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Canines are widely used for real-time detection of explosives and have proven to be on par with instrumental methods. Canines are thought to rely largely upon detection of volatile chemical constituents of the explosives, though not necessarily the explosive itself. Hence, it is crucial to understand the odor available to them as generated by training aids. Previous studies have established that the Training Aid Delivery Device (TADD) developed by SciK9 is a reliable training aid that reduces cross-contamination and doubles as a storage device. A TADD comprises a standardized container, a synthetic membrane, a membrane holder, and a lid. In the work presented, activated charcoal strips were placed above and below the TADD membrane to determine the relative amounts of volatiles emitted by dynamite (i.e., ethylene glycol dinitrate (EGDN) and trinitroglycerin (NG)). The strips were eluted and the extracts tested using gas chromatography-mass spectrometry in negative ion chemical ionization mode. A series of t-tests at 95% confidence level were performed to determine any differences in vapor composition above and below the membranes. Nine synthetic membranes and six glass fiber membranes were tested in this study. It was expected that the relative concentration of volatiles would remain the same on both sides of the membrane; however, selective removal of nitroglycerin by some membranes was observed. Synthetic membranes with larger pore sizes showed no alteration in the vapor composition. Both synthetic and glass fiber membranes did not show a significant change in relative concentration of the other volatile compound in dynamite, i.e., EGDN. Out of all the membranes tested, three synthetic membranes and four glass fiber membranes showed selective alteration in odor availability of nitroglycerin in dynamite. For training purposes, membranes that do not alter the vapor composition should be used in the training aid.
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Sustancias Explosivas , Odorantes , Odorantes/análisis , Sustancias Explosivas/análisis , Sustancias Explosivas/química , Animales , Perros , Membranas Artificiales , Cromatografía de Gases y Espectrometría de Masas/métodos , Compuestos Orgánicos Volátiles/análisisRESUMEN
Pt(II) polypyridine complex-based probe exhibits promising performance in anion detection by the change of the absorption and emission properties based on supramolecular self-assembly. However, whether one can develop a modulation strategy of the counter anion to boost the detection sensitivity and anti-interference capability of the Pt(II) complex-based probe remains a big challenge. Here, an effective modulation strategy was proposed by precisely regulating the interaction energy through adjusting the type of the counter anions, and a series of probes have been synthesized by counter anion (X = Cl-, ClO4-, PF6-) exchange in [Pt(tpy)Cl]·X (tpy=2,2':6',2''-terpyridine), and thus the colorimetric-luminescence dual-mode detection toward nitrate was achieved. The optimal [Pt(tpy)Cl]·Cl probe shows superior nitrate detection performance including a limit of detection (LOD) (8.68 nM), rapid response (<0.5 s), an excellent selectivity and anti-interference capability even facing 14 common anions. Moreover, a polyvinyl alcohol (PVA) sponge-based sensing chip loaded with the probe enables the ultra-sensitive detection of nitrate particles with an ultralow detection limit of 7.6 pg, and it was further integrated into a detection pen for the accurate recognition of nitrate particles in real scenarios. The proposed counter-anion modulation strategy is expected to start a new frontier for the exploration of novel Pt(II) complex-based probes.
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Exposing different facets on metal-organic frameworks (MOFs) is highly desirable to enhance the performance for various applications, however, exploiting a concise and effective approach to achieve facet-controlled synthesis of MOFs remains challenging. Here, by modulating the ratio of metal precursors to ligands, the facet-engineered iron-based MOFs (Fe-MOFs) exhibits enhanced catalytic activity for Fenton reaction are explored, and the mechanism of facet-dependent performance is revealed in detail. Fully exposed (101) and (100) facets on spindle-shaped Fe-MOFs enable rapid oxidation of colorless o-phenylenediamine (OPD) to colored products, thereby establishing a dual-mode platform for the detection of hydrogen peroxide (H2O2) and triacetone triperoxide (TATP). Thus, a detection limit as low as 2.06 nm is achieved, and robust selectivity against a wide range of common substances (>16 types) is obtained, which is further improved by incorporating a deep learning architecture with an SE-VGG16 network model, enabling precise differentiation of oxidizing agents from captured images. The present strategy is expected will shine light on both the rational synthesis of nanomaterials with modulated morphologies and the exploitation of high-performance trace chemical sensors.
