TNT Vapor Research Articles

Pyrene-Based AIEE-Active Vertically Grown Luminescent Material for Selective and Sensitive Detection of TNT Vapor

Pyrene-Based AIEE-Active Vertically Grown Luminescent Material for Selective and Sensitive Detection of TNT Vapor

The Effect of Humidity and Dopants on the Detection of TNT Vapor by Differential Ion Mobility Spectrometry (DMS)

The Effect of Humidity and Dopants on the Detection of TNT Vapor by Differential Ion Mobility Spectrometry (DMS)

Numerical derivation of pressure-impulse (P-I) diagrams of prefabricated RC columns with steel joints subjected to blast loads

In recent decades, terrorist attacks and accidental explosions have occurred frequently. The casualties are not only caused by the shock wave, but also by the structural collapse initialed from the failure of structural columns. In this paper, the dynamic response and damage mechanism of prefabricated reinforced concrete (RC) columns with steel joints (PRC) subjected to blast loads are numerically investigated. By comparing the numerical results with the experimental results, the accuracy of the finite element (FE) model is firstly verified. Then, dynamic responses and damage of PRC under blast loads induced by the TNT explosions and vapor cloud explosions (VCEs) are investigated and compared with each other. The results indicated that PRC damage under VCEs with 9.3 MPa is larger than that under TNT explosions. Conversely, the damage under VCEs with 7 MPa is smaller than that under TNT explosions, and the blast-induced damage and dynamic behavior of PRC under two types of explosions is different. Subsequently, parametric studies are further carried out to investigate the influence of key parameters of PRC, including longitudinal and transverse reinforcement ratio, column dimensions, concrete strength, steel sleeve dimensions on PRC damage. It is revealed that different parameters affect the damage for PRC column in different load regions of P-I diagrams, including the impulsive load region, dynamic load region and quasi-static load region. Increasing the sleeve length, sleeve ratio and transverse reinforcement ratio improves the shear-resistant performance of PRC, and these parameters more easily affected PRC damage in the impulsive load region. Increasing the concrete strength and column depth can increase the blast-resistant performance of PRC in three load regions. Based on parametric studies, pressure-impulse (P-I) diagrams for damage evaluation of PRC under VCEs and TNT explosions are proposed and verified. Finally, Blast-resistant design procedure of PRC based on P-I diagram is developed.

Enhanced TNT vapor sensing through a PMMA-mediated AIPE-active monocyclometalated iridium(III) complex: a leap towards real-time monitoring.

Based on the explosive nature and harmful effects of nitro-based explosive materials on living beings and the environment, it is extremely important to develop luminescence-based probe molecules for their detection with excellent selectivity and sensitivity. Two AIPE (aggregation-induced phosphorescence emission)-active iridium(III) complexes (M1 and M2) were developed for the sensitive detection of TNT in both contact and non-contact modes. The aggregate solutions of both complexes (M1 and M2 in THF/H2O, 1/9 by volume) detected TNT at the pico-molar (pM) level. These complexes showed greatly enhanced emission intensity while embedded in a PMMA(polymethyl methacrylate) matrix film. The amplified quantum efficiency, improved phosphorescence lifetime, and enhanced porous network of M2-PMMA composite helps to improve the sesitivity of TNT vapor detection. Interestingly, the sensitivity of the detection of TNT by the M2 complex was significantly improved (5-fold) in a PMMA-incorporated complex (CP) with an observed limit of detection (LOD) of 12.8 ppb. From the BET analysis of CP, it was observed that the mesoporous network of CP has an average pore diameter of 8.52 nm and a surface area of 2.03 m2 g-1. The porous network of CP assists in trapping TNT vapor in a polymeric network containing an electron-rich probe (iridium(III) complex, M2), which helps to effectively trap TNT, thus enhancing electronic communication. As a result, significant emission quenching was observed.

