Chemiluminescence detection systems for the analysis of explosives

The objective of this paper is to provide a comprehensive review of explosive detection by chemiluminescence (CL) through a summary of the relevant literature in the last 5 years and a synopsis of current research topics and developments. The literature reviewed is specially addressed for the detection of a group of high explosives, containing nitrogen compounds. Most explosives compounds contain either nitro or nitrate groups which make possible their detection and quantification using detection systems based on chemiluminescent reactions. Practical considerations and experimental requirements are indicated, and the possibilities and limitations are evaluated.     

Signal-to-Noise and Resolution Enhancement in Ion Mobility Spectrometry Using Correlation Gating Techniques: Barker Codes

Ion mobility spectroscopy (IMS) is a technology that is ideally suited for the detection of very low levels of analyte due to its extreme sensitivity and ability to speciate. Detection of common military and industrial explosives using IMS is an ideal application, since IMS can be tailored to be sensitive to compounds that form negative ions such as nitrate-laden explosives. However, realization of a miniaturized IMS-based detection system for explosives has been hampered by limitations in resolution of miniaturized IMS tubes and by the need to preconcentrate explosive samples and then rapidly desorb them creating a transient chemical concentration. We have demonstrated a new gating and data processing technique that takes advantage of pulse compression approaches developed for modern radar systems for decreasing granularity in target identification. We will show that closely spaced peaks can be isolated by adding discriminating codes to the gating signal. We will then employ matched filtering for the received ion current signal greatly improving instrument performance. This scheme is most advantageous to small geometry IMS drift cells that suffer from lack of resolution due to their small size but would improve sensitivity and peak location uncertainty in any geometry IMS tube. Specifically, we have demonstrated a 13 fold increase in signal-to-noise ratio and have effectively decreased the uncertainty in the location of the signal peak by a factor of 4.4 using a 13-bit Barker coding pattern to operate our IMS gating.     

Increasing selectivity for TNT-based explosive detection by synchronous luminescence and derivative spectroscopy with quantum yields of selected aromatic amines

The detection of explosive material is at the forefront of current analytical problems. A detection method is desired that is not restricted to detecting only explosive materials, but is also capable of identifying the origin and type of explosive. It is essential that a detection method have the selectivity to distinguish among compounds in a mixture of explosives. The nitro compounds found in explosives have low fluorescent yields or are considered to be non-fluorescent; however, after reduction, the amino compounds exhibit relatively high fluorescence. We discuss how to increase selectivity of explosive detection using fluorescence; this includes synchronous luminescence and derivative spectroscopy with appropriate smoothing. By implementing synchronous luminescence and derivative spectroscopy, we were able to resolve the reduction products of one major TNT-based explosive compound, 2,4-diaminotoluene, and the reduction products of other minor TNT-based explosives in a mixture. We also report for the first time the quantum yields of these important compounds. Relative quantum yields are useful in establishing relative fluorescence intensities and are an important spectroscopic measurement of molecules. Our approach allows for rapid, sensitive, and selective detection with the discrimination necessary to distinguish among various explosives.     

Fast separation and quantification method for nitroguanidine and 2,4-dinitroanisole by ultrafast liquid chromatography-tandem mass spectrometry

Explosives are now persistent environmental pollutants that are targets of remediation and monitoring in a wide array of environmental media. Nitroguanidine (NG) and 2,4-dinitroanisole (DNAN) are two insensitive energetic compounds recently used as munitions explosives. To protect our environment and human health, the levels of these compounds in soils and waters need to be monitored. However, no sensitive analytical methods, such as liquid chromatography-tandem mass spectrometry (LC-MS/MS), have been developed for detecting these new compounds at trace levels and to be concurrently applied to monitor the common explosives. In general, the concentrations of explosives in either soil or water samples are very low and widely distributed. Therefore, a fast and sensitive method is required to monitor those compounds and increase our ability to find and address the threats they pose to human health and ecological receptors. In this study, a fast and sensitive analytical method has been developed to quantitatively determine NG and DNAN in soil, tap water, and river water by using ultrafast LC-MS/MS. To make this method a comprehensive analytical technique for other explosives as well, it has included other commonly used explosives in the method development, such as octahydro-1,3,5,7-tetranitro-1,3,5,7-tetrazocine (HMX), 1,3,5-trinitroper-hydro-1,3,5-triazine (RDX), 2,4,6-trinitrotoluene (TNT), 2-amino-4,6-dinitrotoluene (ADNT), and pentaerythritol tetranitrate (PETN). The method detection limits (MDLs) of these compounds in soil ranged from 0.2 to 5 ppb, and a good linearity was obtained over a concentration range of 0.5-200 ppb. The recoveries of some compounds are equal to or better than the current EPA methods but with much higher sensitivities.     

