Raman spectroscopy and security applications: the detection of explosives and precursors on clothing

This study describes the application of confocal Raman microscopy to the detection and identification of explosives and their precursors in situ on undyed natural and synthetic fibres and coloured textile specimens. Raman spectra were obtained from explosives particles trapped between the fibres of the specimens. The explosives pentaerythritol tetranitrate (PETN), trinitrotoluene (TNT), and ammonium nitrate as well as the explosives precursors hexamethylenetetraamine (HMTA) and pentaerythritol were used in this study. Raman spectra were collected from explosives particles with maximum dimensions in the range 5–10 µm. Despite the presence of spectral bands arising from the natural and synthetic polymers and dyed textiles, the explosive substances could be identified by their characteristic Raman bands. Furthermore, Raman spectra were obtained from explosives particles trapped between highly fluorescent clothing fibres. Raman spectra of the explosive and explosive precursor substances on dyed and undyed clothing substrates were readily obtained in situ within 90 s without sample preparation and with no alteration of the evidential material. Copyright © 2009 John Wiley & Sons, Ltd.     

Trace level detection and identification of nitro‐based explosives by surface‐enhanced Raman spectroscopy

Methods for rapid identification of explosives and their associated compounds at trace level quantities are needed for security screening applications. In this paper, we apply the surface‐enhanced Raman spectroscopy (SERS) to detect and identify traces (as low as tens of pg) of pentaerythritol tetranitrate (PETN), ethylene glycol dinitrate (EGDN), cyclotrimethylene‐trinitramine (RDX) and trinitrotoluene (TNT) using commercially available substrates (Klarite®, Renishaw diagnostics). High quality spectra were achieved within 10 s with a compact Raman spectrometer. Principal component analysis (PCA) of the data was performed to understand what factors affected the spectral variation across the samples. It was found that 76% of the spectral variation was explained by the first three PCs. Score plots for these components showed that the energetic materials can be clearly classified on the basis of SERS spectra also at trace level quantity. Our measurements further demonstrate the potential for using SERS as fast, in situ analytical tool for safety devices, with a sensitivity which competes and, in some cases, overcomes other techniques. Copyright © 2013 John Wiley & Sons, Ltd.     

Confocal Raman microscopy for simultaneous monitoring of partitioning and disordering of tricyclic antidepressants in phospholipid vesicle membranes

Characterization of drug–membrane interactions is important in order to understand the mechanisms of action of drugs and to design more effective drugs and delivery vehicles. Raman spectra provide compositional and conformational information of drugs and lipid membranes, respectively, allowing membrane disordering effects and drug partitioning to be assessed. Traditional Raman spectroscopy and other widely used bioanalytical techniques such as differential scanning calorimetry (DSC) and nuclear magnetic resonance (NMR) typically require high sample concentrations. Here, we describe how temperature‐controlled, optical‐trapping confocal Raman microscopy facilitates the analysis of drug–membrane interactions using micromolar concentrations of drug, while avoiding drug depletion from solution by working at even lower lipid concentrations. The potential for confocal Raman microscopy as an effective bioanalytical tool is illustrated using tricyclic antidepressants (TCAs), which are cationic amphiphilic molecules that bind to phospholipid membranes and influence lipid phase transitions. The interaction of these drugs with vesicle membranes of differing head‐group charge is investigated while varying the ring and side‐chain structure of the drug. Changes in membrane structure are observed in Raman bands that report intra‐ and intermolecular order versus temperature. The partitioning of drugs into the membrane can also be determined from the Raman scattering intensities. These results demonstrate the usefulness of confocal Raman microscopy for the analysis of drug–membrane systems at biologically relevant drug concentrations. Effective tools for monitoring drug–membrane interactions are crucial for rational design of new drugs. Copyright © 2009 John Wiley & Sons, Ltd.     

Non-Destructive In-Situ Study of White and Black Coating on Painted Pottery Sherds From Bancun Site (Henan,China) by Raman Microscopy

Abstract

Pottery sherds from the archaeological site of Bancun (Henan, China) were analyzed by Raman microscopy and the pigments used in the coating of this ancient (c. 4000–5000 BC) pottery were determined. It was found that bauxite was used to make the white pigment. The black coating was identified as a magnetite and its particle size was in the nanometer range. This work also showed that the size of pigment had influence on the color of the coating. In principle, Raman spectra could be used not only to identify the mineral source of the pigment but also to estimate the particle size of the pigments.     