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A novel tellurium (Te) containing fluorophore, 1 and its nickel (2) and copper (3) containing metal organic complex (MOC) have been synthesized to exploit their structural and optical properties and to deploy these molecules as fluorescent probes for the selective and sensitive detection of picric acid (PA) over other commonly available nitro-explosives. Furthermore, density functional theory (DFT) and single crystal X-ray diffraction (SCXRD) techniques revealed the inclusion of "soft" Tellurium (Te) and "hard" Nitrogen (N), Oxygen (O) atoms in the molecular frameworks. Owing to the presence of electron rich "N" and "O" atoms along with "Te" in the molecular framework, 1 could efficiently and selectively sense PA with more than 80 % fluorescence quenching efficiency in organic medium and having detection limit of 4.60â µM. The selective detection of PA compared to other nitro-explosives follows a multi-mechanism based "turn-off" sensing which includes photo-induced electron transfer (PET), electrostatic (π-π stacking and π-anion/cation) interaction, intermolecular hydrogen bonding and inner filter effect (IFE). The test strip study also establishes the sensitivity of 1 for detection of PA.
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Sensitive, accurate, and reliable detection of explosives has become one of the major needs for international security and environmental protection. Colloidal quantum dots, because of their unique chemical, optical, and electrical properties, as well as easy synthesis route and functionalization, have demonstrated high potential to meet the requirements for the development of suitable sensors, boosting the research in the field of explosive detection. Here, we critically review the most relevant research works, highlighting three different mechanisms for explosive detection based on colloidal quantum dots, namely photoluminescence, electrochemical, and chemoresistive sensing. We provide a comprehensive overview and an extensive discussion and comparison in terms of the most relevant sensor parameters. We highlight advantages, limitations, and challenges of quantum dot-based explosive sensors and outline future research directions for the advancement of knowledge in this surging research field.
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Sustancias Explosivas , Puntos Cuánticos , Puntos Cuánticos/químicaRESUMEN
We developed a state-of-the-art, high-sensitivity, low-stray-light standoff deep-ultraviolet (DUV) Raman spectrometer for the trace detection of resonance Raman-enhanced chemical species. As an excitation source for Raman measurements, we utilized our recently developed, second-generation, miniaturized, diode-pumped, solid-state neodymium-doped gadolinium orthovanadate (Nd:GdVO4) laser that generates quasi-continuous wave 228 nm light. This 228 nm excitation enhances the Raman intensities of vibrations of NOx groups in explosive molecules, aromatic groups in biological molecules, and various aromatic hydrocarbons. Our DUV Raman spectrograph utilizes a custom DUV f/8 Cassegrain telescope with an â¼200 mm diameter primary mirror, high-efficiency DUV transmission gratings, custom DUV mirrors, and a custom 228 nm Rayleigh rejection filter. We utilized our new standoff DUV Raman spectrometer to measure high signal-to-noise ratio spectra of â¼50â µg/cm2 drop-cast explosives: ammonium nitrate (AN), trinitrotoluene, pentaerythritol tetranitrate as well as aromatic biological molecules: lysozyme, tryptophan, tyrosine, deoxycytidine monophosphate, deoxyadenosine monophosphate at an â¼3 m distance within 10-30 s accumulation times. We roughly estimate the average ultraviolet resonance Raman (UVRR) detection limits for the relatively homogeneous drop-cast films of explosives and biological molecules to be â¼1 µg/cm2 when utilizing a continuous raster scanning that averages Raman signal over â¼1â cm2 sample area to avoid quick analyte depletion due to ultraviolet (UV) photolysis. We determined 3 m standoff UVRR detection limits for drop-cast AN films and identified factors impacting UVRR detection limits such as analyte photochemistry and analyte morphology. We found a detection limit of â¼0.5â µg/cm2 for drop-cast AN films on glass substrates when the Raman signal is averaged over â¼0.5â cm2 of sample surface using a continuous raster scan. For a step raster scan, when the probed sample area is limited to the laser spot size, the detection limit is approximately tenfold higher (â¼5â µg/cm2) due to the impact of UV photochemistry.