Application of photoassisted electrochemical detection to explosive-containing environmental samples

High-performance liquid chromatography (HPLC) with ultraviolet (UV) absorbance and photoassisted electrochemical detection (PAED) is applied to the determination of explosives in groundwater and soil samples. On-line, solid-phase extraction minimizes sample pretreatment, enabling direct analysis of groundwater samples and soil extracts. Soils are extracted using pressurized fluid extraction, which is compared to the Environmental Protection Agency (EPA) sonication method. Limits of detection for explosives in the matrixes of interest are equivalent or superior (i.e., <10 parts-per-trillion for HMX) to those achieved using the EPA method 8330. HPLC-UV-PAED is also shown here to be more broadly applicable, as it is capable of determining nitro compounds of interest (e.g., nitroglycerin) that have poor UV chromophores. Additional selectivity of amine-substituted nitroaromatic explosives is achieved by using a photochemical reactor with a 366-nm wavelength lamp. By coupling reversed-phase columns of different selectivities together, baseline resolution of all 14 standard explosives is demonstrated.     

基于虚拟仪器的慢速烤燃系统的设计及应用

为了满足不敏感炸药的发展需求,在GJB 772A-1997及行业内标准烤燃装置的基础上,设计并开发了一套慢速烤燃系统。该系统基于LabVIEW程序的控制软件,由以控制器、数据采集卡、热电偶及数字I/O卡等为主的典型硬件构成。参照美军标MIL-STD-2105D和国内行业标准,对该系统的适用性开展了试验研究;采用RDX基与HMX基两种典型的混合炸药装药进行了慢速烤燃试验。结果表明,该慢速烤燃系统具有广泛的温度适用范围,试验数据拟合相关系数不低于0.999 8,在0.055、0.200、1.000、2.000℃/min和3.000℃/min等几种升温速率条件下,炸药均能实现较高精度的线性升温。与RDX基混合炸药相比,HMX基混合炸药响应程度有所缓和。该慢速烤燃系统满足试验需求,可为研究炸药的热不敏感性提供有效手段。     

Fluorescent polymer sensor array for detection and discrimination of explosives in water

A fluorescent polymer sensor array (FPSA) was made from commercially available fluorescent polymers coated onto glass beads and was tested to assess the ability of the array to discriminate between different analytes in aqueous solution. The array was challenged with exposures to 17 different analytes, including the explosives trinitrotoluene (TNT), tetryl, and RDX, various explosive-related compounds (ERCs), and nonexplosive electron-withdrawing compounds (EWCs). The array exhibited a natural selectivity toward EWCs, while the non-electron-withdrawing explosive 1,3,5-trinitroperhydro-1,3,5-triazine (RDX) produced no response. Response signatures were visualized by principal component analysis (PCA), and classified by linear discriminant analysis (LDA). RDX produced the same response signature as the sampled blanks and was classified accordingly. The array exhibited excellent discrimination toward all other compounds, with the exception of the isomers of nitrotoluene and aminodinitrotoluene. Of particular note was the ability of the array to discriminate between the three isomers of dinitrobenzene. The natural selectivity of the FPSA toward EWCs, plus the ability of the FPSA to discriminate between different EWCs, could be used to design a sensor with a low false alarm rate and an excellent ability to discriminate between explosives and explosive-related compounds.     

