Triacetone Triperoxide Research Articles

Thermal decomposition of triacetone triperoxide by differential scanning calorimetry

Triacetone triperoxide (TATP) is an organic peroxide that is sensitive and can be readily synthesized, and is thus used as an explosive. In this study, three sulfuric acid (H2SO4) concentrations (1, 9, and 18 M) were used to synthesize TATP. The higher concentrations of H2SO4 resulted in higher concentrations and swift production of TATP. Each combination was compounded with different thermal hazard characteristics. The thermal decomposition of TATP was studied through differential scanning calorimetry (DSC) to obtain exothermic onset temperature (T0), heat of decomposition (ΔHd), and maximum temperature during the overall reaction (Tmax). The apparent activation energy (Ea) was calculated using the Kissinger method and the Ozawa method. Gas chromatography and mass spectrometry were employed to confirm the synthesized TATP. This study used DSC to evaluate the thermal decomposition and analyze the efficiency of fire-extinguishing reagents. Results showed that different inhibiting reagents had different efficiency levels for TATP. Thus, inhibiting reagents can be expected to diminish the damage caused by TATP explosions. In this study, the mechanism of TATP synthesis was investigated.

TATP isotope ratios as influenced by worldwide acetone variation

Isotope ratio analysis has been shown to discriminate samples of forensic interest and to link many synthesized and natural materials to their precursors when traditional chemical and physical analyses cannot. Successful application of stable isotope analysis to chemicals of interest requires a background of likely variations in stable isotope ratios; often, this background population can be generated from analysis of possible precursors and the relationships of stable isotopes of precursor(s) to product(s), which may depend on synthesis techniques. Here we measured the carbon (13C/12C) and hydrogen (2H/1H) isotope ratios of the oft-illicitly manufactured explosive triacetone triperoxide, TATP, and one of its precursors, acetone. As acetone is the sole source of carbon and hydrogen to TATP, a survey of acetone from 12 countries was conducted to explore the breadth of 13C/12C and 2H/1H variation in the precursor, and therefore, its product. Carbon and hydrogen isotope ratios were measured using continuous flow isotope ratio mass spectrometry (IRMS) techniques. We observed greater ranges in both C and H isotope ratios of acetone than previously published; we also found that country-of-purchase was a large contributing factor to the observed variation, larger than acetone grade and brand. Following clandestine production methods, we observed that the stable isotope ratios of TATP retained the stable isotope signatures of acetone used in synthesis. We confirmed the robustness of TATP carbon isotope ratios to both recrystallization and time-dependent sublimation, important considerations when faced with the task of practical sampling of potential unexploded TATP from a crime scene.

Surface functionalized silica nanoparticles for the off–on fluorogenic detection of an improvised explosive, TATP, in a vapour flow

Silica nanomaterials generate a permanent and strongly fluorescent response in a vapour flow of the improvised explosive triacetone triperoxide (TATP).

Reactions of Organic Peroxides with Alcohols in Atmospheric Pressure Chemical Ionization-the Pitfalls of Quantifying Triacetone Triperoxide (TATP).

Over the last several decades, mass spectrometry has become one of the principle methods for compound identification and quantification. While for analytical purposes, fragments which are not fully characterized in terms of origin and intensity as a function of experimental conditions have been used, understanding the nature of those species is very important. Herein we discuss such issues relative to triacetone triperoxide (TATP) and its frequently observed fragment at m/z 89. This "fragment" has been identified as the gas-phase reaction product of TATP with one or two methanol molecules/ions. Additionally, the origin and conditions of other fragments at m/z 91, 75, and 74 associated with TATP will be addressed. Similar analytical issues associated with other multi-peroxide organic compounds [hexamethylene triperoxide diamine (HMTD), methyl ethyl ketone peroxides (MEKP)] will also be discussed. Solution storage conditions for TATP, HMTD, and tetramethylene diperoxide diamine dialdehyde have been determined. Graphical Abstract ᅟ.

Solvent‐Free Off–On Detection of the Improvised Explosive Triacetone Triperoxide (TATP) with Fluorogenic Materials

A fluorogenic perylenediimide-functionalized polyacrylate capable of generating color and fluorescence changes in the presence of triacetone triperoxide TATP), an improvised explosive used in terrorist attacks, under solvent-free, solid-state conditions has been developed. The material works by accumulating volatile TATP until it reaches a threshold; therefore, triggering colorimetric and fluorescent responses.

Use of Mass Spectrometric Vapor Analysis To Improve Canine Explosive Detection Efficiency.