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The design and development of ultra-accurate probe is of great significance to chemical sensing in complex practical scenarios. Here, a self-accelerating naphthalimide-based probe with fast response and high sensitivity toward hydrogen peroxide (H2O2) is designed. By coupling with the specially selected upconversion nanoparticles (UCNPs), an ultra-accurate colorimetric-fluorescent-upconversion luminescence (UCL) tri-mode platform is constructed. Owing to the promoted reaction process, this platform demonstrates rapid response (< 1 s), an ultra-low detection limit (4.34 nM), and superb anti-interferent ability even in presence of > 21 types of oxidants, explosives, metallic salts, daily compounds, colorful or fluorescent substances. In addition, the effectiveness of this design is further verified by a sponge-based sensing chip loaded with the UCNPs/probe in recognizing trace H2O2 vapor from interferents with the three characteristic colors existing simultaneously. The proposed design of probe and tri-mode visualization detection platform is expected to open up a brand-new methodology for ultra-accurate sensing.
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We study the electrical and morphological properties of random arrays of Ge nanowires (NW) deposited on sapphire substrates. NW-based devices were fabricated with the aim of developing chemiresistive-type sensors for the detection of explosive vapours. We present the results obtained on pristine and annealed NWs and, focusing on the different phenomenology observed, we discuss the critical role played by NW-NW junctions on the electrical conduction and sensing performances. A mechanism is proposed to explain the high efficiency of the annealed arrays of NWs in detecting 2,4,6 trinitrotoluene vapours. This study shows the promising potential of Ge NW-based sensors in the field of civil security.
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With increasing demand for public security and environmental protection, it is highly desirable to develop strategies to identify trace explosives (e. g., 2,4,6-trinitrotoluene (TNT)). Herein, we report novel photonic crystal (PC)-based sensor chips for trace TNT detection by using amplification effect of PCs on fluorescence (FL) signals. The sensor chips are constructed by integrating silica nanoparticles (NPs) modified with (3-aminopropyl)triethoxysilane (APTES) and fluorescein isothiocyanate isomer (FITC) and PC substrates. The amino groups on FITC-APTES-silica NPs can specifically bind with TNT molecules to form Meisenheimer complexes and strongly quench the FL signal of neighboring fluorophores FITC through Förster resonance energy transfer. PCs with matched PBG can amplify the FL signal of FITC-APTES-silica NPs about 24.4-fold and significantly improve sensitivity and resolution of trace TNT detection with the limit of detection of 0.23â nM. The PC-based sensor chips are stable, sensitive, and reliable TNT sensing platforms, showing great potential in homeland safety and environmental protection.
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Canines trained on scents from materials emitting vapours of explosives and related compounds are widely used to detect explosives in civilian, military and forensic applications. Despite the importance of these training materials, there is limited knowledge on how long these subsamples can be stored and whether vapour profiles change over time. We developed a sampling methodology that makes use of a secondary chamber for stabilisation of headspace concentration to allow reliable and reproducible determination of scent profiles. The effect of aging was investigated by following the response of volatile markers emitted from eight common explosives in open and closed containers over two months or two years. The initial headspace air volume consisted of a wide variety of chemical substances related to explosives, with levels varying in magnitude from low ppb to ppm. All included subsamples were affected by aging by demonstrating exponentially lower levels, and five subsamples showed a significant change in their scent profile. The dominant components decreased on a short time scale for plastic explosives based on RDX, PETN and dynamite as well as for granules of octol and ammonium nitrate mixed with fuel. For flakes of TNT, granules of Comp B and nitrocellulose powder, headspace air concentrations declined, but the overall character of their profiles were in general more stable. The overall changes, i.e., lower levels and/or changed profiles, justifies regular checks of the scent status of training materials. Considering these results together with data displaying marginal changes in energetic performance, it is advisable to complement scent training with training materials subjected to different durations of aging.
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Sustancias Explosivas , Perros , Animales , Odorantes , Perros de Trabajo , Nitroglicerina , FeromonasRESUMEN
Five random copolymers comprising styrene and styrene with pendant fluorophore moieties, namely pyrene, naphthalene, phenanthrene, and triphenylamine, in molar ratios of 10:1, were synthesized and employed as fluorescent sensors. Their photophysical properties were investigated using absorption and emission spectral analyses in dichloromethane solution and in solid state. All copolymers possessed relative quantum yields up to 0.3 in solution and absolute quantum yields up to 0.93 in solid state, depending on their fluorophore components. Fluorescence studies showed that the emission of these copolymers is highly sensitive towards various nitroaromatic compounds, both in solution and in the vapor phase. The detection limits of these fluorophores for nitroaromatic compounds in dichloromethane solution proved to be in the range of 10-6 to 10-7 mol/L. The sensor materials for new hand-made sniffers based on these fluorophores were prepared by electrospinning and applied for the reliable detection of nitrobenzene vapors at 1 ppm in less than 5 min.
