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Page 1 of 60 ACS Nano ER
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ACS Nano Page 2 of 60
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4 Recent Developments in the Field of Explosive
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6 Trace Detection
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9 Ka Chuen To,∗,† Sultan Ben-Jaber,‡ and Ivan P. Parkin∗,†
10
11 †Department of Chemistry, University College London, 20 Gordon Street, Bloomsbury,
12 London, WC1H 0AJ, U.K.
13 ‡King Fahad Security College, Department of Science and Forensics, Riyadh, 13232, Saudi
14
15 Arabia
16
17 E-mail: k.to.17@ucl.ac.uk; i.p.parkin@ucl.ac.uk
18
19
20
21
Abstract is important in many fields, including; forensics,
22 environmental monitoring as well as during the
23 Explosive trace detection (ETD) technologies manufacture and storage of explosives. Explo-
24 play a vital role in maintaining national se- sives remain a threat to homeland security and
25 curity. ETD remains an active research area recent events 1–3 emphasize the importance of
26 with many analytical techniques in operational
27
explosive trace detection (ETD) technologies.
28
use. This review details the latest advances A particular concern is the increasing use of
29 in animal olfactory, ion mobility spectrometry home-made explosives (HMEs); their destruc-
30 (IMS), Raman and colorimetric detection meth- tive power, ease in procurement along with the
31 ods. Developments in optical, biological, elec- availability of online tutorials for manufacture
32 trochemical, mass and thermal sensors are also
33
and deployment makes HMEs an easy weapon
34
covered in addition to the use of nanomaterials of choice in many terrorist attacks. As such,
35 technology. Commercially available systems are there is a continuing need to improve existing
36 presented as examples of current detection ca- ETD technologies as well as maintain efforts to
37 pabilities and as benchmarks for improvement. identify new approaches.
38 Attention is also drawn to recent collaborative
39
The aim of this review is to report on the lat-
40
projects involving government, academia and est developments in key ETD technologies. An-
41 industry, to highlight the emergence of multi- imal olfaction has been included as it remains
42 modal screening approaches and applications. the benchmark which emerging technologies are
43 The objective of the review is to provide a compared with. Other traditional approaches
44 comprehensive overview of ETD by; highlight-
45 used in ETD include; ion mobility spectrometry
46
ing challenges in ETD and providing an under- (IMS), colorimetry and Raman spectroscopy.
47 standing of the principles, advantages and lim- For each technology, general principles are de-
48 itations of each technology and relating this to scribed as well as advances in these areas along
49 current systems. with examples of in-field devices. Developing
50
51 technologies are discussed and include sensor
52 platforms used in artificial olfaction systems
53
Keywords and nanomaterials technology. The review will
54 conclude with a discussion of the advantages
55 explosives detection, Raman spectroscopy,
SERS, sensors, nanomaterials, quantum dots, and limitations of each technology with respect
56
57 IMS, artificial intelligence to the feasibility of operational deployment and
58 The detection of trace quantities of explosives future perspectives in ETD.
59
1
Page 3 of 60 ACS Nano
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18 Figure 1: Classification of explosives by chemical groups. 2,4,6-trinitrotoluene (TNT), 2,4,6-
19 trinitrophenol (TNP), 2,4,6-trinitrophenylmethylnitramine (tetryl), triacetone triperoxide (TATP),
20 hexamethylene triperoxide diamine (HMTD), ethylene glycol dinitrate (EGDN), nitroglycer-
21
ine (NG), pentaerythritol tetranitrate (PETN), 1,3,5-trinitroperhydro-1,3,5-triazine (RDX) and
22
23 Octahydro-1,3,5,7-tetranitro-1,3,5,7-tetrazocine (HMX).
24
25
26 Explosive trace detection (ETD) task. The majority of particulate sampling
27 challenges is achieved through use of sampling wands so
28 direction, pressure and technique are impor-
29 A wide range of explosives exist and they can be tant factors for successful collection of material.
30 categorised according to their composition (Fig- Sampling also requires intuition from the secu-
31
ure 1). Nitroaromatic explosives such as TNT rity agent to select areas most likely to contain
32
33 and TNP are used in munitions and are an envi- explosive trace. Vapour sampling is even more
34 ronmental concern as they can contaminate soil challenging since many explosives have very low
35 and groundwater. 4 Dinitrotoluenes have high vapour pressures. 7 Sampling liquids raises prac-
36 vapour pressures and are present in composi-
37
tical issues and through-barrier screening is lim-
tions of blasting gelatine as well as impurities ited to a small number of technologies. Many
38
39 in TNT manufacture. 5 Many nitrate esters are explosives are also considered "sticky" and will
40 liquids and military applications include; pro- adhere to a range of surfaces. 8,9 For materials
41 pellants, detonators and plastic explosives. 6 In with high surface energies, this could result in
42 addition, brisant explosives such as RDX and
43
accumulation of explosive particles, thus limit-
HMX are also components of plastic explosives. ing the number of analyte molecules per volume