Canines remain the gold standard for explosives detection in many situations, and there is an ongoing desire for them to perform at the highest level. This goal requires canine training to be approached similarly to scientific sensor design. Developing a canine training regimen is made challenging by a lack of understanding of the canine's odor environment, which is dynamic and typically contains multiple odorants. Existing methodology assumes that the handler's intention is an adequate surrogate for actual knowledge of the odors cuing the canine, but canines are easily exposed to unintentional explosive odors through training material cross-contamination. A sensitive, real-time (∼1 s) vapor analysis mass spectrometer was developed to provide tools, techniques, and knowledge to better understand, train, and utilize canines. The instrument has a detection library of nine explosives and explosive-related materials consisting of 2,4-dinitrotoluene (2,4-DNT), 2,6-dinitrotoluene (2,6-DNT), 2,4,6-trinitrotoluene (TNT), nitroglycerin (NG), 1,3,5-trinitroperhydro-1,3,5-triazine (RDX), pentaerythritol tetranitrate (PETN), triacetone triperoxide (TATP), hexamethylene triperoxide diamine (HMTD), and cyclohexanone, with detection limits in the parts-per-trillion to parts-per-quadrillion range by volume. The instrument can illustrate aspects of vapor plume dynamics, such as detecting plume filaments at a distance. The instrument was deployed to support canine training in the field, detecting cross-contamination among training materials, and developing an evaluation method based on the odor environment. Support for training material production and handling was provided by studying the dynamic headspace of a nonexplosive HMTD training aid that is in development. These results supported existing canine training and identified certain areas that may be improved.

Direct Detection of Triacetone Triperoxide (TATP) in Real Banknotes from ATM Explosion by EASI‐MS

AbstractIn Brazil, automated teller machine (ATM) has become a major target of theft incursions toward explosion. Efficient analysis of explosives residues on suspect banknotes is a serious issue in forensic labs, and guide to the crime solution. Easy ambient sonic‐spray ionization mass spectrometry (EASI‐MS) is shown to be a simple and selective screening tool to identify peroxide explosives on real banknotes collected from ATM explosion. Analyses were carried out directly on the banknotes surfaces without any sample preparation, identifying triacetone triperoxide (TATP) and diacetone diperoxide (DADP). Homemade EASI source was coupled to ultrahigh‐resolution and ultrahigh accuracy FT‐ICR MS and revealed the ion of m/z 245 correspondent to sodiated TATP [C9H18O6Na]+ and the ion of m/z 171 related to sodiated DADP [C6H12O4Na]+, ions that is the sodiated DADP and the ions of m/z 173 and 189 related to [C6H14O4Na]+ and [C6H14O4K]+, respectively, which are associated to chemical markers of TATP domestic route synthesis. EASI source coupled to a single quadrupole mass spectrometer provides an intelligent and simple way to identify the explosives TATP, DADP and its domestic synthesis markers.

Gas-phase Concentration of Triacetone Triperoxide (TATP) and Diacetone Diperoxide (DADP)

The present investigation is about the determination of the gas phase concentration parameters of the notorious explosives triacetone triperoxide (TATP, 1) and diacetone diperoxide (DADP, 2), which have been frequently used in improvised explosive devices. According to calculations with EXPLO5 the energetic performance of both explosives is similar. The enthalpy of sublimation Delta(g)(cr)Eta(o)(m) (298.15K) (1: 76.7 +/- 0.7 kJmol(-1);2: 75.0 +/- 0.5 kJmol(-1)) and vapor pressures p(sat)(298.15K) (1: 6.7Pa, 2: 26.6 Pa) of both compounds have been studied using the transpiration method in the ambient temperature range of 274-314K. The results obtained in this work were compared critically with the existing literature values. Data for DADP (2) mostly shows agreement with literature ones. However data of TATP (1) obtained in this work revealed insufficient agreement of all sets of data available in literature, which might be explained by the rich polymorphism of TATP 1. The saturation and diffusion equilibrium concentration of both analytes was calculated at 298.15K. In comparison to the saturation equilibrium concentration measured in this work (1: 600gL(-1), 2: 1589gL(-1)) the corresponding estimated diffusion condition air concentrations (1: 3.1ngL(-1), 2: 10ngL(-1), for a surface of 200cm(2)) are lower by five orders of magnitude.

Determination of Peroxide Explosive TATP and Related Compounds by Dielectric Barrier Discharge Ionization-Mass Spectrometry (DBDI-MS).