Electrochemical detectors prepared by electroless deposition for microfabricated electrophoresis chips

Microfabricated capillary electrophoresis (CE) chips with integrated electrochemical detection have been developed on glass substrates. An electroless deposition procedure was used to deposit a gold film directly onto the capillary outlet to provide high-sensitivity electrochemical detection for catechol and several nitroaromatic explosives. Scanning electron microscopy revealed that the electroless gold film contains nanoscopic gold aggregates (100-150 nm) with an average thickness of 79 nm. The electroless deposition procedure can be easily and routinely performed in any wet-chemistry laboratory, and electroless gold can be deposited onto complex and internal surfaces. Intimate coupling of electrochemical detection and CE chips obviates the need for a coupling mechanism or tedious alignment procedures. With nitroaromatic compounds as a working model, microchip capillary electrophoresis equipped with electroless gold has proven to provide high sensitivity and fast response times for sensor applications. The CE microchip system was capable of separation and determination of explosive compounds including TNT in less than 130 s with detection limits ranging from 24 to 36 microg/L, i.e., 4-fold enhancements in detection efficiency in comparison to thick-film technology.     

Nanoscale porosity in polymer films: fabrication and therapeutic applications

This review focuses on current developments in the field of nanostructured bulk polymers and their application in bioengineering and therapeutic sciences. In contrast to well-established nanoscale materials, such as nanoparticles and nanofibers, bulk nanostructured polymers combine nanoscale structure in a macroscopic construct, which enables unique application of these materials. Contemporary fabrication and processing techniques capable of producing nanoporous polymer films are reviewed. Focus is placed on techniques capable of sub-100 nm features since this range approaches the size scale of biological components, such as proteins and viruses. The attributes of these techniques are compared, with an emphasis on the characteristic advantages and limitations of each method. Finally, application of these materials to biofiltration, immunoisolation, and drug delivery are reviewed.     

Identification and measurement of fibers in scanning electronmicroscopy images using a high-order correlation process

This work describes the development of a dedicated system capable of identifying, measuring and counting various types of fibers and other objects in digitized scanning electron micrograph (SEM) imagery. The system uses a recursive high order correlation (HOC) process to extract the corner pixels of the fibers. The objects are defined by grouping connected corners, so that morphometric analysis can be performed. The method developed performs satisfactorily when the density of fibers per image ranges from low to medium. Simulation results for several cases are presented, along with a discussion on the capabilities and limitations of the current version of the system     

Separation of explosives using capillary electrochromatography

The identification of explosives and their degradation products is important in forensic and environmental applications. Complete separation of these structurally similar compounds using reversed-phase liquid chromatography has proven to be a challenge. Here we present a demonstration of the use of capillary electrochromatography on the separation of a series of 14 nitroaromatic and nitramine explosive compounds. A separation with baseline resolution is achieved for all of the compounds in under 7 min, featuring efficiencies of over 500?000 theoretical plates/m. Using more aggressive running conditions, 13 of the 14 compounds are separated in under 2 min.     

Demonstration of submersible high-throughput microfluidic immunosensors for underwater explosives detection

Significant security threats posed by highly energetic nitroaromatic compounds in aquatic environments and the demilitarization and pending cleanup of areas previously used for munitions manufacture and storage represent a challenge for less expensive, faster, and more sensitive systems capable of analyzing groundwater and seawater samples for trace levels of explosive materials. Presented here is an inexpensive high throughput microfluidic immunosensor (HTMI) platform intended for the rapid, highly selective quantitation of nitroaromatic compounds in the field. Immunoaffinity and fluorescence detection schemes were implemented in tandem on a novel microfluidic device containing 39 parallel microchannels that were 500 μm tall, 250 μm wide, and 2.54 cm long with covalently tethered antibodies that was engineered for high-throughput high-volume sample processing. The devices were produced via a combination of high precision micromilling and hot embossing. Mass transfer limitations were found in conventional microsystems and were minimized due to higher surface area to volume ratios that exceeded those possessed by conventional microdevices and capillaries. Until now, these assays were limited to maximum total volume flow rates of ~1 mL/min due in part to kinetics and high head pressures of single microchannels. In the design demonstrated here, highly parallelized microchannels afforded up to a 100-fold increase in total volume flow rate while maintaining favorable kinetic constraints for efficient antigen-antibody interaction. The assay employed total volume throughput of up to 6 mL/min while yielding signal-to-noise ratios of >15 in all cases. In addition to samples being processed up to 60 times faster than in conventional displacement-based immunoassays, the current system was capable of quantitating 0.01 ng/mL TNT samples without implementing offline preconcentration, thereby, demonstrating the ability to improve sensitivity by as much as 2 orders of magnitude while decreasing total analysis times up to 60-fold.     