Surface‐enhanced Raman scattering on colloid gels originated from low molecular weight gelator

Surface‐enhanced Raman scattering (SERS) on silver and gold colloid gels formed by a low molecular weight organic gelator, bis‐(S‐phenylalanine) oxalyl amide, was obtained. Strong Raman signals dominate in the SERS spectra of hydrogels containing silver nanoparticles prepared by citrate and borohydride reduction methods, whereas broad bands of low intensity are detected in the spectra of gold colloid gels. Resemblance between Raman spectrum of the crystalline substance and the SERS spectra of the silver nanoparticle–hydrogel composites implies the electromagnetic nature of the signal enhancement. A change in Raman intensity of the benzene and amide II bands caused by an increase in temperature and concentration indicates that the gelling molecules are strongly attached through the benzene moieties to the metal nanoparticles while participating in gel formation by intermolecular hydrogen bonding between the adjacent oxalyl amide groups. Transmission electron microscopy reveals a dense gel structure in the close vicinity of the enhancing metal particles for both silver colloid gels. Copyright © 2008 John Wiley & Sons, Ltd.     

Fast detection of sulphate minerals (gypsum,anglesite, baryte) by a portable Raman spectrometer

Well‐resolved Raman spectra of gypsum, anglesite and baryte were detected using a portable Raman instrument (Ahura First Defender XL) in the laboratory and outdoor under atmospheric conditions. Spectra were obtained using a 785‐nm excitation. The portable spectrometers display generally lower spectral resolution compared with the laboratory confocal instrument but permit the fast, unambiguous detection of minerals under field conditions. Portable Raman instruments can be advocated as excellent tools for field geological, environmental as well as exobiological applications. A miniaturized Raman instrument will be included in the Pasteur analytical package of the ESA ExoMars mission and interesting research applications can now be proposed for in situ field planetary studies. Additionally, portable Raman instruments represent an ideal tool for demonstrating possible applications of Raman spectroscopic techniques outdoor. In geosciences this approach represents a new field which could completely change classical field work. Copyright © 2009 John Wiley & Sons, Ltd.     

Confocal Raman microscopy for monitoring the membrane polymerization and thermochromism of individual,optically trapped diacetylenic phospholipid vesicles

Optical‐trapping confocal Raman microscopy allows the 1, 4‐addition reaction of diacetylenic functional groups in 1,2‐bis(10,12‐tricosadiynoyl)‐sn‐glycero‐3‐phosphocholine lipids to be monitored in individual phospholipid vesicles. Optical trapping allows a single vesicle to be observed over time, allowing the direct observation of structural changes in the vesicle membrane during polymerization. Confocal Raman microscopy excludes light collection outside the optical‐trap region avoiding interferences from the surrounding solution, while chemical reactions occurring in the membrane of the trapped vesicle can be measured with high sensitivity. Individual, optically trapped liposomes (0.6 µm in diameter) were exposed to photolysis radiation at 254 nm. Upon exposure to UV light, the cross‐linking polymerization reaction formed a conjugated ene–yne backbone in the bilayer of the optically trapped vesicle. Polymerization produces two different polymers, red and yellow in color, which can be distinguished structurally by their Raman spectra. Rates of red and yellow polymer formation were monitored by the Raman scattering intensities from both C = C stretching vibrations at 1455 cm^–1 and 1508 cm^–1 and C ≡ C stretching vibrations at 2080 and 2110 cm^–1, respectively. Polymer formation rates depended linearly on 254‐nm light intensity, consistent with a one‐photon excited polymerization reacting in a photostationary state. Relative populations of red and yellow polymer in a polymerized vesicle depend sensitively on the sample temperature. From temperature‐dependent Raman spectra, the enthalpy change of the red‐to‐yellow thermochromic response and corresponding structural changes in the polymer could be determined. Copyright © 2011 John Wiley & Sons, Ltd.     

