The detection of explosives, energetic materials, and their associated compounds for security screening, demining, detection of unexploded ordnance, and pollution monitoring is an active area of research. A wide variety of detection methods and an even wider range of physical chemistry issues are involved in this very challenging area. This review focuses on techniques such as optical and mass spectrometry and chromatography for detection of trace amounts of explosives with short response times. We also review techniques for detecting the decomposition fragments of these materials. Molecular data for explosive compounds are reviewed where available.

EXPLOSIVES DETECTION: A Challenge for Physical Chemistry

Skin cancer and new treatment perspectives: a review.

Materials Research Bulletinについて

We present the first results using a new technique that combines femtosecond pump–probe methods with energy- and angle-resolved photoelectron–photoion coincidence imaging. The dominant dissociative multiphoton ionization (DMI) pathway for NO2 at 375.3 nm is identified as three-photon excitation to a repulsive potential surface correlating to NO(C 2Π)+O(3P) followed by one-photon ionization to NO+(X 1Σ+). Dissociation along this surface is followed on a femtosecond timescale.

Femtosecond time-resolved photoelectron-photoion coincidence imaging studies of dissociation dynamics

Detection of explosives is important for public safety. A recently developed low-temperature plasma (LTP) probe for desorption and ionization of samples in the ambient environment ( Anal. Chem. 2008 , 80 , 9097 ) is applied in a comprehensive evaluation of analytical performance for rapid detection of 13 explosives and explosives-related compounds. The selected chemicals [pentaerythritol tetranitrate (PETN), trinitrotoluene (TNT), cyclo-1,3,5-trimethylenetrinitramine (RDX), tetryl, cyclo-1,3,5,7-tetramethylenetetranitrate (HMX), hexamethylene triperoxide diamine (HMTD), 2,4-dinitrotoluene, 1,3-dinitrobenzene, 1,3,5-trinitrobenzene, 2-amino-4,6-dinitrotoluene, 4-amino-2,6-dinitrotoluene, 2,6-dinitrotoluene, and 4-nitrotoluene) were tested at levels in the range 1 pg-10 ng. Most showed remarkable sensitivity in the negative-ion mode, yielding limits of detection in the low picogram range, particularly when analyzed from a glass substrate heated to 120 °C. Ions typically formed from these molecules (M) by LTP include [M + NO(2)](-), [M](-), and [M - NO(2)](-). The LTP-mass spectrometry methodology displayed a linear signal response over three orders of magnitude of analyte amount for the studied explosives. In addition, the effects of synthetic matrices and different types of surfaces were evaluated. The data obtained demonstrate that LTP-MS allows detection of ultratrace amounts of explosives and confirmation of their identity. Tandem mass spectrometry (MS/MS) was used to confirm the presence of selected explosives at low levels; for example, TNT was confirmed at absolute levels as low as 0.6 pg. Linearity and intra- and interday precision were also evaluated, yielding results that demonstrate the potential usefulness and ruggedness of LTP-MS for the detection of explosives of different classes. The use of ion/molecule reactions to form adducts with particular explosives such as RDX and HMX was shown to enhance the selectivity and specificity. This was accomplished by merging the discharge gas with an appropriate reagent headspace vapor (e.g., from a 0.2% trifluoracetic acid solution).

Detection of explosives and related compounds by low-temperature plasma ambient ionization mass spectrometry.

The photodissociation of nitrobenzene and the nitrotoluene isomers at 375 nm, induced by a 90 femtosecond laser, is analyzed and compared with the fragmentation by a 10 nanosecond laser at the same wavelength. The molecular ionization is attributed to a nonresonant multiphoton process, and the observed fragmentation can be explained predominantly by an above ionization mechanism (ladder climbing). The mass spectra of the three nitrotoluene isomers show differences which can be used for analytical purposes. The molecular rearrangement taking place prior to the dissociation is also discussed. For nitrobenzene, it is suggested that most of the dissociation occurs from the nitrobenzene structure rather than that of phenyl nitrite. In the case of o-nitrotoluene, it seems that the hydrogen transfer from the −CH3 to the NO2 group (ortho effect) is favored in ionic states, while the rearrangement to a nitrite structure is possible in the excited electronic states.

On the Fragmentation of Nitrobenzene and Nitrotoluenes Induced by a Femtosecond Laser at 375 nm

In the present Letter we report that a number of polyatomic molecules (M) when irradiated with short pulse lasers <90 fs at 750−790 nm and intensities up to 1015 W cm-2 produce multiply charged parent ions and do not fragment to any great degree. This surprising observation is found in both linear and ring structured molecules and is very similar to the behavior of inert atoms such as xenon under the same irradiation conditions. This is a very different behavior from irradiating with nanosecond pulses at 109 W cm-2 where low-mass fragments dominate the spectrum. For the hydrocarbon molecules presented in this work, there exists an envelope of 2+ ionized peaks, which corresponds to the parent and a number of (M − nH) satellites. This feature is characteristic of these molecules in the intensity region 1014-15 W cm-2 and is interpreted as evidence for tunneling or barrier suppression. Coulomb explosion leading to multiply charged atoms, which is evident for CS2, does not seem to be operating for the larger ...

Behavior of Polyatomic Molecules in Intense Infrared Laser Beams

A comparison of femtosecond and nanosecond multiphoton ionization and dissociation for some nitro-molecules

The photochemistry of nitromethane has been studied extensively for many years. Although it is generally agreed that the principal photodissociative process is cleavage of the C−N bond to yield the...

Multiphoton Ionization and Dissociation of Nitromethane Using Femtosecond Laser Pulses at 375 and 750 nm

It is well-known that aromatic molecules, when irradiated by UV laser beams in the nanosecond pulse width regime, yield exclusive parent ions at laser intensities of 107 W cm-2 (soft ionization). As the laser intensities increase up to 109 W cm-2, however, extensive fragmentation takes place such that small mass fragments dominate the spectra at the expense of parent signature ions. The reason for this is that the dissociative lifetimes are shorter than the laser pulse width and ladder-switching fragmentation takes place. With the development of high power femtosecond lasers, these dissociative lifetimes can often be bypassed. Presently, at laser intensities up to the order of 1015 W cm-2 with pulse widths as short as 50 fs at near-infrared (IR) wavelengths (790 nm), soft ionization again takes place. This has been seen using a technique known as femtosecond laser mass spectrometry (FLMS). Under such conditions, stable multiply charged parent and adjacent satellite ions are observed and the fragmentation ...

Hamdi Şükür Kiliç

Papers

On the Fragmentation of Nitrobenzene and Nitrotoluenes Induced by a Femtosecond Laser at 375 nm

Behavior of Polyatomic Molecules in Intense Infrared Laser Beams

A comparison of femtosecond and nanosecond multiphoton ionization and dissociation for some nitro-molecules

Multiphoton Ionization and Dissociation of Nitromethane Using Femtosecond Laser Pulses at 375 and 750 nm

Multiply Charged Ions from Aromatic Molecules Following Irradiation in Intense Laser Fields