44
45 Heat, shock and friction sensitive organic per- of sample.
46 oxides are commonly used in HMEs. Ammo- The operational environment also presents
47 nium nitrate/fuel oil (ANFO) is used as a blast- challenges. Passenger screening requires tech-
48 ing explosive but is also commonly used as a
49
nologies with fast analysis times, low false
fertiliser. Along with urea nitrate (UN), both alarm rates and minimal disruption. Cargo is
50
51 have also been used in improvised explosive de- usually wrapped in protective materials which
52 vices (IEDs). Due to the different chemical and may restrict efficient sampling. Screening bag-
53 physical properties of explosives, many types of gage poses logistical issues. In all cases, there
54 ETD technologies exist with sampling accom-
55
will be interference from benign materials which
56
plished through particulates, vapours and liq- could cause false positive alarms, so technolo-
57 uids. gies need to be selective. As such, deployment
58 Explosive trace detection is a challenging of new detection technologies requires careful
59
2
consideration of the regulatory (threats, sensi- pressures for various explosives at room tem-
1
2 tivity, selectivity), operational, civilian and fi- perature can be found in a papers by Östmark
3 nancial requirements. and Ewing. 7,18 Heating can increase the vapour
4 pressure of non-volatile explosives and improve
5 detection. Pre-concentration by whole-air col-
6 Reviews by other authors
lection and sorbent enrichment are additional
7
8
There are a number of technologies used in the techniques which can be used. 19,20 To achieve
9 detection of explosives, for bulk and trace quan- selectivity, many techniques incorporate the use
10 tities. ETD remains a dynamic research area of chemical modification to facilitate binding
11 and it is pertinent to mention several recent of specific explosives/explosive groups. For ex-
12 articles in the area. For an overview of bulk ample, to exploit the electron deficient nature
13
14 and trace detection technologies including prin- of many nitro-explosives, chemically modified
15 ciples, Caygill 10 and Brown 11,12 provide com- silanes containing electron donating groups are
16 prehensive reports. Mokalled 13 and Buryakov 14 frequently used. 21,22 Charge-transfer complexes
17 reviewed the use of sensors in ETD and Gi- are formed and exploited as transducing ele-
18 annoukos provides an overview of ‘electronic ments in sensors. Example functional moieties
19
20 noses’ and in-field devices. 15 include; amines, thiols and pyrroles. 23–26 Com-
21 putational and experimental studies have found
22
Types of detection methods a number of ions to form strong complexes
23 with TATP, including Co2+ , Zn2+ , In3+ 27–29
24 As the name suggests, ‘trace’ refers to quanti-
25
and these properties have been utilised into
26
ties of materials difficult to see with the naked a range of sensors. 30–32 Standoff technologies
27 eye. In ETD, this quantity can be considered to involve non-contact detection at distance and
28 be < 1 mg. ETD technologies differ from bulk generally involve optical methods and imaging
29 detection methods, which screen for anomalies linked to identification software. These tech-
30 in composition. Examples include; X-ray de-
31
nologies have recently been covered by other
32
tection, where materials are identified by their authors. 33,34
33 density and effective nuclear charge (Z eff ) 16 and
34 nuclear-based techniques which compares nitro-
35 gen content. 17 Many spectroscopic techniques
European projects concerning ex-
36 are used in ETD to identify explosives from plosives detection
37
38 their unique molecular signatures (Figure 2). In addition to screening at critical locations
39 The various properties of explosives has led to such as borders and transport hubs, there is
40 different approaches to enhance detection capa- a need to pre-empt threats through advance
41 bility. For example, the taggant 2,3-dimethyl-
42
warning systems. EMPHASIS (Explosive Ma-
2,3-dinitrobutane (DMNB) is added to plastic terial Production (Hidden) Agile Search and In-
43
44 explosives 5 due to its high vapour pressure, per- telligence System), BONAS (BOmb factory de-
45 meability through clothing and limited com- tection by Networks of Advanced Sensors) and
46 mercial use. The vapour pressures of explosives LOTUS (Localisation of Threat Substances in
47 vary widely across the different classes, from
48 Urban Society) are complimentary EU-funded
high vapour pressure materials in the parts-per- projects involving partnerships between govern-
49
50 billion to parts-per-million (ppb-ppm) range ment, academia and industry, with the aim
51 such as DNT, EGDN and TATP, to low vapour of developing systems for identifying bomb-
52 pressure materials in the parts-per-trillion (ppt) making facilities. With focus on using stand-
53 region, such as HMX and nitroguanidine. TNT
54 off detection technologies to identify perox-
and TNP, which have been extensively studied ide explosive precursors, 35 the approach in-
55
56 as target molecules in gas sensors, have equilib- volves developing sensors (LOTUS) which can
57 rium vapour concentrations in air at ppb quan- be wirelessly networked (BONAS) and embed-
58 tities. 7 A comparison of the different vapour ded within urban infrastructure to carry out
59
3
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6
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10
11
12
13
14 Figure 2: Examples of spectroscopic phenomena used for explosives trace detection. Diagram
15 representing phenomena shown in addition to Jablonski diagram comparing energy transitions.
16
17
18 real-time monitoring (EMPHASIS). 36–38 The honeybees and pigs. For a comprehensive re-
19 multi-sensor system consists of several optical view of biological detection systems, includ-
20 techniques including surface-enhanced Raman ing genetically-modified plants, microbial and
21
spectroscopy (SERS), quartz-enhanced photo- immunological-based techniques, please refer to
22
23 acoustic spectroscopy (QEPAS), electrochemi- papers by Habib 42 and Brown. 11
24 cal (EC) sensing, a light detection and ranging Sniffer dogs are the most common animals
25 (LIDAR)/differential absorption LIDAR detec- which are trained for contraband detection and
26 tion system (DIAL) sensor. 39 The COSMIC are widely used for their ability to achieve
27
28
project, due to be completed in 2021, aims to fast, real-time and directional screening. Many
29 develop new screening technologies for the de- breeds of dogs are used and a thorough review
30 tection of Chemical, Biological, Radiological, of ideal traits for detection dogs is provided by
31 Nuclear and Explosive (CBRNE) materials con- Jamieson et al. 43 The environmental, training
32 cealed in shipping containers. 40 The NATO- and physiological factors affecting detection dog
33
34
funded STANDEX (STANdoff Detection of EX- performance is provided by Hayes et. al . 44
35 plosives) program is another example of an inte- A limitation of sniffer dogs is the amount of
36 grated early-warning system, for deployment in training required before deployment. Training
37 mass transit infrastructure locations. Of par- takes several months, which is time-consuming
38 ticular relevance, is the RAman Detection of and costly. The dog-handler interface also
39
40
EXplosives (RADEX) system, which uses an affects performance, 45 as can screening con-
41 eye-safe laser and has standoff detection capa- ditions, with indications that increased pant-
42 bility. 41 ing, as result of overheating, can reduce the
43 ability of dogs to detect explosives. 46 Despite
44 these limitations, efforts have been made to
45 Animal olfactory systems
46
re-produce aspects of canine olfactory systems.