Detection of TNT Vapors by Fluorescence Quenching and Self-Recovery Using Highly Fluorescent Conjugated Silole Polymers

Detection of TNT Vapors by Fluorescence Quenching and Self-Recovery Using Highly Fluorescent Conjugated Silole Polymers

Advanced functional rGO@MoS2@PEDOT: PSS multicomponent-based nanocomposite films for rapid and ultra-sensitive TNT detection

Ultra-sensitive and highly selective detectors are attracting increasing attention to combat any undesired terrorist activities. High sensitivity and selectivity are the two major concerns for the development of the sensor for explosive detection. Herein, 2,4,6 TNT explosive sensor based on multicomponent nanocomposite film (Mc-NFs) is fabricated through an interface modulation technique. The Mc-NFs, porphyrin functionalized rGO@MoS2 @PEDOT: PSS (TPP-rGO@MoS2 @PEDOT: PSS) films, exhibit excellent selectivity and ultra-sensitivity towards TNT vapor at room temperature with outstanding sensing response (246% for 1.5 ppb), a rapid response time (3.5 s). The obtained results reveal the synergistic actions of the individual sensor components, where the rich active sites of MoS2 are playing a major role in high sensing response, π-π interactions between TPP-rGO and TNT lead to rapid adsorption/desorption of TNT vapors, and PEDOT: PSS assures the homogenous dispersion of the components in the sensor film. Further, the film exhibits excellent selectivity towards highly oxidizing TNT vapors due to strong N-type nature of the film along with the functionalization of rGO with porphyrin. The sensor has also been investigated for different concentrations of TNT vapors in the concentration range of 1.5–47ppb, showing an average rapid response time of 2 s, and recovery time of 42.5 s. The sensor has a high sensitivity of 4.09% /ppb, remarkable linearity (R-value > 0.976), good reproducibility and repeatability, low limit of detection (0.1 ppb), and good sensing stability. The prepared TPP-rGO-10%@MoS2-5%@PEDOT: PSS film has the potential to be used as an ultra-sensitive TNT detector in handheld devices.

Chemical reduction as a facile colorimetric approach for selective TNT detection by spectrophotometry and photothermal lens spectroscopy

In this study, the simple determination of TNT is achieved through the vivid stable red color products generated after chemically reduction by NaBH4 as a common and accessible reducing/colorimetric reagent. Some other nitroaromatics were impressed under reduction reaction and led to the colorful products. The color of these reduced nitroaromatics were unstable and approximately vanished after some few minutes which ameliorated the selectivity in TNT determination. Utilizing the time-dependent selectivity, the method was applied specifically for discriminating of TNT from other nitroaromatic compounds (NACs). UV–vis spectrophotometry and photothermal lens spectrometry were employed as detection techniques. The former was simpler and more available in various laboratories while the latter provides higher sensitivity. It was revealed that the photothermal lens responses were linear from 2.0 to 55.0 nM with a limit of detection (LOD) of about 0.8 nM. The LOD of the photothermal lens measurement were found to be 241 times lower than that of the UV–vis spectrophotometry in TNT quantification. The evolved method was successfully carried out for TNT vapor determination after trapping into the colorimetric reagent. The recoveries and relative standard deviations (RSD, n = 3) calculated for 3 gas samples were ≥91% and ≤7%, respectively.

Vapor-Phase Substrate Nitroreductase Reaction and Its Application as TNT Electrochemical Gas Sensor

Nitroreductase (NTR) is an enzyme that specifically reduces nitroaromatic activity. Some nitroaromatic explosives are exploited by terrorists. Among these highly explosive materials, 2,4,6-trinitrotoluene (TNT) is often used, which makes the detection of TNT an important research topic in the fight against terrorism. TNT vapor detection by gas sensor is an approach that has been under active investigation for several years. Despite this effort, presently, there is limited practical success, in part, due to the ultralow volatility nature of TNT. In this work, we propose an application of the NTR reaction in a hydrogel gas sensor to detect TNT vapor. First, NTR activity in the hydrogel was confirmed by adding TNT and 2,4-dinitrotoluene (DNT) solutions to the NTR-hydrogel sensor conducting cyclic voltammetry (CV) experiments. Then, further CV experiments were carried out with gas phase samples. The CV graphs of NTR-hydrogels detecting vapors containing the explosive substrates and negative controls were compared. Results showed that the signal from the nitroaromatics increased with exposure time, where the TNT signal was the highest of all tested compounds. The gas sensor was sensitive enough to detect TNT gas presented in an ambient air at room temperature.

Influence of Air Flow on Luminescence Quenching in Polymer Films towards Explosives Detection Using Drones.

