, the nanofibrous film sensor exhibited a highly sensitive response towards parts-per-billion levels of 2,4,6-trinitrotoluene vapor, and parts-per-trillion levels of picric acid vapor, respectively. This work provides a facile and promising strategy to construct portable optical devices for nitroaromatic explosive detection.

Textile‐based Electrochemical Sensing: Effect of Fabric Substrate and Detection of Nitroaromatic Explosives

AbstractThis study examines the influence of textile substrates upon the behavior of wearable screen‐printed electrodes and demonstrates the attractive sensing properties of these sensors towards the detection of nitroaromatic explosives. Compared to electrodes printed on common cotton or polyester substrates, GORE‐TEX‐based electrochemical sensors display reproducible background cyclic voltammograms, reflecting the excellent water‐repellant properties of the GORE‐TEX fabric. The wetting properties of different printed textile electrodes are elucidated using contact angle measurements. The influence of laundry washing and mechanical stress is explored. The GORE‐TEX‐based printed electrodes exhibit favorable detection of 2,4‐dinitrotoluene (DNT) and 2,4,6‐trinitrotoluene (TNT) explosives, including rapid detection of DNT vapor.

Challenge of false alarms in nitroaromatic explosive detection—a detection device based on surface-enhanced Raman spectroscopy

A challenge in the detection of explosives is the differentiation between explosives and contaminants. Synthetic musk-containing perfumes can cause false alarms, as these perfumes are nitroaromatic compounds, which can be mistaken for trinitro toluene (TNT) by some detectors. We present a detection principle based on surface-enhanced Raman scattering (SERS). A stream of the airborne compounds is focused and resublimated on a cooled nanostructured gold surface. We recorded high-resolution SERS spectra of TNT, musk xylene, and musk ketone. The nitroaromatic compounds can be identified unambiguously by their SERS spectra. Even the dominant bands containing nitro-group scissoring and symmetric stretching modes are significantly shifted by the difference in molecular structure.

Carbon nanotubes-based chemiresistive immunosensor for small molecules: Detection of nitroaromatic explosives

In recent years, there has been a growing focus on use of one-dimensional (1-D) nanostructures, such as carbon nanotubes and nanowires, as transducer elements for label-free chemiresistive/field-effect transistor biosensors as they provide label-free and high sensitivity detection. While research to-date has elucidated the power of carbon nanotubes- and other 1-D nanostructure-based field effect transistors immunosensors for large charged macromolecules such as proteins and viruses, their application to small uncharged or charged molecules has not been demonstrated. In this paper we report a single-walled carbon nanotubes (SWNTs)-based chemiresistive immunosensor for label-free, rapid, sensitive and selective detection of 2,4,6-trinitrotoluene (TNT), a small molecule. The newly developed immunosensor employed a displacement mode/format in which SWNTs network forming conduction channel of the sensor was first modified with trinitrophenyl (TNP), an analog of TNT, and then ligated with the anti-TNP single chain antibody. Upon exposure to TNT or its derivatives the bound antibodies were displaced producing a large change, several folds higher than the noise, in the resistance/conductance of SWNTs giving excellent limit of detection, sensitivity and selectivity. The sensor detected between 0.5 ppb and 5000 ppb TNT with good selectivity to other nitroaromatic explosives and demonstrated good accuracy for monitoring TNT in untreated environmental water matrix. We believe this new displacement format can be easily generalized to other one-dimensional nanostructure-based chemiresistive immuno/affinity-sensors for detecting small and/or uncharged molecules of interest in environmental monitoring and health care.

Synthesis of Poly(4‐vinylpyridine) Thin Films by Initiated Chemical Vapor Deposition (iCVD) for Selective Nanotrench‐Based Sensing of Nitroaromatics

AbstractA new nanoscale sensing concept for the detection of nitroaromatic explosives is described. The design consists of nitroaromatic‐selective polymeric layers deposited inside microfabricated trenches. As the layers are exposed to nitroaromatic vapors, they swell and contact each other to close an electrical circuit. The nitroaromatic selective polymer, poly(4‐vinylpyridine) (P4VP), is deposited in the trenches using initiated chemical vapor deposition (iCVD). P4VP is characterized for the first time as a selective layer for the absorption of nitroaromatic vapors. The Flory–Huggins equation is used to model the swelling response to nitroaromatic vapors. The Flory–Huggins interaction parameter for the P4VP–nitrobenzene system at 40 °C is 0.71 and 0.25 for P4VP–4‐nitrotoluene at 60 °C. Sensing of nitrobenzene vapors is demonstrated in a prototype device, while techniques to improve the performance of the design in terms of response time and sensitivities are described. Modeling shows that concentration and mass limits of detection of 0.95 ppb and 3 fg, respectively, can be achieved.