47 Staymates et. al connected a 3D-printed struc-
The detection capabilities of animals far ex-
48 ture of a dog’s nose with a pump to produce
49 ceeds many of the current technologies in use
a system which mimics the "sniffing" action of
50 today and as such, there is a continuing need
canines. 47 The bio-inspired system showed bet-
51 for animals in explosives detection. One of the
52 ter detection compared with a commercial ETD
key advantages of biological systems is concur-
53 device, suggesting active sniffing to be a crucial
rent detection of multiple analytes of interest
54 part of the sample delivery process.
55 in real-time which is a challenging task and
Rats have also been trained to detect explo-
56 difficult to achieve even with integrated sens-
sives and have the benefit of being lightweight,
57 ing technologies. Examples of animal systems
58 which makes them ideal for landmine detec-
used in explosives detection include; dogs, rats,
59
4
tion. 48 In addition, rats have lower training,

1
2 maintenance and transportation costs com-
3 pared with sniffer dogs. Honey bees have been
4 trained to detect TNT, C4 and TATP explo-
5 sives at parts-per-trillion levels. Similar to rats,
6
training costs are low and can be completed
7
8 within days. Their abundant populations and
9 ability to cover large areas quickly and the abil-
10 ity to sample solid, liquid and gaseous sam-
11 ples make them ideal detection tools. However,
12
honey bees can be affected by the weather, can-
13
14 not sample at night and are highly unlikely to
15 be deployed in screening environments where
16 humans are present. The development of a
17 transportable sensor using honey bees can be
18
exemplified by the Inscentinel Vasor (Volatile
19
20 Analysis by Specific Odour Recognition) 136.
21 Initially developed in the UK, the device ex-
22 ploits the Proboscis Extension Reflex (PER), 49
23 whereby honey bees extend their tongues when
24
25
their anntenae touch a sugar/honey solution.
26 With pavolovian conditioning, honey bees were
27 trained to respond to TNT, Semtex, PE-4 and
28 C-4 down to detection limits of 78 ppt 50 (Fig-
29 ure 3). The device consists of 36 bees held in
30
31
a self-contained unit, integrated with an imag-
32 ing system to detect PER. The EU-funded ‘Bi-
33 ological Method (Bees) for Explosive Detection’
34 project utilises trained bee colonies to iden-
35 tify landmines. 51 This is realised through ac-
36
37
tive and passive methods, with the former in-
38 tegrating artificial intelligence and drone tech-
39 nology to track bee colonies hovering over land-
40 mines. The passive approach involves using a
41 commercially available semiconducting polymer
42
43
as a pre-concentrator, installed at the entrance
44 of beehives. Sensing is achieved through des-
45 orption of analytes and luminescence quenching
46 of a conjugated polymer, Super Yellow. 52,53
47
48
49
50
51
52
53
54
55
56
57
58
59
5
1
2
3
4
5
6
7
8
9
10 Figure 3: Inscentinel Vasor 136 system. Rothamsted Research Ltd.
11
12
13 Sensors range of molecular interactions can be identified
14
through use of combinations of reagents which
15
Efforts to mimic mammalian olfactory sys- produce patterns of colour, thus allowing ‘op-
16
17 tems has led to the development of electronic tical fingerprinting’ to be achieved. 60 Examples
18 noses (E-noses). First proposed in 1982, E- of such colorimetric agents exploited for sens-
19 noses broadly describe systems consisting of a ing include; pH and redox indicators 61,62 and
20 sensor combined with pattern matching soft- derivatives of xanthene dyes, the latter of which
21
ware to achieve vapour detection. 54 Single sen- is used in the DETECHIP® sensor. 63
22
23 sors, for individual analyte detection or sen-
24 sor arrays, for simultaneous detection of mul-
25 tiple targets can be used. Many sensor tech-
26 nologies have since been used to develop E-
27
noses and examples include; field effect tran-
28
29 sistors (FET), chemoresistors, quartz crystal
30 microbalance (QCM) and electrochemical sen-
31 sors. 55 However, even the most advanced sys-
32 tems have yet to reach the capability of their
33
mammalian counterparts. The following sub-
34
35 sections will describe some of the sensing tech-
36 nologies used in E-noses.
37
38
39 Colorimetric sensor arrays
40
41 Colorimetric sensor arrays contain different
42 reagent dyes which can change colour on inter-
43 action with solid, liquid and vapour analytes.