Explosive detection has become an increased priority in recent years for homeland security and counter-terrorism applications. Although drones may not be able to pinpoint the exact location of the landmines and explosives, the identification of the explosive vapor present in the surrounding air provides significant information and comfort to the personnel and explosives removal equipment operators. Several optical methods, such as the luminescence quenching of fluorescent polymers, have been used for explosive detection. In order to utilize sensing technique via unmanned vehicles or drones, it is very important to study how the air flow affects the luminescence quenching. We investigated the effects of air flow on the quenching efficiency of Poly(2,5-di(2′-ethylhexyl)-1,4-ethynylene) (PEE) by TNT molecules. We treated the TNT molecules incorporated into the polymer film as non-radiative recombination centers, and found that the time derivative of the non-radiative recombination rates was greater with faster air flows. Our investigations show that relatively high air flow into an optical sensing part is crucial to achieving fast PL quenching. We also found that a “continuous light excitation” condition during the exposure of TNT vapor greatly influences the PL quenching.

Multi-stimuli distinct responsive D–A based fluorogen oligomeric tool and efficient detection of TNT vapor

P1 shows distinct emission responses with multi-stimuli, i.e., quenching for TNT sensing, red shifting for acid and base vapors, blue shifting against MFC behavior, and solvent polarity-dependent emission.

The Effect of Soil Moisture on the Ability to Detect TNT Pairs from the Sand Layer in Order to Prevent Environmental Pollution and Groundwater

The aim of the study was to investigate the influence of sand bed moisture on TNT transport from under the sand layer. The MO-2M explosive vapor detector was used, the detection mechanism of which is based on the FAIMS method. In addition, it was determined after what time the detector alarm appears, signaling the presence of TNT vapors, and how it affects the thickness of the sand layer. The performed work allowed us to assess the suitability and possibly adapt the MO-2M detector to detect non-metal mines, which will help develop new application possibilities for this device. These tests can also be used to eliminate environmental contamination resulting from the deposition of explosives in the ground and the migration of harmful compounds to groundwater.

Empirical determination of explosive vapor transport efficiencies.

The transport efficiency of 2,4-dinitrotoluene (2,4-DNT), 2,4,6-trinitrotoluene (TNT) and 1,3,5-trinitro-1,3,5-triazinane (RDX) trace vapors through tubing materials that commonly constitute vapor handling infrastructures have been determined for a variety of tubing dimensions and sampling conditions. Using a programmable temperature vaporization inlet coupled with a gas chromatography mass spectrometer (PTV-GC-MS), the explosive vapors were quantified both with and without a length of tubing of a specific material in the sampling flow path. At vapor temperatures of 30 °C and 66 °C, minimal attenuations were observed for 2,4-DNT and TNT vapor concentrations when the tubing material was in-line with the sampling flow path, indicating that the transport is largely unaffected by interactions with the surface of the tubing materials. In contrast, RDX vapors showed large attenuations as a function of both sampling conditions and tubing materials/dimensions. For those experiments where attenuated RDX vapor transport was observed, the mass sequestered by interactions between the flowing vapor and the internal tubing surface was determined to be in the range of tens to hundreds of picograms. Of all the materials examined for RDX transport, fluorinated ethylene propylene (FEP) tubing resulted in the least amount of mass loss to surface interactions, with vapor transport efficiencies (VTEs) between 95-100%. However, for some materials, the combination of tubing dimensions and sampling conditions resulted in no RDX transport, even after sampling more than 250.0 L of vapor through the tubing.

Novel laser induced fluorescence with hyperspectral imaging of amplifying fluorescent melamine resin for TNT vapor detection

Terrorism by means of explosive is an imminent threat; instant detection of explosive vapors is a vital demand. Explosives are electron deficient molecules; the vicinity of explosives to fluorescent material could hinder excitation migration resulting in fluorescence quenching. This study reports on the facile synthesis of porous melamine–formaldehyde–diethylenetriaminepentaacetic acid (MF–DTPA) resin with surface area of 162 m2/g, and average pore diameter is 94.7 (Å). MF–DTPA resin demonstrated unique ability to capture TNT vapors with complete change in its color from white to reddish. Furthermore, MF–DTPA resin demonstrated novel fluorescence properties over visible band (400–560 nm) and infrared band (700–760 nm) when stimulated with UVA LED source at 385 nm of 100 mW power. These two emission bands were completely quenched when MF–DTPA was subjected to TNT vapors. Amplified chemosensory response was archived via wired receptors in a series. Hyperspectral imaging associated with 2D moving average filter was employed to develop enhanced color intensity maps.