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Fenantrenos , Estireno , Cloruro de Metileno , Pirenos , Colorantes Fluorescentes , Nitrobencenos/análisis , Polímeros , Naftalenos , IonóforosRESUMEN
Although it is well-known that nitroaromatic compounds quench the fluorescence of different conjugated polymers and form colored Meisenheimer complexes with proper nucleophiles, the potential of paper as a substrate for those macromolecules can be further developed. This work undertakes this task, impregnating paper strips with a fluorene-phenylene copolymer with quaternary ammonium groups, a bisfluorene-based cationic polyelectrolyte, and poly(2-(dimethylamino)ethyl methacrylate) (polyDMAEMA). Cationic groups make the aforementioned polyfluorenes attachable to paper, whose surface possesses a slightly negative charge and avoid interference from cationic quenchers. While conjugated polymers had their fluorescence quenched with nitroaromatic vapors in a non-selective way, polyDMAEMA-coated papers had a visual response that was selective to 2,4,6-trinitrotoluene (TNT), and that could be easily identified, and even quantified, under natural light. Far from implying that polyfluorenes should be ruled out, it must be taken into account that TNT-filled mines emit vapors from 2,4-dinitrotoluene (DNT) and dinitrobenzene isomers, which are more volatile than TNT itself. Atmospheres with only 790 ppbv TNT or 277 ppbv DNT were enough to trigger a distinguishable response, although the requirement for certain exposure times is an important limitation.
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Sustancias Explosivas , Trinitrotolueno , Aminas , Dinitrobencenos , Sustancias Explosivas/química , Gases , Polímeros/químicaRESUMEN
Poly(4-trimethylsilyl diphenyl acetylene) (PTMSDPA) has strong fluorescence emission, but its application is limited by the effect of aggregation-caused quenching (ACQ). Copolymerization is a commonly used method to adjust the properties of polymers. Through the copolymerization of 4-trimethylsilyl diphenyl acetylene and 1-trimethylsilyl-1-propyne (TMSP), we successfully realized the conversion of PTMSDPA from ACQ to aggregation-induced emission (AIE) and aggregation-induced emission enhancement (AEE). By controlling the monomer feeding ratio and with the increase of the content of TMSDPA inserted into the copolymer, the emission peak was red-shifted, and a series of copolymers of poly(TMSDPA-co-TMSP) that emit blue-purple to orange-red light was obtained, and the feasibility of the application in explosive detection was verified. With picric acid (PA) as a model explosive, a super-quenching process has been observed, and the quenching constant (KSV) calculated from the Stern-Volmer equation is 24,000 M-1, which means that the polymer is potentially used for explosive detection.
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2,4,6-Trinitrophenol (TNP) has been widely used for a long time. The adverse effects of TNP on ecological environment and human health have promoted researchers to develop various methods for detecting TNP. Among multifarious technologies utilized for the TNP detection, fluorescence strategy based on different functional materials has become an effective and efficient method attributed to its merits such as preferable sensitivity and selectivity, rapid response speed, simple operation, and lower cost, which is also the focus of review. This review summarizes the development status of fluorescence sensors for TNP in a detailed and systematic way, especially focusing on the research progress since 2015. The sensing properties of fluorescent materials for TNP are the core of this review, including nanomaterials, organic small molecules, emerging supramolecular systems, aggregation induced emission materials and others. Moreover, the development direction and prospect of fluorescence sensing method in the field of TNP detection are introduced and discussed at the end of review.