44 Chromophores and fluorophores are common
45
reagents and the colour change is measured as
46
47 a result of the change in absorbance or fluores-
48 cence. Advances in image capture technologies
49 have led to the development of sensor arrays
50 which carry out analysis by perturbing the red,
51
green and blue (RGB) intensities of digital im-
52
53 ages. 56 RGB analysis has already been demon-
54 strated on conventional colorimetric kits using
55 iphone cameras. 57–59 The combination of a sen-
56 sor array with digital image analysis provides a
57
much greater discriminatory power. As such, a
58
59
6
A B
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4
5
6
7
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9
10
11
12
13
14 Figure 4: Examples of colorimetric arrays. A) 40-reagent colorimetric sensor array as described in. 64
15 B) CRIM-TRACK colorimetric sensor for explosive vapours. A) Reproduced from ref. 64 Copyright
16
2016 RSC. B) Reproduced with permission from ref. 65
17
18
19
Salles et al. report detection of peroxide and Immunosensors
20
21 nitroaromatic explosives using a 3-reagent sen-
Immunosensors function through specific
22 sor consisting of potassium iodide, creatine, and
antibody-antigen conjugations to detect an-
23 aniline. Colour discrimination was achieved
24 alytes of interest. For explosives detection,
through software evaluation of RGB values ac-
25 competitive assays are the most common
quired from images on an iPhone. Detection
26 type of immunosensor reported. Here, an
27 limits between 0.2 µg - 0.1 mg were achieved
antibody is affixed onto a platform and an
28 for TATP, HMTD, picric acid and nitroben-
unlabelled substrate in a sample competes with
29 zene (NB), within 15 minutes. 66 Simultaneous
30 a labelled analogue to bind to the antibody.
detection of 16 explosive vapours was achieved
31 The amount of labelled, unbound substrate is
32
using a colorimetric sensor array made up of
measured. If the labelled substrate contains
33 40 components. 64 Detection limits were in the
a fluorophore, then detection can be achieved
34 mg-scale, which falls within the levels consid-
through measuring an increase or quenching of
35 ered for trace detection but lacks the sensitivity
36 the fluorescence signal. The latter technique
achievable in IMS systems (Figure 4). Another
37 provides greater sensitivity since benign mate-
38
study by the same research group, report the
rials which fluoresce can lead to false signals.
39 detection TATP and HMTD vapours 67 with a
Detection can also be achieved by changes in
40 limit of detection (LOD) at µg quantities. The
41 colour, absorbance or electrochemical signal. 71
CRIM-TRACK system uses 26 chemoselective
42 Monoclonal antibodies for high explosives
dyes spotted onto a chip to form a colorimetric
43 TNT, RDX and PETN are commercially avail-
44
sensor array (Figure 4). Detection of HMTD,
able through BBI Detection. 72 The BioSENS®
45 TATP and drug molecules are reported, with
300 device combines an immunoassay with
46 initial testing in mixed air conditions showing
surface acoustic wave (SAW) technology (Fig-
47 detection limits in the ppt range. 65,68 In ad-
48 ure 5). The system was tested as part of an
dition, machine learning was successfully used
49 EU project 73,74 and detection occurs through
50 to detect target analytes in contaminated sam-
monitoring the change in mass on a surface
51 ples. A fluorescence quenching sensor pre-
which contains antibody-antigen immunocom-
52 pared using aerosol-jet printing was reported
53 plexes immobilised onto SAW sensors. In the
by Bolse et. al. Detection of nitrobenzene,
54 presence of analyte antigens, antibodies are
1,3-dinitrobenzene and DNT was achieved at
55 displaced from the immunocomplex, generating
56 ppb levels with high classification rates, us-
a measurable signal. Nanogram detection is
57 ing an array of six fluorescent spiro and homo-
possible for a range of nitro-based explosives
58 polymers. 69,70
59
7
in addition to PETN and NG, within 30 sec- (ISFET) for signal transduction. 84 The LOD
1
2 onds. 75,76 Surface-plasmon resonance (SPR), for TNT was 5 ppb.
3 frequently used in lab-on-a-chip sensors, has
4 also been reported for the detection of TNT, Nanomaterials
5 EGDN and RDX. 77–79
6 Nanotechnology is a rapidly expanding area
7
8
and the tunable nature of nanomaterials makes
9 them desirable for use as sensor arrays. Nanos-
10 tructured materials provide high surface areas
11 for detection and selectivity can be achieved
12 by utilising their unique electrical, optical, cat-
13
14 alytic, magnetic and mechanical properties.
15 Nanomaterials can be classified in many differ-
16 ent ways and Table 1 lists some examples ac-
17 cording to chemical composition. The rest of
18 this section will focus on semiconductor mate-
19
20 rials used as sensors for ETD.
21
22
23 Figure 5: BIOSENS® 300 from Biosen-
24 sor Applications® AB utilising antibody im-
25 munosensors with SAW detection technology.
26 Biosensor Applications International AB.
27
28
29 The U.S. Naval Research Laboratory has de-
30 veloped several microfluidic immunosensors for
31
32
the detection of TNT. In one study, a de-
33 vice for detection in seawater was developed.