A multicomponent mobile phase for ion chromatography applied to the separation of anions from the residue of low explosives

A multicomponent mobile phase utilizing ion-exchange, ion-exclusion, and ion-pairing principles for the rapid isocratic separation of anions in low explosives residue by ion chromatography (IC) has been developed. The notable feature of this system is that an ion-pairing reagent and an ion-exclusion reagent are combined in the same mobile phase. Contrary to expectation, these reagents act independently of each other in solution. The stock mobile-phase composition consisted of boric acid, D-gluconic acid, lithium hydroxide, and glycerol. Tetrapropylammonium hydroxide, an ion-interaction reagent was used to achieve pH 8.5. Acetonitrile (ACN) was added to enhance resolution and octanesulfonic acid, an ion-exclusion reagent, was added to adjust the retention time of perchlorate. Separation of a mixture of anions common to low explosives residue was achieved in less than 16 min using a Waters IC-Pak Anion HR column. Optimization studies were performed by changing the concentration of the ACN and by altering the pH or the type of ion-interaction or -exclusion agents. Simulated case studies were performed using postblast residues from pipe bombs. The results show this method to be a valid and reproducible procedure for forensic casework analysis. The practical significance of this system is that a reduction in the analysis time and an improvement in efficiency of late-eluting peaks can be achieved without resorting to gradient elution techniques. For the analysis of anions detected in explosives residue, the Waters IC-Pak Anion HR column has proven to be a suitable replacement for the Vydac 300IC405 column, which has been discontinued by the manufacturer.     

Synthesis,characterization and thermal studies of 2-oxo-1,3,5-trinitro-1,3,5-triazacyclohexane (Keto-RDX or K-6)

2-Oxo-1,3,5-trinitro-1,3,5-triazacyclohexane (Keto-RDX or K-6), the most powerful energetic material among nitrourea explosives, has been prepared and scaled up at laboratory level. The identity and purity of the product are tested by elemental analysis, IR, NMR, mass and HPLC techniques. Thermal response and sensitivity experiments on K-6 are also described. The data on sensitivity shows that K-6 can be utilised practically only in phlegmatized form.     

Use of a portable infra-red analyzer for low-level hydrocarbon emissions

During some on-site tests, a portable infra-red (IR) analyzer was used successfully to monitor for hydrocarbon vapors. The detection limit of the IR analyzer is much lower than that of most other hydrocarbon vapor monitors and can be used in situations where, as in most ambient air monitoring situations, the levels are often less than a milligram per cubic metre (mg/m(3)). Traditional procedures used to measure hydrocarbon concentrations at lower levels involves the collection of samples on-site, which are then transported to a laboratory for analysis. The advantage of providing continuous sampling data is that it may indicate trends in the hydrocarbon vapor emissions that may not be apparent using a grab-type sample. The initial tests were designed to determine if the IR analyzer was capable of monitoring the low-level hydrocarbons in a field situation. The findings from that initial work was followed by modification of the test procedure to include an upwind IR analyzer, shortened sampling cycles to produce more data, and additional canister samples collected outside the burn period. The metered grab samples, using Summa canisters, were collected over a 1h period and any results would therefore, reflect an average value over the hour. The IR analyzer, with a sampling cycle of approximately 1min, was able to produce a near real-time distribution of the hydrocarbon vapors in the test site emissions. Because the testing parameters and methods are quite different, it is difficult to compare these two methods, but indications suggest strongly that the use of this portable IR instrument could help to describe the hydrocarbon emissions downwind from a source, as well as to monitor for these hydrocarbons continuously, including situations where the levels are below detection limits of most portable detectors.     

A Disposable Plastic-Silicon Micro PCR Chip Using Flexible Printed Circuit Board Protocols and Its Application to Genomic DNA Amplification

This paper describes a novel disposable and portable plastic-silicon polymerase chain reaction (PCR) system using microfabrication technologies for the realization of miniaturized nucleic acid analyses. The system consists of a polyimide-based film microheating system, embedding with a microheater and a temperature sensor made entirely with flexible printed circuit board (FPCB) process protocols, and a bulk-micromachined silicon reaction chamber. Reduction of the thermal mass by employing a 25 mum-thick polyimide film substrate, which has chemical and thermal resistance suitable for photolithography processes, and integration of a temperature sensor as well as a heater on the film facilitates rapid and precise temperature control. The microfabricated PCR chip demonstrated precise heat control and rapid thermal response in the chip. In addition, the chip successfully amplified a genomic DNA template (breast cancer suppressor gene, BRCA 1 127 base pairs), extracted from the human whole blood containing approximately 100 copies in a 3 muL-volume chamber within 18 min. Thus, it is applicable to a portable system for precise, fast, efficient and cost-effective nucleic analysis, and can be utilized with microscale biochemical analysis and sensing systems as well.     