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Colorantes Fluorescentes , Nanoestructuras , Humanos , Picratos , Espectrometría de FluorescenciaRESUMEN
This work has prepared polymeric self-assembled monolayer (SAM) sensors for the detection of trace volatile nitroaromatic compound (NAC) explosives by fluorescence quenching. A typical aggregation-induced emission (AIE) luminogen 1,1,2,2-tetraphenylethene (TPE) polymerizes into PTPE to increase the fluorescence intensity in the SAMs, and the phosphoric acid acts as the anchor group to form stable covalent bonds with the Al2 O3 substrate. This design takes advantage of the high sensitivity and good stability of SAMs, and high fluorescence intensity, and "wire effect" of the conjugated polymers. The polymeric SAM sensors are prepared on the Al2 O3 silicon wafer and testing paper. Both of them show good response speed, reversibility, selectivity, and sensitivity. The detection limits down to 0.07, 0.35, and 4.11 ppm for TNT, DNB, and NB, respectively, are achieved on the inorganic testing paper. Furthermore, due to the higher fluorescence intensity by interlacing and overlapping of fibers, the detection of the paper can be distinguished by naked eyes even with a low-power handheld UV lamp, which provides an experimental basis for the development of cheap and easy trace NAC explosive sensors.
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Sustancias Explosivas , Fluorescencia , PolímerosRESUMEN
Authentication of the explosives in nuclear warheads is a key point for the global nuclear disarmament. In this paper, a detection method of the explosives in nuclear warheads based on API-TOF (associated α particle imaging - time of flight) is proposed. First, the basic principles and current research situation of API-TOF are introduced. Second, a numerical simulation platform of the detection method of the explosives in nuclear warheads based on API-TOF was established, and a numerical simulation study of the feasibility of this method was carried out. The research results show that, this method can detect the nuclides of 12C, 14N and 16O of the explosive in the nuclear warhead in 15 min, and reconstruct the carbon-oxygen number ratio and nitrogen-oxygen number ratio of the explosive accurately, and reconstruct the spatial distribution of the explosive nuclei with the explosive profile clearly discriminated in the reconstruction image. From the simulation results, the detection method of the explosive in the nuclear warhead based on API-TOF is confirmed.
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Partículas alfa , Simulación por Computador , Sustancias Explosivas , Carbono , OxígenoRESUMEN
Hidden or buried explosives are the most common scenario by terrorist attacks; therefore explosive vapour detection is a vital demand. Explosives are electron deficient materials; the vicinity of explosives to fluorescent material can encounter electron migration. This study reports on facile synthesis of cerium (III)-melamine coordination polymer (CeM-CP) with exclusive optical properties. CeM-CP demonstrated novel spectral fluorescence properties over visible and infrared bands when stimulated with UVA LED source at 385 nm of 100 mW power. Stimulated CeM-CP demonstrated unique spectral fluorescence signal at 400, 700, and 785 nm. These fluorescent signals were correlated to cerium coordination with four nitrogen atoms; vacant orbital will be available for electron excitation migration. Spectral fluorescent signals were quenched as CeM-CP was subjected to TNT vapours. Hyperspectral imaging offered 3D plot of fluorescence signature. The main outcome is that complete fluorescence signal attenuation was achieved at 785 nm. CeM-CP could act as as a novel sensing element for explosive vapour detection.
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Resumen After an internal conflict that lasted over half a century, the detection and removal of antipersonnel landmines in Colombia have become cumbersome challenges. Antipersonnel landmines remain scattered in Colombia and with a considerable impact on the central-western region. Most of these devices are handmade (therefore, they can also be classified as improvised explosive devices) and composed of ammonium nitrate and fossil fuel blend, a mixture known as ANFO. Due to several unique factors, including concealment tactics and non-conventional manufacturing techniques employed by guerrilla fighters, the most efficient method for the detection of ANFO-based antipersonnel landmines is the use of trained canines. This review aims at describing the current chemical strategies used in the detection of ANFO-based antipersonnel landmines. First, a detailed description of the different techniques used in the detection of explosives is made. Then, all the strategies reported in the world for antipersonnel landmines detection are described. Finally, the importance of the use of canines for antipersonnel landmines detection is explained.