34 Monoclonal antibodies with high affinity for
35 TNT were immobilised onto a device consist-
36 ing of poly(methylmethacrylate) (PMMA). De-
37
38
tection was achieved by measuring the in-
39 crease in fluorescence upon binding of TNT,
40 with the LOD reported as 1 ppb. 80 Similarly,
41 a fluorescence-based displacement immunoas-
42 say using neutravidin-coated biotinylated anti-
43
44
TNT achieved detection limits of 10 ppt. 81 An-
45 other device, by the same group, using recom-
46 binant proteins, achieved detection limits of 0.5
47 ppb. 82
48 Wang et al. used peptide-functionalised SPR
49
50 for the detection of TNT with an LOD of 1.35
51 ppm. 83 In contrast to protein antigens, pep-
52 tide antigens are synthetically produced from
53 carefully-selected amino acid sequences of a na-
54 tive target protein, thus offering greater speci-
55
56 ficity. Gubanova et al. report the development
57 of an enzymatic biosensor microfluidic system
58 which uses an ion sensitive field effect transistor
59
8
Table 1: Different classes of nanomaterial sensors used for the detection of explosives
1
2 Type Detection method Materials LOD Reference
3 detected
4 Au nanoparticles functionalised with 4- PETN 0.15 mg L-1 85
Aminothiophenol and N-(1-Naphthyl)-
5 Plasmonic
ethylenediamine dichloride (NED)
6 Electrochemical sensor consisting of Ag TATP, 200 ppb (TATP), 250 ppb (HMTD) 86
7 nanoparticles on carbon fibre electrodes HMTD

Cu nanoparticle-incorporated polyfurfural film TNT 41.6 ppb
8 electrochemical sensor
87
9 TiO2 sensor contained within a quartz crystal NG 1-10 ppm 88

10 Semiconductors
microbalance
11 Optoelectronic sensor using polyoxometalate- TATP 50 ppb 89
doped TiO2
12 In2 O3 amperometric sensor TATP 2.9 ppb - 2.8 ppm 90
13 WO3 and chromium titanium oxide gas sensor Ammonia, Ppm 91
14 ni-
15 tromethane,
NO2
16 Fluorescent silicon nanodots TNP 0.92 nM 92
17 Quantum Fluorescent graphene oxide dots TNP 92 nM 93
18 dots L-cysteine-coated CdS quantum dots TNP 39 ng mL-1 94
19 Electrochemiluminescence (ECL) resonance TNT 0.65 ppm 95

energy transfer (ERET) sensor using CdTe
20 quantum dots
21 Electrochemical sensor using MIP cast on RDX 20 pmol L-1 96
Carbon-
22 based
multi-walled carbon nanotube (MWCNT)
23 SWCNT TNT 772 ppb 97
Electrochemical sensor using boron-doped di- TNT 73 ppb (TNT), 270 ppb (TNA)
24 amond/graphene nanowall electrodes and 2,4,6-
98
25 trinitroanisol
26 (TNA)
27 Chemically modified polypyrrole-bromophenol TNT, 500 ppt (TNT), 800 ppt (PETN), 1 26
Composite blue QCM sensor PETN, ppb (RDX) and 2 ppb (HMX)
28 RDX and
29 HMX
30 Functionalised SU-8 polymer nano-composite TNT, RDX 1.30 pg (TNT), 0.07 fg (RDX), 0.23 fg 99
31 microcantilevers and PETN (PETN)
MoS2 /reduced graphene oxide composite TATP 0.65 ppm
32
100
(precur-
33 sors)
34
35
36 Inorganic semiconductors sorption of O2 onto the surface of the MOx leads
37 to the formation of oxygen ions. The conduc-
38 Metal oxide (MOx ) semiconductors are promis-
tivity of the MOx sensor is determined by both
39 ing materials for sensing applications due to
40
1) the nature of the charge carrier, either elec-
their low production costs, ease of use, high
41 trons or holes in n and p-type semiconductors,
thermal, chemical and electrical stability. 101
42 respectively and 2) the oxidative/reductive na-
43 These properties have led to a range of ap-
ture of the target gas (Figure 6).
44 plications, including; monitoring of volatile
Many n- and p-type semiconductor mate-
45 organic compounds, environmental and toxic
46 rials have been used for explosives detection
gases. 102,103 MOx semiconductors have charac-
47 and examples include; TiO2 , 28,105 ZnO, 32,106
teristic wide band gaps (> 2 eV) and elec-
48 Sn2 O 107,108 and Cu2 O. 109 Tang et.al synthe-
49 tron transition energies in the UV/visible wave-
sised TiO2 nanostructures onto indium tin ox-
50 lengths of light. Not only is this favourable
ide (ITO) and fluorine-doped tin oxide (FTO)
51 for optoelectronic and electronic sensors, but
52 conducting glasses. The photoresponse towards
a wide tunable spectral range can also be ex-
53 TATP was highest for TiO2 -FTO homojunction
ploited to improve sensitivity and selectivity.
54 structures with detection possible at ppb levels.
55 Resistive gas sensors are the most common and
The authors found positioning of the conduct-
56 the sensing mechanism is based on measuring
ing glass during synthesis of TiO2 was impor-
57 the change in conductance on adsorption of a
58 tant for the types of nanostructures formed. 110
target molecule. 104 In ambient conditions, ad-
59
9
1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
18
19
20
21
22
23 Figure 6: Mechanisms of metal oxide (MOx ) semiconductor gas sensors for a reducing gas target
24 analyte. When the sensor is exposed to air, adsorption of O2 onto the surface leads to uptake of
25 electrons from the conduction band (CB ), creating oxygen ions (O2 - ). A) In n-type semiconductors,
26
27
a redox reaction occurs between the O2 - and target analyte, leading to injection of electrons into the
28 CB . As a result, conductance increases and resistance decreases. B) In p-type semiconductors, holes
29 are the dominant charge carriers. However, since the concentration of hole carriers has increased,
30 there is an increase in conductivity. In the presence of a reducing target analyte, reaction between
31 the O2 - and analyte will lead to injection of electrons into the MOx and the filling of holes. This
32
33
results in decrease in the concentration of hole charge carriers, a decrease in conductivity and
34 increase in resistance.