Leveraging Preconcentration and Partial Separations with Silicon Nanowire Arrays to Improve the Detection of Low Volatility Trace Explosive Vapors

Trace detection of explosive vapors in real world environments is hindered by strict sensitivity and selectivity requirements that need to be met in order for these techniques to be effective. The physical properties of most explosive molecules limit environmentally relevant vapor concentrations to the part per billion (ppbv) – part per trillion (pptv) range due to their saturated vapor pressures under real world conditions. Additionally, trace explosive vapor detectors must be able to discriminate against a number of potential chemical and biological interferents present in complex real world environments. In this work, we present silicon nanowire arrays (SiNW) as a novel tunable material aimed at providing trace explosive vapor detectors with the sensitivity and selectivity necessary for operational use.Dense, highly ordered silicon nanowires are fabricated through a nanosphere lithography process and topped with a porous gold electrode resulting in a high surface area adsorptive substrate intrinsically capable of rapid, precise temperature control via Joule heating. Explosive vapors are selectively preconcentrated onto the SiNW array by exploiting their affinities for the SiO2 surface of the nanowires. Chromatographic like partial separations of preconcentrated material on the array can be achieved through careful selection of desorption parameters. Using a multichannel detector such as an IMS or MS we demonstrate the preconcentration of a number of explosive vapors including 2,6-DNT, TNT, and RDX above and below their saturated vapor concentrations at room temperature, in addition to exploring the effects of desorption flow rates and temperatures on the partial separation of 2,6-DNT, 2,4-DNT, and TNT vapors. Figure 1

Detection of Nitroaromatics by Pyrene-Labeled Starch Nanoparticles

Starch nanoparticles (SNPs) were hydrophobically modified by using 1-pyrenebutyric acid (PyBA) with degrees of substitution (DS) between 0.0006 and 0.11. Fluorescence quenching studies were conducted on the pyrene-labeled starch nanoparticles (Py-SNPs) in dimethyl sulfoxide (DMSO) and water with nitromethane (NM), 4-mononitrotoluene (MNT), 2,6-dinitrotoluene (DNT), and 2,4,6-trinitrotoluene (TNT) to assess the mode of quenching of the pyrene labels in the two solvents. In DMSO where pyrene, starch, and the quenchers were soluble, a decrease in fluorescence signal was the result of dynamic encounters between the excited pyrene labels and the nitrated quenchers. In water where starch could be dispersed but pyrene and the nitroaromatic compounds (NACs) were sparingly soluble, quenching took place through the binding of NACs to pyrene aggregates. Py(11)-SNPs (Py-SNPs with a DS of 0.11)-coated filter papers (Py-CFPs) were prepared as fluorescence sensors. The fluorescence emitted by Py-CFPs was quenched to 25% of its original value within 10 ± 2, 72 ± 20, and 23 ± 4 s upon exposure to vapors of MNT, DNT, and TNT, respectively. When known amounts of NACs were deposited onto Py-CFPs, their limit of detection (LOD) when the fluorescence decreased by more than 3 standard deviations (3σ) from its original value equaled 9.2 ± 0.8, 3.3 ± 0.5, and 0.20 ± 0.02 ng/mm2 for MNT, DNT, and TNT, respectively. These response times and LODs were among the best values reported to date in the scientific literature for fluorescence sensors. The selectivity of the Py-CFPs toward NACs was also investigated by comparing their response to the presence of non-nitrated aromatics, amines, and aromatic ketones. Quenching was only observed with the latter family of chemicals tested, but with much lower efficiency compared to TNT, thus reflecting some level of selectivity toward this specific NAC.

