Emergency responders attending an incident can inadvertently encounter explosive materials that can put their safety and that of the general public at risk. Ensuring that teams have suitable detection equipment is of vital importance to mitigate the impact of the incident and assist in the early return to normality. This study examines the use of Spatially Offset Raman Spectroscopy (SORS) technology for rapid identification of a wide range of explosives, improvised explosive precursors and flash powders either directly or through a range of barriers, with the potential to improve safety, efficiency and critical decision making in incident management and search operations.
In the past decade, consumption of illegal and controlled street drugs has steadily increased. According to the latest World Drug Report, released by the United Nations Office on Drugs and Crime (UNODC)1, more people are using drugs, and there are more drugs, and more types of drugs, than ever. Around 269 million people used drugs worldwide in 2018, which is 30 per cent more than in 20091. The growth in global drug supply and demand poses challenges to law enforcement, compounds health risks and complicates efforts to prevent and treat drug use disorders. Due to COVID-19, traffickers may have to find new routes and methods and opioid shortages may result in people seeking out more readily available substances such as alcohol, benzodiazepines or mixing with synthetic drugs.1 Herein, we study the use of Raman SORS technology for rapid identification of narcotics in a range of concentrations – from pure form (as it is smuggled or transported) to street forms and products, often mixed with conventional cutting agents, with the potential to improve safety, efficiency and critical decision making in incident management, search operations, policing and ports and border operations.
Raman spectroscopy allows the acquisition of molecularly specific signatures of pure compounds and mixtures making it a popular method for material identification applications. In hazardous materials, security and counter terrorism applications, conventional handheld Raman systems are typically limited to operation by line-of-sight or through relatively transparent plastic bags / clear glass vials. If materials are concealed behind thicker, coloured or opaque barriers it can be necessary to open and take a sample. Spatially Offset Raman Spectroscopy (SORS)[1] is a novel variant of Raman spectroscopy whereby multiple measurements at differing positions are used to separate the spectrum arising from the sub layers of a sample from the spectrum at the surface. For the first time, a handheld system based on SORS has been developed and applied to hazardous materials identification. The system - "Resolve" - enables new capabilities in the rapid identification of materials concealed by a wide variety of non-metallic sealed containers such as; coloured and opaque plastics, paper, card, sacks, fabric and glass. The range of potential target materials includes toxic industrial chemicals, explosives, narcotics, chemical warfare agents and biological materials. Resolve has the potential to improve the safety, efficiency and critical decision making in incident management, search operations, policing and ports and border operations. The operator is able to obtain a positive identification of a potentially hazardous material without opening or disturbing the container - to gain access to take a sample - thus improving safety. The technique is fast and simple thus suit and breathing gear time is used more efficiently. SORS also allows Raman to be deployed at an earlier stage in an event before more intrusive techniques are used. Evidential information is preserved and the chain of custody protected. Examples of detection capability for a number of materials and barrier types are presented below.
Advances in the application of Quantum Cascade Lasers (QCL) to trace gas detection will be presented. The
solution is real time (~1 μsec per scan), is insensitive to turbulence and vibration, and performs multiple
measurements in one sweep. The QCL provides a large dynamic range, which is a linear response from ppt to
% level. The concentration can be derived with excellent immunity from cross interference. Point sensing
sensors developed by Cascade for home made and commercial explosives operate by monitoring key
constituents in real time and matching this to a spatial event (i.e. sniffer device placed close to an object or
person walking through portal (overt or covert). Programmable signature detection capability allows for
detection of multiple chemical compounds along the most likely array of explosive chemical formulation.
The advantages of configuration as "point sensing" or "stand off" will be discussed. In addition to explosives
this method is highly applicable to the detection of mobile drugs labs through volatile chemical release.
We demonstrate how molecular spectroscopy methods using NIR and MIR lasers can provide rapid detection and
identification of many threat materials. It is increasingly recognised that one spectroscopic method will not be suited to
every target in every scenario, both in terms of spectroscopic selectivity and the context e.g. vapour phase or within a
sealed container. The orthogonal selection rules and capabilities of IR and Raman in combination allow the identification
of a very broad range of targets, both in liquid and vapour phase. Therefore, we introduce the benefits of the combining
infra-red absorbance based on Quantum Cascade lasers (QC-IR) and NIR Raman spectroscopy for nitrogenous and
peroxide based materials. Rapid scan rates up to 10Hz for QC-IR and Raman and are demonstrated using current
technology. However, understanding of the chemistry and spectroscopic signatures behind such materials is necessary
for accurate fast fitting algorithms to benefit of the full advantage with advances in hardware. This is especially true as
future users requirements move towards rapid multiplexed analysis and data fusion from a variety of sensors.
Following the development of point sensing improvised explosive device (IED) technology[1] Cascade Technologies have
initial work in the development of equivalent stand-off capability. Stand-off detection of IEDs is a very important technical
requirement that would enable the safe identification and quantification of hazardous materials prior to a terrorist attack. This
could provide advanced warning of potential danger allowing evacuation and mitigation measures to be implemented.
With support from the UK government, Cascade Technologies is currently investigating technology developments aimed at
addressing the above stand-off IED detection capability gap. To demonstrate and validate the concept, a novel stand-off
platform will target the detection and identification of common high vapor pressure IED precursor compounds, such as
hydrogen peroxide (H2O2), emanating from a point source. By actively probing a scene with polarized light, the novel
platform will offer both enhanced selectivity and sensitivity as compared to traditional hyperspectral sensors, etc. The
presentation will highlight the concept of this novel detection technique as well as illustrating preliminary results.