35
36
37 Bastatas et. al fabricated a chemiresistive sen- by Bastatas and Qu) at low temperatures is a
38 sor using ZnO-coated silica nanosprings for the promising development, not only in terms of re-
39 detection of ammonium nitrate (AN). UV-A ir- duced energy consumption but also in reduction
40 radiation was used to improve the activation of of potential hazards for use in an operational
41
42 charge carriers as well as facilitate analyte des- environment.
43 orption and reuse of the sensor. 111 Qu et.al de- Efforts to improve the selectivity of MOx
44 veloped a chemiresistive sensor array for the de- semiconductors towards specific explosives in-
45 tection of TNT, DNT, TNP, RDX and AN. The clude; changing the operating temperature,
46
authors doped ZnO with Co, Ni and Fe to pro- using sensor arrays and composite materials.
47
48 duce p-type semiconductor films to improve the Temperature modulation affects the charge and
49 adsorption of explosives onto the MOx surface rate of oxygen adsorbed onto the MOx sur-
50 and sensor response. Detection was achieved face. As such, sensor response can be used
51 at ppb-ppt levels with response times within to profile specific gases. Further selectiv-
52
12 seconds. The authors attribute the rapid ity can be achieved by combing information
53
54 response of the doped sensors to reduction in from a several sensors with different operat-
55 the charge transfer distance between the charge ing temperatures. 101,113 Composite MOx struc-
56 reservoir layer and surface defect centres of the tures can be designed whereby each material
57 MOx nanoparticles 112 (Figure 7). The ability is chosen with selectivity to a specific gas an-
58
of some MOx sensors to function (as shown alyte. 114 Warmer et. al used SnO2 and WO3
59
10
B C
1
2 A
3
4
5
6
7
8 D E
9
10
11
12
13
14
15
16 Figure 7: Fe-doped ZnO chemiresistive sensor A) Models showing the charge transfer mechanism
17 of undoped and doped ZnO. In Fe-doped ZnO, a charge reservoir layer exists from which charge
18 carriers migrate, to the surface of Fe-doped ZnO nanoparticles B) Schematic showing the gas sensor
19 array composed of three doped sensors; Fe-ZnO, Co-ZnO, and Ni-ZnO, (C) PCA analysis of analytes
20
detected using the sensor array in B), D) Schematic showing the gas sensor array composed of four
21
22 sensors; ZnO, Fe-ZnO, Co-ZnO, and Ni-ZnO, E) PCA analysis of analytes detected using the sensor
23 array in D). 112 Reproduced from ref. 112 Copyright 2016 Small.
24
25
26 to detect TATP and DADP. The authors note form of thermodynamic sensors. Here, a typ-
27 the oxidising and reducing properties of or- ical setup involves scanning two microheaters,
28 ganic peroxides is temperature dependent and one of which is coated in the catalytic material.
29
utilise this feature for selectivity towards TATP By comparing the electrical power required to
30
31 by temperature cycling of WO3 films. An maintain both heaters at a constant tempera-
32 LOD in the ppb range is reported. 115 An E- ture, thermodynamic data can be collected at-
33 nose using silicon nanowire-field effect tran- tributed to the catalytic activity specific to the
34 sistors (SiNW-FETs) has been developed by analyte. 120 SnO2-x and ZnO were used in this
35
Tracense Systems. Chemically modified sili- way by Amani et. al for detection of TATP
36
37 con nanowire arrays provide selective binding at ppm levels. 31 A similar system developed by
38 of nitro-containing and peroxide-based explo- Rossi et. al, using sensors with lower thermal
39 sives, with detection achieved through mea- mass improved detection to ppb levels. Fur-
40 suring the change in conductance on adsorp- thermore, the trend in the sensitivity of metal
41
42
tion of explosives. Parts-per-quadrillion (ppq)- oxide catalysts towards TATP was observed to
43 ppt detection was achieved for TNT and per- be SnO > ZnO > CuO. The authors report the
44 oxides explosives TATP and HMTD, respec- mechanism of TATP detection as due to the oxi-
45 tively. 116,117 A Schottky optoelectronic sensor dation/reduction of the catalyst from decompo-
46 array consisting of SiNW’s incorporated with sition of TATP. 32 Further improvements to this
47
48
TiO2 and reduced graphene oxide was devel- system involved the addition of a conductomet-
49 oped by Yang et. al. Detection limits were ric platform to collect the electrical resistance
50 reported between 0.05 ppq–74 ppb for a range of the catalytic MOx sensor in addition to the
51 of nitro-based explosives. 118 Further adaptation thermodyamic response. 121
52 by the same group, which involved replacing
53
54
TiO2 with ZnO, showed discrimination between Organic semiconductors
55 urea, black powder, nitrate- and nitro- explo-
56 sives. 119 Conjugated polymers generally have alternat-
57 Selectivity can also be achieved by using the ing single and double bonds in the polymer
58 catalytic activities of some metal oxides, in the chain which provides a π-conjugated structure
59
11
A B
1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
Figure 8: Sensing of nitroaromatic explosives using carbon nanotubes A) Sensor using single-walled
16
17 carbon nanotubes (CNTs) modified with Tg-Car oligomer (structure inset). The schematic shows
18 charge carriers moving in the Tg-Car/CNTs before and after exposure to nitroaromatic explosives
19 (NT, DNT and TNT) 122 B) Piezoresistive microcantilever sensor coated in CNT film. Explosive
20 vapours adsorbed onto the sensors are heated to induce micro deflagration, leading to bending of
21
the microcantilever and detection by the piezoresistors. 123 Reproduced from ref. 123 Copyright 2013