Photothermal lens microfluidic sensor for femtomole detection of 2,4,6-trinitrotoluene based on Meisenheimer complexation

Since the simple and accurate quantification of 2,4,6-trinitrotoluene (TNT) traces is still a challenge for analytical chemists, we employed a recently developed crossed-beam photothermal lens spectrometer for highly sensitive and selective determination of TNT through a well-known Meisenheimer complexation with n-butylamine (nBA). The colorless solution of TNT in dimethyl sulfoxide (DMSO) was changed to deep-red after the addition of nBA. Hence, we used a 532 nm diode laser as excitation source in photothermal lens investigations. All the instrumental parameters and chemical conditions such as chopper frequency, sample flow velocity, amine concentration and etc. were optimized. Photothermal lens measurements yielded a linear signal dependence on TNT quantity from 5 to 100 nM. The limit of detection (LOD) was 1.6 nM (˜5 fmol). The method was successfully carried out for determination of the TNT vapor extracted into the 300 μL dimethyl sulfoxide (DMSO).

Controlled Phase Separation in Poly( p-phenyleneethynylene) Thin Films and Its Relationship to Vapor-Sensing Properties.

In this paper, we report the synthesis and mesoporous film formation of hydrophobic rodlike poly( p-phenyleneethynylene)s (PPEs) and present porosity-dependent quenching studies using 1,3,5-trinitrotoluene (TNT) vapors. Nonsolvent vapor-induced phase separation was used to induce pore formation during film casting, and the concentration of PPEs in the casting solution was controlled carefully to prevent excimer formation. We found that the structures of the sidechains of the PPEs strongly influence the range of relative humidity at which controlled pore generation occurs, which could be rationalized from interfacial energies calculated from contact angle measurements. Porosity of the PPE films resulted in increased efficiency of fluorescence quenching toward TNT vapors, which previously required very thin films (below 5 nm) for sensing applications. The control of the porous structure as well as film thickness constitutes a promising strategy for enhancing the efficiency of chemosensors and in more general applications requiring fine-tuned polymer-gas interactions.

Tetraphenylethylene Foldamers with Double Hairpin-Turn Linkers, TNT-Binding Mode and Detection of Highly Diluted TNT Vapor.

Tetraphenylethylene (TPE) foldamers with double hairpin-turn linkers showing an aggregation-induced emission (AIE) effect have been synthesized for the first time. A crystal structure of a foldamer-TNT complex has been obtained, enabling unprecedented direct observation of the interactions between TNT molecules and the chromophores of the foldamer. Instead of π-π stacking interactions, which have often been considered to be the key mechanism in the binding of TNT by chromophoric receptors, strong n-π interactions between the nitro groups of TNT and the aromatic rings of the foldamer have been found. Exceptionally, by addition of 1 % NaF to a suspension of the foldamer in H2 O/THF (95:5), the fluorescence quenching efficiency by TNT vapor significantly increased from about 20 % to more than 90 %. Even after diluting TNT-saturated air at 25 °C by a factor of 2×104 , an obvious quenching response was observed, indicating that ultratrace TNT vapor (down to 3.4 fg per mL of air) could be detected.

Porous Interdigitation Molecular Cage from Tetraphenylethylene Trimeric Macrocycles That Showed Highly Selective Adsorption of CO2 and TNT Vapor in Air.

A new [3 + 3] trimeric macrocycle, based on tetraphenylethylene having an aggregation-induced emission effect, could form a interdigitation molecular cage with a big void by host-guest interactions. The cage could accommodate two TNT molecules and detect TNT at the 1.7 fg level per mL of air. Moreover, the cage could give permanent pores that had a BET surface area of 347 m2/g and could adsorb 7.8 wt % CO2 with high CO2/N2 selectivity up to 32 (273 K, 1 bar).

Quartz Crystal Microbalance Coated with 18-Crown-6 Ether Film for 2,4,6-Trinitrotolurene (TNT) Vapor Detection

The 2, 4, 6-trinitrotoluene (TNT) vapor detection by quartz crystal microbalance (QCM) coated with 18-crown-6 ether film is introduced. The film acts as selective or sensitive layer for detecting TNT molecule. The frequency shift response is depend on the amount of mass of molecule adhere on the coated film surface. In this study, the concentrations of TNT vapor which is related to responses are studied. It shows that the TNT vapor concentration is related to the time for steady state condition and the frequency shift response. The high concentration vapor will increase the frequency shift response but increase the steady state time.