Dielectric barrier discharge ionization-mass spectrometry (DBDI-MS), which is based on the use of a low temperature helium plasma as ionization source, is used for the determination of trace amounts of triacetone triperoxide (TATP) and its homologue diacetone diperoxide (DADP) from surfaces. TATP is observed as [M+NH4]+ adduct, whereas DADP is observed as [M+O+NH4]+. Measurement of DADP with varying deuteration degrees (DADP, DADP-d6, and DADP-d12) indicates that DADP undergoes oxidation when ionized by DBDI. If acetonitrile is used as deposition solvent, TATP tends to show fragmentation and is not only detected as [M+NH4]+ but as [M-CH4+NH4]+ and [M-C2H4+NH4]+ as well. Quantification of TATP solutions from glass surfaces by DBDI-MS, using TATP-3,6,9-13C as internal standard, was done and validated using an LC/APCI-MS method. Achievable limits of detection (LOD) for TATP are equivalent to the deposition of 15 ng TATP and are comparable with other ambient desorption/ionization mass spectrometric techniques like desorption electrospray ionization (DESI).

Determination of hydrogen peroxide and triacetone triperoxide (TATP) with a silver nanoparticles—based turn-on colorimetric sensor

Hydrogen peroxide (H2O2) is a synthetic precursor and degradation product of peroxide-based explosives, such as TATP. We developed a colorimetric sensor that is selective, sensitive, cost-efficient and easy-to-use in conventional laboratories for the naked eye detection of hydrogen peroxide and for indirect determination of peroxide-based explosives (which are devoid of chromogenic/fluorogenic functional groups). We were able to partly oxidize zero-valent silver nanoparticles (Ag0NPs) by H2O2 to Ag+ under special conditions, and thus devise an indirect method for trace H2O2 quantification by measuring the absorbance of the blue-colored diimine of TMB (3,3′,5,5′- tetramethylbenzidine) at 655nm, arising from TMB oxidation with Ag+. TATP was acid-hydrolyzed to H2O2 by an acidic cation-exchanger (Amberlyst-15) for potential field use. The limit of detection (LOD) of the sensor was 20nM for H2O2 and 0.31mgL−1 for TATP. Common soil ions did not interfere, and TATP was analyzed in synthetic mixtures of other energetic materials. The responses of detergents, sweeteners, acetylsalicylic acid (aspirin) and paracetamol-based painkiller drugs, used as camouflage material in passenger belongings, were also examined. The developed method was statistically validated against the standard analytical methods of titanium(IV) oxysulfate (TiOSO4) for H2O2 and GC–MS for TATP using t- and F- tests.

Trace explosives sensor testbed (TESTbed).

A novel vapor delivery testbed, referred to as the Trace Explosives Sensor Testbed, or TESTbed, is demonstrated that is amenable to both high- and low-volatility explosives vapors including nitromethane, nitroglycerine, ethylene glycol dinitrate, triacetone triperoxide, 2,4,6-trinitrotoluene, pentaerythritol tetranitrate, and hexahydro-1,3,5-trinitro-1,3,5-triazine. The TESTbed incorporates a six-port dual-line manifold system allowing for rapid actuation between a dedicated clean air source and a trace explosives vapor source. Explosives and explosives-related vapors can be sourced through a number of means including gas cylinders, permeation tube ovens, dynamic headspace chambers, and a Pneumatically Modulated Liquid Delivery System coupled to a perfluoroalkoxy total-consumption microflow nebulizer. Key features of the TESTbed include continuous and pulseless control of trace vapor concentrations with wide dynamic range of concentration generation, six sampling ports with reproducible vapor profile outputs, limited low-volatility explosives adsorption to the manifold surface, temperature and humidity control of the vapor stream, and a graphical user interface for system operation and testing protocol implementation.

Conjugated Covalent Organic Frameworks via Michael Addition–Elimination

Dynamic covalent chemistry enables self-assembly of reactive building blocks into structurally complex yet robust materials, such as covalent organic frameworks (COFs). However, the synthetic toolbox used to prepare such materials, and thus the spectrum of attainable properties, is very limited. For π-conjugated COFs, the Schiff base condensation of aldehydes and amines is the only general dynamic reaction, but the resulting imine-linked COFs display only a moderate electron delocalization and are susceptible to hydrolysis, particularly in acidic conditions. Here we report a new dynamic polymerization based on Michael addition-elimination reaction of structurally diverse β-ketoenols with amines, and use it to prepare novel two-dimensional (2D) π-conjugated COFs, as crystalline powders and exfoliated micron-size sheets. π-Conjugation is manifested in these COFs in significantly reduced band gap (1.8-2.2 eV), solid state luminescence and reversible electrochemical doping creating midgap (NIR absorbing) polaronic states. The β-ketoenamine moiety enables protonation control of electron delocalization through the 2D COF sheets. It also gives rise to direct sensing of triacetone triperoxide (TATP) explosive through fluorescence quenching.