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.

A fluorescence-based cyclodextrin sensor to detect nitroaromatic explosives

We report the use of a cyclodextrin inclusion complex (CIC) in fluorescence sensing to provide a method to classify energetic nitroaromatic compounds. A CIC was prepared by the inclusion of 9,10-bis(phenylethynyl)anthracene (BPEA) with γ-cyclodextrin (CD) (BPEA/CD) in water with 5% tetrahydrofuran by volume. The inclusion behaviour of BPEA with γ-CD was studied by fluorescence spectroscopy. The effect of α- and β-CD with BPEA was also studied. In this system, the inclusion complex BPEA/CD acted as the host and the guests were the explosives 2,4,6-trinitrotoluene (TNT), hexahydro-1,3,5-trinitro-1,3,5-triazine (RDX), 2,4,6-trinitrophenyl-N-ethylnitramine (Tetryl), octahydro-1,3,5,7-tetranitro-1,3,5,7-tetrazine (HMX) and pentaerythritoltetranitrate (PETN). The binding of TNT, RDX, Tetryl, HMX and PETN with CD/BPEA was studied for the potential use of BPEA/CD in a sensing application. Experiments were also conducted with explosives and BPEA in the absence of CD. The optical response found for the explosives TNT, RDX, Tetryl, HMX and PETN with BPEA/CD was modelled with a modified Stern–Volmer relationship. This investigation showed successful classification of aromatic and non-aromatic explosives. The approach using a CD-based fluorescence sensor has the potential to be a sensing technology for the detection of nitroaromatic explosives.

Organic nanofibrils based on linear carbazole trimer for explosive sensing

Organic fluorescent nanofibrils were fabricated from a linear carbazole trimer and employed for expedient detection of nitroaromatic explosives (DNT and TNT) and highly volatile nitroaliphatic explosives (nitromethane).

Pyrene-Functionalized Ruthenium Nanoparticles as Effective Chemosensors for Nitroaromatic Derivatives

Pyrene-functionalized Ru nanoparticles were synthesized by olefin metathesis reactions of carbene-stabilized Ru nanoparticles with 1-vinylpyrene and 1-allylpyrene (the resulting particles were denoted as Ru=VPy and Ru=APy, respectively) and examined as sensitive chemosensors for the detection of nitroaromatic compounds, such as 2,4,6-trinitrotoluene (TNT), 2,4-dinitrotoluene (2,4-DNT), 2,6-dinitrotoluene (2,6-DNT), 1-chloro-nitrobenzene (CNB), and nitrobenzene (NB), by their effective quenching of the nanoparticle fluorescence. It was found that the detection sensitivity increased with increasing nitration of the molecules. Additionally, in comparison to monomeric pyrene derivatives, both Ru=VPy and Ru=APy nanoparticles exhibited markedly enhanced performance in the detection of nitroaromatic explosives, most probably as a result of the enhanced collision frequency between the fluorophores and the quencher molecules. Furthermore, Ru=VPy nanoparticles displayed much higher sensitivity (down to the nanomolar regime for TNT) than Ru=APy in the detection of these nitroaromatic explosives, which was ascribed to the extended intraparticle conjugation that provided efficient pathways for energy/electron transfer and consequently amplified the analyte binding events.

Synthesis, Luminescence Properties, and Explosives Sensing with 1,1-Tetraphenylsilole- and 1,1-Silafluorene-vinylene Polymers