Abstract Después de un conflicto interno que duró más de medio siglo, la detección y eliminación de minas antipersonales en Colombia se han convertido en desafíos engorrosos. Las minas antipersonales siguen dispersas en la región centro-occidental de Colombia. La mayoría de estos dispositivos están hechos a mano (hecho que puede clasificarlos como artefactos explosivos improvisados, AEI) y están compuestos por una mezcla de nitrato de amonio y un combustible fósil, una mezcla conocida como ANFO. Debido a varios factores únicos, que incluyen tácticas de ocultación y técnicas de fabricación no convencionales empleadas por guerrilleros, el método más eficiente para la detección minas antipersonales basadas en ANFO es el uso de caninos entrenados. Esta revisión tiene como objetivo describir las estrategias químicas actuales utilizadas en la detección de minas antipersonales basadas en ANFO. En primer lugar, se hace una descripcion detallada de las diferentes técnicas utilizadas en la detección de explosivos; luego, se describen todas las estrategias reportadas en el mundo para la detección de minas antipersonales y, finalmente, se explica la importancia del uso de caninos para la detección de minas antipersonales.
Resumo Após um conflito interno que durou mais de meio século, a detecção e remoção de minas antipessoal na Colômbia se tornaram desafios complexos. As minas antipessoal continuam espalhadas na região centro-oeste da Colômbia. A maioria desses dispositivos é feita à mão (fato que pode classificá-los como dispositivos explosivos improvisados, DEI) e composta de uma mistura de nitrato de amônio e um combustível fóssil - uma mistura conhecida como ANFO. Devido a vários fatores únicos, incluindo táticas de ocultação e técnicas de fabricação não convencionais empregadas por guerrilheiros, o método mais eficiente para a detecção de minas antipessoal baseadas em ANFO é o uso de caninos treinados. Esta revisão visa descrever as estratégias químicas atuais usadas na detecção de minas antipessoal baseadas em ANFO. Primeiro, é feita uma descrição detalhada das diferentes técnicas utilizadas na detecção de explosivos; Em seguida, são descritas todas as estratégias relatadas no mundo para a detecção de minas antipessoal e, finalmente, é explicada a importância do uso de caninos para a detecção de minas antipessoal.
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Bacterial reaction centers (BRC) from Rhodobacter sphaeroides were found to accelerate, about 100-fold, the reaction between tetryl (2,4,6-trinitrophenylmethylnitramine) explosive and n-lauryl-N-N-dimethylamine-N-oxide (LDAO) that results in the formation of picric acid-like product with characteristic UV-VIS absorption spectrum with peaks at 345 and 415 nm. Moreover, this product also affects the spectra of BRC cofactors in the NIR spectral region and stabilizes the conformational changes associated with slow charge recombination. The evolution of the NIR absorption changes correlated with the kinetics of the product formation. Comparison between the wild-type and the R26 carotenoid-less strain indicates that tetryl-LDAO reaction is roughly five times faster for R26, which allows for identifying the carotenoid binding site as the optimal reaction site. Another, less-defined reaction site is located in the BRC's hydrophobic cavity. These effects are highly selective for tetryl and not observed for several other widespread nitric explosives; slowed-down charge recombination allows for distinguishing between tetryl and QB-site herbicides. The current limit of detection is in the ppb range or ~ 100 nM. Details of the molecular mechanisms of the reactions and perspectives of using these effects in bioassays or biosensors for explosives detection are also discussed.
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Compuestos de Anilina/metabolismo , Detergentes/metabolismo , Dimetilaminas/metabolismo , Sustancias Explosivas/metabolismo , Nitrobencenos/metabolismo , Proteínas del Complejo del Centro de Reacción Fotosintética/metabolismo , Rhodobacter sphaeroides/metabolismo , Compuestos de Anilina/química , Carotenoides/metabolismo , Detergentes/química , Dimetilaminas/química , Transporte de Electrón , Sustancias Explosivas/química , Cinética , Límite de Detección , Nitrobencenos/química , Proteínas del Complejo del Centro de Reacción Fotosintética/química , Rhodobacter sphaeroides/químicaRESUMEN
Precise analysis of explosives is important for environmental pollution evaluation and terrorist prevention. However, rapid assay of explosives with high selectivity and sensitivity remains difficult. Here, we show that the gold nanocluster-modified metal-organic frameworks are excellent optical probes for explosive detection. The nanoclusters exhibit enhanced luminescence and selectively respond toward 2,4,6-trinitrotoluene over other explosives with a detection limit of 5 nM and fast response within 1 min. The efficient assay is resulted from the framework-mediated cluster aggregation and TNT binding.