22
23 Elsevier.
24
25
26 resulting in a continuous delocalized electron rene and carbazole as fluorophore moieties were
27 system. These features give rise to unique pho- developed by Loch et. al for the detection
28 toconductive, photoluminescent and mechani- of DNT and the explosive taggant DMNB. 129
29 cal properties. For explosives detection, re- Blue et. al developed polymer-based microsen-
30
31
search surrounding conjugated polymers has sors for vapour detection of nitro and peroxide-
32 primarily focused on their fluorescent proper- based explosive precursors. The authors syn-
33 ties and tuning these to improve sensitivity and thesised copolymers using a Bromine deriva-
34 selectivity. Examples of such materials are dis- tive of the conductive polymer PRODOT (3,4-
35 cussed later in the paper. This section will cover Propylenedioxythiophene), Br-ProDOT, as the
36
37
work on conducting polymers, a sub-category starting material. The resultant copolymers
38 of conjugated polymers and also part of the or- were electrochemically deposited onto interdig-
39 ganic semiconductors class of materials. 124,125 itated electrodes (IDEs) with sensing achieved
40 An attractive feature of semiconducting poly- through measuring the change in capacitance
41 mers is having both tunable electronic prop- on adsorption of target vapours. Detection lim-
42
43
erties and mechanical plasticity. In addi- its of 200 ppb were achieved for nitrobenzene
44 tion, a range of facile deposition methods ex- and 2-nitrotoluene and for peroxide vapours,
45 ist, making them ideal for composite sensors ppm levels were achieved. 130
46 in E-noses. 126,127 Surya et. al developed an
47 organic field effect transistor (OFET) sensor
48
Graphene and carbon nanotubes
49 using diketopyrrolopyrrole and metal organic
framework as the sensing element. In this Carbon-based semiconductors such as graphene
50
51 system, the Cd(II) MOF acted as the recep- and carbon nanotubes (CNTs) have been ex-
52 tor and pre-concentrator and the thienylene- tensively researched as sensing materials due
53 vinylene- thienylene (PDPP-TVT) semicon- to their favourable electrical, mechanical and
54 chemical properties over inorganic equivalents.
55 ducting polymer was used as the channel mate-
rial. The system detected TNT and RDX at These materials are amenable to chemical func-
56
57 ppb and ppt levels, respectively. 128 Semicon- tionalisation and many can be printed us-
58 ducting poly(dendrimer)s modified with fluo- ing low-cost methods. 131 The 2D structure of
59
12
graphene provides a high surface area to vol- cations for sensors, due to their fluorescence
1
2 ume ratio and the sp2 network facilitates π-π properties and chemical inertness. Ran et.
3 interactions, which is favourable for the detec- al used nitrogen-doped carbon dots modified
4 tion of electron deficient nitroaromatic explo- with the macrocyclic structure pillar[6]arene,
5 sives. 132,133 Introducing oxygen functional moi- for selective detection of TNT. The electro-
6
eties, either chemically as graphene oxide 134 chemical sensor achieved a detection limit of
7
8 or through the fabrication process 135 can fur- 0.95 nM. 145 A magnetic carbon dot-based MIP
9 ther improve sensitivity through van der waals composite was developed by Wang et al. for
10 interactions with the NO2 groups. Efforts the detection of TNP with a LOD of 0.5
11 to improve the selectivity of graphene materi- nM. 146 Ju et. al synthesised carbon dots us-
12
als for ETD include; peptide modifications, 136 ing a simple solvothermal approach involving
13
14 nanoparticles, 137 doping 98,138 and organic poly- o-phenylenediamine and chloroform. The col-
15 mers. 139,140 orimetric sensor showed a LOD of 2 µM. Practi-
16 The high conductivity of single walled (SW), cality of this method was demonstrated by im-
17 multi-walled (MW) carbon nanotubes, have mobilising the carbon dots on standard filter
18
also been investigated for explosives detection paper. 147
19
20 with the majority of studies focused on ni-
21 troaromatic materials. Studies by Woods and Quantum dots
22 Star show the interactions between CNTs and
23 nitroaromatic explosives involve a combina- Quantum dots (QDs) are nanocrystalline semi-
24
tion of π-π stacking and charge-transfer ef- conductor materials with excellent fluorescent
25 properties due to their quantum confinement ef-
26 fects. 141,142 Kumar et.al developed a SWCNT
27 sensor on a flexible polycarbonate membrane. fects. QDs also have high quantum yield, broad
28 Detection of DNT was possible at ppb levels excitation spectra, narrow emission spectra and
29 and the sensor could be recovered through UV high stability, making them favourable for use
30 as colorimetric probes. The small size of QDs,
31
irradiation. 143 Stefano et. al compared the re-
sponse of an electrochemical sensor for TNT typically 2-10 nm, gives rise to their unique op-
32
33 using pure and acid-treated CNT-coated elec- tical properties. At these dimensions, semicon-
34 trodes. The study found that residual metal- ductor crystals are similar in size to the Bohr
35 lic impurities in pure CNTs can improve the radius and hence distance between an electron-
36 hole pair. At these distances, the conduction
37
electrochemical response for TNT due to cat-
alytic effects and increased surface roughness band of the semiconductor material separates
38
39 of the electrodes. 144 Ruan et. al fabricated into sub-bands of discrete energy states and
40 a piezoelectrical microcantilever sensor coated the bandgap changes with respect to the size
41 with CNTs for the detection of TNT 123 (Figure of the crystal 148,149 (Figure 9). This greatly
42 increases the tunability of QDs with emission
43
8). As with graphene-based sensors, selectivity
of pure CNT materials is limited and chemi- wavelengths achievable from UV to near-IR. 150
44
45 cal modifications are often required. Zhang et. QDs can be grouped by their semiconductor
46 al coated SWCNTs with carbazolylethynylene components, with the majority of developments
47 oligomers for the detection of 4-nitrotoluene seen in groups II-IV 151,152 and IV. 153,154 QDs
48 can also include carbon nanostructures with
49 (NT), TNT and DNT. Differential sensing was
achieved by using both coated and uncoated sizes < 10 nm, which includes graphene QDs
50
51 SWCNTs on the same sensor. The resultant and carbon QDs, 155 examples of which have
52 n-type and p-type semiconductor properties been described previously. Semiconductor QDs
53 showed different trends in conductance which can also be grouped according to their compo-
54 sition, such as core-type, core-shell and alloyed.