Characterization of tetragonal SAT0.3: LA0.075: CAT0.625 perovskite crystal: spectroscopic and microscopic investigations

We report room temperature measurements of X‐ray diffraction (XRD), optical transmission microscopy (OTM), atomic force microscopy (AFM), infrared‐absorption (IR), and micro‐Raman spectroscopy (µ‐RS) of the oriented SAT_0.3: LA_0.075: CAT_0.625 single crystal. The final structure refinement of SAT_0.3: LA_0.075: CAT_0.625 crystal was performed for I4/m space group at room temperature. Vibrational spectra of the crystal were discussed in terms of group‐theoretical predictions for untilted (Fm3 m) and tilted tetragonal (I4/m) perovskite structure. The confocal µ‐Raman measurements of depth profiling of SAT_0.3: LA_0.075: CAT_0.625 crystal suggest a relationship between sensitivities of the ordering‐related Raman‐active modes and the variation of order parameter η. Copyright © 2009 John Wiley & Sons, Ltd.     

Detection of explosives and latent fingerprint residues utilizing laser pointer–based Raman spectroscopy

A modular, compact Raman spectrometer, based on a green laser pointer, an air cooled intensified charged coupled device and a x, y motorized translation stage was developed and applied for point detection. Its performance was tested for measurements of Raman spectra of liquids, trace amounts of explosives and individual particles, as well as for locating individual particles of interest and for chemical imaging of residues of latent human fingerprints. This system was found to be highly sensitive, identifying masses as low as ~1 ng in short times. The point and real-time detection capabilities of the spectrometer, together with the portability that it offers, make it a potential candidate for replacing existing Raman microscopes and for field applications.     

Spectrochemical properties of some explosives in the vapor state

The FTIR spectra of 1,3,5-trinitro-1,3,5-triazacyclohexane (RDX) and pentaerythritol tetranitrate (PETN) in the vapor phase over wide frequency (3500–500 cm^?1) and temperature ranges (293–383 K) is experimentally studied and the assignment of the observed vibrational bands is performed. To clarify the nature of the physicochemical processes that occur during the heating and evaporation of RDX and PETN and to detect and identify their characteristic components, the mass spectra and sub-THz spectra of these explosives are studied. To obtain spectroscopic information, special experimental techniques for recording of IR, sub-THz, and mass spectra of vapors of explosives and for preparation of high-purity RDX and PETN samples (with a main substance content of >99.7%) are developed based on modern methods of synthesis and purification.     

Temperature‐depending Raman line‐shift of silicon carbide

Silicon carbide (SiC) is often used for electronic devices operating at elevated temperatures. Spectroscopic temperature measurements are of high interest for device monitoring because confocal Raman microscopy provides a very high spatial resolution. To this end, calibration data are needed that relate Raman line‐shift and temperature. The shift of the phonon wavenumbers of single crystal SiC was investigated by Raman spectroscopy in the temperature range from 3 to 112°C. Spectra were obtained in undoped 6H SiC as well as in undoped and nitrogen‐doped 4H SiC. All spectra were acquired with the incident laser beam oriented parallel as well as perpendicular to the c‐axis to account for the anisotropy of the phonon dispersion. Nearly all individual peak centers were shifting linearly towards smaller wavenumbers with increasing temperature. Only the peak of the longitudinal optical phonon A₁(LO) in nitrogen‐doped 4H SiC was shifting to larger wavenumbers. For all phonons, a linear dependence of the Raman peaks on both parameters, temperature and phonon frequency, was found in the given temperature range. The linearity of the temperature shift allows for precise spectroscopic temperature measurements. Temperature correction of Raman line‐shifts also provides the ability to separate thermal shifts from mechanically induced ones. Copyright © 2009 John Wiley & Sons, Ltd.     

In situ detection of cocaine hydrochloride in clothing impregnated with the drug using benchtop and portable Raman spectroscopy

This study describes the application of benchtop and portable Raman spectroscopy for the in situ detection of cocaine hydrochloride in clothing impregnated with the drug. Raman spectra were obtained from a set of undyed natural and synthetic fibres and dyed textiles impregnated with the drug. The spectra were collected using three Raman spectrometers: one benchtop dispersive spectrometer coupled to a fibre‐optic probe and two portable spectrometers. Despite the presence of some spectral bands arising from the natural and synthetic polymer and dyed textiles, the drug could be identified by its characteristic Raman bands. High‐quality spectra of the drug could be acquired in situ within seconds and without any sample preparation or alteration of the evidential material. A field‐portable Raman spectrometer is a reliable technique that can be used by emergency response teams to rapidly identify unknown samples. Copyright © 2009 John Wiley & Sons, Ltd.     