Analysis of Explosives by GC-UV.

A mixture of explosives was analyzed by gas chromatography (GC) linked to ultraviolet (UV) spectrophotometry that enabled detection in the range of 178-330 nm. The gas-phase UV spectra of 2,4,6-trinitrotoluene (TNT), 2,4-dinitrotoluene (DNT), ethylene glycol dinitrate (EGDN), glycerine trinitrate (NG, nitroglycerine), triacetone triperoxide (TATP), and pentaerythritol tetranitrate (PETN) were successfully recorded. The most interesting aspect of the current application is that it enabled simultaneous detection of both the target analyte and its decomposition products. At suitable elevated temperatures of the transfer line between the GC instrument and the UV detector, a partial decomposition was accomplished. Detection was made in real time and resulted in overlaid spectra of the mother compound and its decomposition product. Hence, the presented approach added another level to the qualitative identification of the explosives in comparison with traditional methods that relies only on the detection of the target analyte. As expected, the decomposition product of EGDN, NG, and PETN was NO, while TATP degraded to acetone. DNT and TNT did not exhibit any decomposition at the temperatures used.

Detection of trace peroxide explosives in environmental samples using solid phase extraction and liquid chromatography mass spectrometry

ABSTRACTThis article presents solid phase extraction (SPE) and liquid chromatography-mass spectrometry (LC-MS) methods for the trace detection of the peroxide explosives triacetone triperoxide (TATP) and hexamethylene triperoxide diamine (HMTD). Furthermore, experimental studies use these methods to explore the efficiency of wastewater treatment plant (WWTP) processes at removing trace levels of peroxide explosives from water samples to assess the application of the developed methods for the detection of explosives in the environment. The principal results of this study showed that the greatest removal of TATP and HMTD from spiked water samples occurred following the biological treatment stage, however, the WWTP processing did not completely remove all of the analytes from the water, suggesting that such chemicals could contaminate downstream river water samples. The toxicity of chemical pollutants is often determined by their concentration, however, even at trace levels, the monitoring of explosives in the natural environment could be extremely informative for the detection of criminal activity as well as long-term effects upon aquatic life. These findings also have significant implications for crime prevention and disruption approaches that can use this type of data as intelligence to guide investigations regarding the source and attribution of detected explosives.

Ultrasensitive photoacoustic sensor based on quantum cascade laser spectroscopy

The paper focuses on development of ultra-sonic detection system based on laser photoacoustic spectroscopic technique and processing of signal for detection of very low quantity chemicals, explosive materials, and mixtures of these hazardous molecules. The detection system has been developed for the first time with specially designed one side open photo-acoustic cell having high quality factor. Explosive and Hazardous materials like RDX, DNT, PETN, Gun Powder, TATP (Tri acetone tri-peroxide) and their simulants like Acetone were detected in 7 to 9μm wavelength band. Lock in amplifier electronic instrument was used for the detection of hazardous chemicals and mixture of explosives in very low quantity. Detection limit of the photoacoustic ultrasonic sensor was also carried out of powder, liquid and adsorbed on surfaces.

Energetic Materials Trends in 5‐ and 6‐Membered Cyclic Peroxides Containing Hydroperoxy and Hydroxy Substituents

Ten peroxide compounds based upon the 3,6‐di(hydroperoxy)‐1,2‐dioxane, 2‐hydroxy‐6‐hydroperoxy‐1,2‐dioxane, 3,5‐di(hydroperoxy)‐1,2‐dioxolane, and 3‐hydroxy‐5‐hydroperoxy‐1,2‐dioxolane skeletons have been synthesized, structurally characterized, and fully evaluated for their energetic materials properties. The solid‐state structures of these compounds are dominated by hydrogen bonding interactions involving the hydroperoxy and hydroxy groups. Energetic materials testing shows that most of the compounds are highly sensitive toward impact and friction, with similar properties to highly sensitive peroxides such as triacetone triperoxide. 3,5‐Diethyl‐5‐hydroperoxy‐1,2‐dioxolan‐3‐ol (3b) and 3,5‐dimethyl‐5‐hydroperoxy‐1,2‐dioxolan‐3‐ol (5b) have lower impact and friction sensitivities than the other compounds, with values that are appropriate for use as primary explosives.

The Potential of Isotope Ratio Mass Spectrometry (IRMS) and Gas Chromatography-IRMS Analysis of Triacetone Triperoxide in Forensic Explosives Investigations.