There is a need for fast, reliable and sensitive biosensor arrays. We have used nanostructured plasmonic gold surfaces for
the detection of biological species by surface enhanced resonance Raman scattering (SERRS). Careful, directed
placement by Dip-Pen Nanolithography (DPN) of the biological species or capture chemistry, within the array facilitates
efficient read out via fast Raman line mapping. In addition, we can apply parallel deposition methods to enhance the
throughput of these combined techniques. SERRS is an extremely sensitive spectroscopic technique that offers several
advantages over conventional fluorescence detection. For example, the high sensitivity of the method allows detection of
DNA capture from single plasmonic array "pixels" ~1 μm2 in area. Additionally, the information rich nature of the
SERRS spectrum allows multiple levels of detection to be embedded into each pixel, further increasing the information
depth of the array. By moving from micro- to nano-scale features, sensor chips can contain up to 105 times more
information, dramatically increasing the capacity for disease screening.
Functionalised nanoparticles have been used in a number of studies including detection of DNA at ultra low
concentrations, immuno-histochemistry and more recently as substrates for surface enhanced resonance Raman
scattering (SERRS) based imaging approaches. The advantages of using metallic nanoparticles are that they are
very bright in terms of their optical characteristics and also can be functionalised to provide a SERRS response and
hence provide a unique Raman fingerprint. Here we present the functionalisation of gold and silver nanoparticles in
such a way that the enhancement effect can be greatly increased through biological interaction and as such
effectively turn on the SERRS effect. In an advancement of this nanoparticles have been used as imaging agents for
single cells when functionalised with an appropriate antibody and can give information on the expression of specific
receptors on cell surfaces as well as sub-cellular compartmentalisation information.
A low cost technique is reported for the rapid screening of containers for materials that potentially could be used for terrorist activities. For peroxide based samples it is demonstrated that full characterisation can be achieved in a continuous curve fitting monitoring mode acquiring up to 10 spectra per second. This clearly demonstrates the potential for a Raman based method to be incorporated into a check-point whilst retaining fast throughput. A number of precursor compounds to nerve agents and peroxide and nitrate based improvised explosive materials have been studied. The potential strengths and weaknesses of using Raman for multiple target identification are discussed with regard to the common vibrations associated with each group of agents. Within this context we also introduce the use of fast Raman line mapping into the trace analysis of multiple component targets. The method presented is suited to volatile or light sensitive samples (such as derived peroxides) and can be employed on a variety of surfaces. As speed and throughput are traded against spectral bandwidth categorising threat compounds into groups based on common functionalities allows the full potential for multiplexed targeting to be realised.
Gold and silver nanoparticles functionalized with oligonucleotides can be used for the detection of specific
sequences of DNA. We show that gold nanoparticles modified with locked nucleic acid (LNA) form stronger
duplexes with a single stranded DNA target and offer better discrimination against single base pair mismatches
than analogous DNA probes. Our LNA nanoparticle probes have also been used to detect double stranded DNA
through triplex formation, whilst still maintaining selectivity for only complementary targets. Nanoparticle
conjugates embedded with suitable surface enhanced resonance Raman scattering (SERRS) labels have been
synthesized enabling simultaneous detection and identification of multiple DNA targets.
There is a growing need for fast reliable biosensor arrays for disease screening. We have used nanostructured plasmonic gold
surfaces for the detection of biological species by surface enhanced resonance Raman scattering (SERRS). Careful, directed
placement by Dip-pen Nanolithography (DPN) of the biological species or capture chemistry, within the array facilitates
efficient read out via ultra fast Raman line mapping. Further, we can transition the serial placement of biological species /
capture chemistry to a massively parallel deposition method, and this flexibility is key to enhancing the throughput of these
combined techniques by many orders of magnitude. SERRS is an extremely sensitive spectroscopic technique that offers
several advantages over conventional fluorescence detection. For example, the high sensitivity of the method allows
detection of DNA capture from single plasmonic array "pixels" ~1 μm2 in area. Additionally, the information rich nature of
the SERRS spectrum allows multiple levels of detection to be embedded into each pixel, further increasing the information
depth of the array. By moving from micro- to nano-scale features, sensor chips can contain up to 105 times more information,
dramatically increasing the capacity for disease screening.
Raman spectroscopy provides a very effective method of identifying an illicit substance in situ without separation or contact other than with a laser beam. The equipment required is steadily improving and is now reliable and simple to operate. Costs are also coming down and hand held portable spectrometers are proving very effective. The main limitations on the use of the technique are that it is insensitive in terms of the number of incident photons converted into Raman scattered photons and fluorescence produced in the sample by the incident radiation interferes. Newer methods, still largely in the development phase, will increase the potential for selected applications. The use of picosecond pulsed lasers can discriminate between fluorescence and Raman scattering and this has been used in the laboratory to examine street samples of illicit drugs. Surface-enhanced Raman scattering, in which the analyte requires to be adsorbed onto a roughened metal surface, creates a sensitivity to compete with fluorescence and quenches fluorescence for molecules on a surface. This provides the ability to detect trace amounts of substances in some cases. The improving optics, detection capability and the reliability of the new methods indicate that the potential for the use of Raman spectroscopy for security purposes will increase with time.
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