Drop‐coating deposition Raman spectroscopy of liposomes

Drop‐coating deposition Raman (DCDR) spectroscopy was tested as a potential technique for studying liposomes at very low sample concentrations. We used model liposomes prepared either from 1,2‐distearoyl‐sn‐glycero‐3‐phospocholine or from soybean asolectin, which is composed of various lipids and thus represents a good model of natural membranes. In both cases, deposited samples formed a dried drop with a circular shape with a ring of concentrated liposomes at the edge. Spectral mapping showed that maximum Raman intensity originated from the inner part of the edge ring, while Raman signal gradually decreased in both radial directions. The Raman spectra exhibited excellent reproducibility of spectral characteristics at different locations in the drop, indicating similar conformation and ordering of hydrocarbon lipid chains in the sample. Our results suggest that DCDR spectroscopy can be used for studying lipids in situ, and sensitivity of this technique is at least two orders of magnitude higher than that of conventional Raman microscopy. Copyright © 2011 John Wiley & Sons, Ltd.     

Time resolved Raman spectroscopy for depth analysis of multi‐layered mineral samples

Time resolved Raman spectroscopy (TRRS) can provide subsurface information from multi‐layered samples of transparent and translucent evaporative and silicate minerals up to several centimetres thick. Depth information was obtained using 3‐ps pulsed laser excitation at 720 nm and a gated intensified charge‐coupled device detector with stepwise increasing delay times. Blocks of different minerals were used as first, second or third layers, and Raman spectra from deeper layers could be detected through 10 mm of translucent calcite and up to 40 mm of transparent halite crystals. Measurements by conventional confocal Raman, as well as spatially offset Raman spectroscopy were also successful in distinguishing different mineral layers. This study establishes the great potential for the use of Raman spectroscopy in future planetary exploration, where TRRS could be used as a non‐invasive tool for profiling the (sub‐)surface at millimetre‐depth resolution. Copyright © 2013 John Wiley & Sons, Ltd.     

Detection and identification of explosives by surface enhanced Raman scattering

Surface Enhanced Raman Scattering (SERS) has undergone an important development over the last few years, particularly in the detection and identification of extremely low traces of explosives. The large number of studies and results generated by this increasing research makes a comprehensive overview necessary. This work reviews in detail that research focused on the identification of explosives by SERS, including TNT, DNT, RDX, PETN, TATP, HMTD, perchlorate, etc. either in bulk state, in solution or in vapor phase. In brief, TNT and DNT have been widely studied by SERS due to its aromatic structure and LODs down to 5–10 zg and 10^?17–10^?13 M have been achieved. The other explosives have been quite less researched; therefore, few results are available to be compared and a bit more modest LODs have been reached such as 10^?13 M for RDX, 10^?4 M for TATP, 5 pg for PETN, or 10^?9 M for perchlorate. In addition, the challenges of detecting both explosives vapors and perchlorate anion by SERS are thoroughly discussed.     

Si/polyaniline-based porous carbon composites with an enhanced electrochemical performance as anode materials for Li-ion batteries

Silicon/polyaniline-based porous carbon (Si/PANI-AC) composites have been prepared by a three-step method: coating polyaniline on Si particles using in situ polymerization, carbonizing, and further activating by steam. The morphology and structure of Si/PANI-AC composites have been characterized by scanning electron microscopy, transmission electron microscopy, X-ray diffraction, and Raman spectra, respectively. The content and pore structure of the carbon coating layer in Si/PANI-AC have been measured by thermogravimetric analysis and N₂ adsorption-desorption isotherm, respectively. The results indicate some micropores about 1~2 nm in the carbon layer appear during activation and that crystal structure and morphology of Si particles can be retained during preparation. Si/PANI-AC composites exhibit high discharge capacity about 1000 mAh g^?1 at 1.5 A g^?1; moreover, when the current density returns to 0.2 A g^?1, the discharge capacity is still 1692 mAh g^?1 and remains 1453 mAh g^?1 after 70 cycles. The results indicate that the porous carbon coating layer in composites plays an important role in the improvement of the electrochemical performance of pure Si.     