Fluorescence quenching as an indirect detection method for nitrated explosives

A novel approach based on fluorescence quenching is presented for the analysis of nitrated explosives. Seventeen common explosives and their degradation products are shown to be potent quenchers of pyrene, having Stern-Volmer constants that generally increase with the degree of nitration. Aromatic explosives such as 2,4,6-trinitrotoluene (2,4,6-TNT) are more effective quenchers than aliphatic or nitramine explosives. In addition, nitroaromatic explosives are found to have unique interactions with pyrene that lead to a wavelength dependence of their Stern-Volmer constants. This phenomenon allows for their differentiation from other nitrated explosives. The fluorescence quenching method is then applied to the determination of hexahydro-1,3,5-trinitro-1,3,5-triazine (RDX), octahydro-1,3,5,7-tetranitro-1,3,5,7-tetrazine(HMX), 2,4,6-TNT, nitromethane, and ammonium nitrate in various commercial explosive samples. The samples are separated by capillary liquid chromatography with post-column addition of the pyrene solution and detection by laser-induced fluorescence. The indirect fluorescence quenching method shows increased sensitivity and selectivity over traditional UV-visible absorbance as well as the ability to detect a wider range of organic and inorganic nitrated compounds.     

Advances in science and technology of modern energetic materials: an overview

Energetic materials such as explosives, propellants and pyrotechnics are widely used for both civilian and military explosives applications. The present review focuses briefly on the synthesis aspects and some of the physico-chemical properties of energetic materials of the class: (a) aminopyridine-N-oxides, (b) energetic azides, (c) high nitrogen content energetic materials, (d) imidazoles, (e) insensitive energetic materials, (f) oxidizers, (g) nitramines, (h) nitrate esters and (i) thermally stable explosives. A brief comment is also made on the emerging nitration concepts. This paper also reviews work done on primary explosives of current and futuristic interest based on energetic co-ordination compounds. Lead-free co-ordination compounds are the candidates of tomorrow's choice in view of their additional advantage of being eco-friendly. Another desirable attribute of lead free class of energetic compounds is the presence of almost equivalent quantity of fuel and oxidizer moieties. These compounds may find wide spectrum of futuristic applications in the area of energetic materials. The over all aim of the high energy materials research community is to develop the more powerful energetic materials/explosive formulations/propellant formulations in comparison to currently known benchmark materials/compositions. Therefore, an attempt is also made to highlight the important contributions made by the various researchers in the frontier areas energetic ballistic modifiers, energetic binders and energetic plasticizers.     

A comparison of the quantitative methods for the analysis of the platinum-containing anticancer drug [cis-[amminedichloro(2-methylpyridine)]platinum(II)] (ZD0473) by HPLC coupled to either a triple quadrupole mass spectrometer or an inductively coupled plasma mass spectrometer

The use of high performance liquid chromatography coupled with inductively coupled plasma mass spectrometry (HPLC-ICPMS) as means for the quantitative determination of ZD0473, a platinum anticancer drug, and its related biologically active "aqua" compounds in biofluid samples is described. The performance of the resulting HPLC-ICPMS method was compared with that of a conventional HPLC-triple quadrupole mass spectrometer-based (HPLC-MS/MS) system for properties such as limit of detection, linearity, and reproducibility using spiked samples. The methods were then applied to the determination of plasma ultrafitrate concentrations of ZD0473 in dog plasma samples obtained following intravenous and oral administration at 0.5 and 6 mg/kg, respectively. These experiments showed that both methods were capable of providing accurate and precise results but that the HPLC-ICPMS method had advantages of extended linear range and superior sensitivity, providing a limit of quantification of 0.1 ng/mL for ZD0473, as compared to 5 ng/mL using the current HPLC-MS/MS method. In addition, by using a single combined HPLC-ICPMS/MS/MS system, it was possible to determine the relative MS/MS response of the aqua compounds for the first time.