The syntheses, spectroscopic characterizations, and fluorescence quenching efficiencies of polymers and copolymers containing tetraphenylsilole- or silafluorene-vinylene repeat units are reported. These materials were prepared by catalytic hydrosilylation reactions between appropriate monomeric metallole alkynes and hydrides. Trimeric model compounds methyl(tetraphenyl)silole-vinylene trimer (1), methyl(tetraphenyl)silole-silafluorene-vinylene cotrimer (2), and methylsilafluorene-vinylene trimer (3) were synthesized to provide detailed structural and spectroscopic characteristics of the polymer backbone and to assess the extent of delocalization in the luminescent excited state. Poly(tetraphenylsilole-vinylene) (4), poly(tetraphenylsilole-silafluorene-vinylene) (5), and poly(silafluorene-vinylene) (6) maintain a regio-regular trans-vinylene Si−C backbone with possible ground state σ*−π and excited state σ*−π* conjugation through the vinylene bridge between metallole units. Fluorescence spectra of the polymers show an ∼13 nm bathochromic shift in λflu from their respective model compounds. Molecular weights (Mn) for these polymers and copolymers are in the range of 4000–4500. Detection of nitroaromatic explosives by solution-phase fluorescence quenching of polymers 4−6 was observed with Stern−Volmer constants in the range of 400−20 000 for TNT, DNT, and picric acid (PA). A surface detection method for the analysis of solid particulates of TNT, DNT, PA, RDX, HMX, Tetryl, TNG, and PETN is also described for silafluorene-containing polymers. Polymer 6 exhibited detection for all the preceding types of explosive residues with a 200 pg cm−2 detection limit for Tetryl. Polymers 4 and 5 exhibited only luminescence quenching with nitroaromatic explosives, revealing that the excited-state energy of the sensor plays a key role in the fluorescence detection of explosives.

Atmospheric pressure ion/molecule reactions for the selective detection of nitroaromatic explosives using acetonitrile and air as reagents

Acetonitrile vapor and air are useful reagents for the selective detection of nitroaromatic compounds using atmospheric pressure ion/molecule reactions. Reagent ions CH2CN- and CN- generated from acetonitrile, and O-*, OH- and OOH- produced from the oxygen in air, react with vapor-phase and condensed-phase nitroaromatics in the course of atmospheric pressure chemical ionization (APCI) and desorption atmospheric pressure chemical ionization (DAPCI), respectively. The homogeneous and the heterogeneous phase reactions both lead to the formation of the same anionic adducts. These adducts have characteristic fragmentation patterns upon collisional activation, which makes these two reagents valuable for the selective detection of particular nitroaromatics, including explosives present as components of complex mixtures. Complementary information is available from the two reagents because their different chemistry facilitates analyte identification. DAPCI is demonstrated to be a useful ambient detection method for nitroaromatic explosives absorbed on surfaces.

Rapid voltammetric determination of nitroaromatic explosives at electrochemically activated carbon-fibre electrodes

The electrochemical behaviour of some nitroaromatic explosives (2,4,6-trinitrotoluene, TNT; 2,6-dinitrotoluene, 2,6-DNT; 2-nitrotoluene, 2-NT; 2-amino-4,6-dinitrotoluene, 2-A-4,6-DNT; 3,5-dinitroaniline, 3,5-DNA; and nitrobenzene, NB) at electrochemically activated carbon-fibre microelectrodes is reported. Electrochemical activation of such electrode material by repeated square-wave (SW) voltammetric scans between 0.0 and +2.6 V versus Ag/AgCl, produced a dramatic increase in the cathodic response from these compounds. This is attributed to the increase of the carbon-fibre surface area, because of its fracture, and the appearance of deep fissures along the main fibre axis into which the nitroaromatic compounds penetrate. Based on the important contribution of adsorption and/or thin layer electrolysis to the total voltammetric response, a SW voltammetric method for rapid detection of nitroaromatic explosives was developed. No interference was found from compounds such as hydrazine, phenolic compounds, carbamates, triazines or surfactants. The limits of detection obtained are approximately 0.03 microg mL(-1) for all the nitroaromatic compounds tested. The method was applied for the determination of TNT in water and soil spiked samples; recoveries were higher than 95% in all cases.

Determination of nitroaromatic and nitramine explosives from a PTFE wipe using thermal desorption-gas chromatography with electron-capture detection

A method for the detection of nitroaromatic and nitramine explosives from a PTFE wipe has been developed using thermal desorption andgas chromatography with electron-capture detection (TD-GC-ECD). For method development a standard mixture containing eight nitroaromatic and two nitramine (HMX and RDX) explosive compounds was spiked onto a PTFE wipe. Explosives were desorbed from the wipe in a commercial thermal desorption system and trapped onto a cooled injection system, which was incorporated into the injection port of the GC. A dual column, dual ECD configuration was adopted to enable simultaneous confirmation analysis of the explosives desorbed. For the desorption of 50 ng of each explosive, desorption efficiencies ranged between 80.0 and 117%, for both columns. Linearity over the range 2.5-50 ng was demonstrated for each explosive on both columns with r2 values ranging from 0.979 to 0.991 and limits of detection less than 4 ng. Desorption of HMX from a PTFE wipe has also been demonstrated for the first time, albeit at relatively high loadings (100 ng).