Fast mapping of inhomogeneities in the popular metallic perovskite Nb:SrTiO3 by confocal Raman microscopy

Confocal Raman microscopy was applied in order to investigate the homogeneity of donor doping in Nb:SrTiO₃ single crystals. Measurements of local Raman spectra revealed a systematic relation between the intensity of the Raman signal and the donor content of the crystals. We successfully elaborated a correspondence between the electronic structure and the intensity of the Raman lines using a crystal with macroscopic inhomogeneity as a demonstration sample. By mapping the distribution of the intensity of the Raman signal, we identified a characteristic inhomogeneous structure related to the presence of clusters with sizes of 5 µm to 20 µm, indicating inhomogeneous donor distribution caused by flaws introduced during crystal growth. Hence, we propose confocal Raman microscopy as a convenient technique for investigating the homogeneity and quality of doped perovskite surfaces, which are needed for various technological applications. (© 2014 WILEY‐VCH Verlag GmbH &Co. KGaA, Weinheim)     

Confocal Raman spectroscopy to monitor intracellular penetration of TiO2 nanoparticles

Confocal Raman microscopy, a noninvasive, label‐free, and high‐spatial resolution imaging technique, in combination with K‐mean cluster analysis and a correlation coefficient map, was employed to trace titanium dioxide (TiO₂) nanoparticles in living MCF‐7 and TERT cells. The penetration of TiO₂ nanoparticles into cells revealed a gradual time‐dependent diffusion of nanoparticles over the entire cell. Cell apoptosis was monitored by tracing cytochrome c diffusion into the cytoplasm. A comparison with the mitochondrial clustering indicated that cytochrome c was inside the mitochondria for TiO₂ concentration of 2 µg ml⁻¹. This result demonstrates that the presence of TiO₂ particles within a cell does not induce apoptosis. We demonstrated that confocal Raman microscopy allow to follow penetration of TiO₂ particles in cell and to monitor the apoptotic status of the penetrated cells. Copyright © 2014 John Wiley & Sons, Ltd.     

Carbon-encapsulated cobalt nanoparticles: synthesis,properties, and magnetic particle hyperthermia efficiency

A facile and low-cost method for structuring carbon-encapsulated cobalt nanoparticles (Co@C) is presented. Three samples were solvothermally prepared in one step at 220 °C and one in two steps at 200 °C. Three different polyols such as propylene glycol, triethylene glycol, and tetraethylene glycol were used as carbon sources, solvents, and reducing agents. The samples were characterized by X-ray powder diffraction (XRD), transmission electron microscopy (TEM), and Raman spectroscopy. Concerning the crystal structure of the particles, a mixture of hcp/fcc Co phases was obtained in three of the samples, independently of the polyol used. The coexistence of cubic and hexagonal phases was revealed both from XRD and high-resolution TEM (HRTEM). The formation of the cubic fcc structure, despite the relatively low reaction temperature, is attributed to the role of the interface between carbon coating and metallic core. The presence of carbon coating was demonstrated by Raman spectrometry, exhibiting the characteristic D and G graphitic bands, and by HRTEM observations. All samples showed ferromagnetic behavior with saturation magnetization up to 158 emu/g and coercivity up to 206 Oe. From the magnetic particle hyperthermia measurements recorded at a frequency of 765 kHz, a maximum SLP value of 241 W/g was obtained.     

Nuclear quadrupole resonance of explosives: Simultaneous detection of RDX and PETN in semtex

We have used nuclear quadrupole resonance (NQR) for the detection of¹⁴N in explosives and introduce a new method for the simultaneous detection of the explosives cyclotrimethylene trinitramine (RDX) and pentaerythritol tetranitrate (PETN). We have developed an interleaved pulse sequence, which provides efficient excitation of both RDX and PETN, to drive a solenoid coil that is doubly resonant at 3.41 and 0.89 MHz (suitable resonant frequencies of RDX and PETN, respectively). The excitation of RDX and PETN is carried out alternately within the pulse sequence via frequency hops in the spectrometer; no electronic switching is required to alternately returne the doubly resonant probe to the resonant frequency of each material. The signals from RDX and PETN, which are separated by about 2.52 MHz, are brought into the same audio window by mixing with a suitable intermediate frequency. We have tested the doubly resonant probe and interleaved pulse sequence on plastic formulations of RDX and PETN, on their own (PE-4 and Detasheet respectively) and as a mixture in Semtex.