Studying links between triacetone triperoxide (TATP) samples from crime scenes and suspects can assist in criminal investigations. Isotope ratio mass spectrometry (IRMS) and gas chromatography (GC)-IRMS were used to measure the isotopic compositions of TATP and its precursors acetone and hydrogen peroxide. In total, 31 TATP samples were synthesized with different raw material combinations and reaction conditions. For carbon, a good differentiation and a linear relationship were observed for acetone-TATP combinations. The extent of negative (δ(13) C) fractionation depended on the reaction yield. Limited enrichment was observed for the hydrogen isotope (δ(2) H) values of the TATP samples probably due to a constant exchange of hydrogen atoms in aqueous solution. For oxygen (δ(18) O), the small isotopic range and excess of water in hydrogen peroxide resulted in poor differentiation. GC-IRMS and IRMS data were comparable except for one TATP sample prepared with high acid concentration demonstrating the potential of compound-specific isotope analysis. Carbon IRMS has practical use in forensic TATP investigations.

Factors affecting the intramolecular decomposition of hexamethylene triperoxide diamine and implications for detection

Hexamethylene triperoxide diamine (HMTD) is an easily synthesized and highly sensitive organic peroxide frequently used as a primary explosive. The vapor pressure of HMTD is very low, impeding vapor detection, especially when compared to other peroxide explosives, such as triacetone triperoxide (TATP) or diacetone diperoxide (DADP). Despite this fact, HMTD has a perceptible odor that could be utilized in the indirect detection of HMTD vapor. Headspace measurements above solid HMTD samples confirm that HMTD readily decomposes under ambient conditions to form highly volatile products that include formic acid, ammonia, trimethylamine and formamides. The presence and quantity of these compounds are affected by storage condition, time, and synthetic method, with synthetic method having the most significant effect on the content of the headspace. A kinetic study of HMTD decomposition in solution indicated a correlation between degradation rate and the presence of decomposition species identified in the headspace, and provided further insight into the mechanism of decomposition. The study provided evidence for a proton assisted decomposition reaction with water, as well as an intramolecular decomposition process facilitated by the presence of water.

Detecting peroxide explosives

Triacetone triperoxide (TATP) is a highly unstable explosive prone to unintended detonation. Yet terrorists, such as those responsible for the March 22 bombings in Brussels and the November 2015 attacks in Paris, are increasingly using the compound to inflict carnage. Despite its instability, TATP is attractive as a terror weapon because it is relatively easy to prepare and, until recently, was difficult to detect by standard explosives screening methods. Those methods, which are based on X-ray computed tomography (CT) and ion mobility spectrometry (IMS), have been modified and can now routinely detect TATP in airports and at other security checkpoints. Several other methods in various stages of commercialization, including some based on handheld scanners, can also detect TATP. The problem that remains unsolved is figuring out how to stop terrorists from detonating explosives in crowded, unscreened public areas, such as subway stations and the unsecured sides of airports, which is

Dopant-Assisted Positive Photoionization Ion Mobility Spectrometry Coupled with Time-Resolved Thermal Desorption for On-Site Detection of Triacetone Triperoxide and Hexamethylene Trioxide Diamine in Complex Matrices.

Peroxide explosives, such as triacetone triperoxide (TATP) and hexamethylene trioxide diamine (HMTD), were often used in the terrorist attacks due to their easy synthesis from readily starting materials. Therefore, an on-site detection method for TATP and HMTD is urgently needed. Herein, we developed a stand-alone dopant-assisted positive photoionization ion mobility spectrometry (DAPP-IMS) coupled with time-resolved thermal desorption introduction for rapid and sensitive detection of TATP and HMTD in complex matrices, such as white solids, soft drinks, and cosmetics. Acetone was chosen as the optimal dopant for better separation between reactant ion peaks and product ion peaks as well as higher sensitivity, and the limits of detection (LODs) of TATP and HMTD standard samples were 23.3 and 0.2 ng, respectively. Explosives on the sampling swab were thermally desorbed and carried into the ionization region dynamically within 10 s, and the maximum released concentration of TATP or HMTD could be time-resolved from the matrix interference owing to the different volatility. Furthermore, with the combination of the fast response thermal desorber (within 0.8 s) and the quick data acquisition software to DAPP-IMS, two-dimensional data related to drift time (TATP: 6.98 ms, K0 = 2.05 cm(2) V(-1) s(-1); HMTD: 9.36 ms, K0 = 1.53 cm(2) V(-1) s(-1)) and desorption time was obtained for TATP and HMTD, which is beneficial for their identification in complex matrices.