55 could then used to differentiate each analyte 122
(Figure 8). The electron-rich nature of QDs are suitable
56
57 Other nanoforms of carbon used in ETD infor the detection of nitroaromatic explosives as
58 clude carbon dots which have promising appli- the electron-withdrawing nitro groups can act
59
13
tion of host-guest binding, electrostatics, and π-

1
2 π stacking, resulting in fluorescence quenching
3 of the QDs (Figure 11). The system was able to
4 differentiate between DNT, TNT, tetryl, RDX
5 and PETN at ppb levels. Application of ma-
6
chine learning also showed good classification
7
8 results. 161,162 Komikawa et. al report a chemi-
9 cal sensor for TNT using TNT binding peptides
10 conjugated to CdTe/CdS quantum dots. Detec-
11 tion is observed through fluorescence quenching
12
in the presence of TNT. 163 Qian et. al devel-
13
14 oped a two-component composite sensor using
15 3-mercaptopropionic acid-capped SiO2 spheres
16 and L–cysteine capped CdTe quantum dots
17 (QDs). Detection of TNT was achieved through
18 Figure 9: Properties of semiconductor quan-
the formation of Meisenheimer complexes be-
19 tum dots A) Comparison of the band gap en-
20 tween TNT and the amine moiety of cysteine.
ergy (Eg ) between metals, bulk semiconductors
21 A relationship between TNT concentration and
and semiconductor quantum dots, B) Relation-
22 fluorescence emission was established by com-
23 ship between the size of semiconductor quan-
paring the ratio between the fluorescence inten-
24 tum dots and Eg , resulting in different emission
25
sities of the two probes. A limit of detection of
energies.
26 3.3 nM was reported. 164 Other approaches to
27 improve the selectivity of QDs towards explo-
28 as fluorescence quenchers. Two mechanisms sives include using molecular-imprinted poly-
29 widely used to achieve such sensing are fluo- mers (MIPs) 146,165 and doping. 166,167
30
31 rescence resonance energy transfer (FRET) and
32 photo-induced electron transfer (PET) (Figure Micro-electromechanical systems
33 10). 156,157 A FRET-based sensor consisting of N
34 and S co-doped carbon QDs was used by Khan The miniaturisation of E-noses towards
35 et. al for the detection of TNP. The nascent portable, easy to use and cost effective devices
36
donor QDs showed maximum fluorescence emis- for use in the field is a challenging task. One
37
38 sion at 300 nm which was quenched in the pres- approach is to use micro-electromechanical sys-
39 ence of TNP. 158 Ganiga et. al used CdS QDs tems (MEMS). MEMS is a process technology
40 and diphenylamine for the detection of RDX which describes the fabrication of microscopic
41 devices consisting of a microprocessor and
and PETN. In this system, the fluorescent CdS
42
QDs acted as the acceptor and is quenched by a mechanical component, contained in an
43
44 the diphenylamine. Electrostatic interactions integrated system, typically a silicon chip. 168
45 between explosives and diphenylamine result in The products of MEMS, or micro-machined
46 the formation of a complex and restoration of devices, are used in a variety of industries and
47 the versatility of MEMS devices lies in the
fluorescence, with maximum emission at 355
48
49 nm. 159 Gong et.al synthesised QDs consisting of variety of miniaturised mechanical components
50 core-shell CdSe/silica functionalised with NH3 available such as micro-structures, sensors,
51 for the detection of TNP. 160 actuators and electronics. These provide a
52 A fluorescent sensor array consisting of mod- means to sense, control or perform work at the
53 microscale. As such, many sensor technologies
ified core-shell CdSe/ZnS QDs was developed
54
55 by Peveler et. al containing calixarene, cy- already discussed above can be incorporated
56 clodextrin -OH and -OMe surface modifica- into MEMS, provided there is a means of
57 tions. Interactions between explosive targets miniaturisation.
58 and surface receptors occur through a combina- Microcantilevers are versatile sensing plat-
59
14
1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
Figure 10: Energy level diagrams showing generalised FRET and PET processes. A) FRET involves
16 transfer of non-radiative energy from an excited donor moiety to an acceptor. The interaction
17 between donor and acceptor is distance dependent. B) PET involves electron transfer between a
18 donor and acceptor moiety. Fluorescence is quenched in the PET-ON system (i.e. the system is
19 in an ‘off’ state). Fluorescence emission is observed on disruption of the donor-acceptor system,
20
21
whereby the system is in an ‘on’ state (not shown in diagram).
22
23 B
24 A
25
26
27
28
29
30
31
32 C D
33
34
35
36
37
38
39 Figure 11: Fluorescent assay consisting of modified CdO/ZnS quantum dots (QDs) A) Schematic
40 showing sensing mechanism using the QD system B) Plots showing %Quenching for each QD for
41
42
a range of analyte concentrations. Machine learning classification of sensor data with C) showing
43 Canonical plot (LDA) for %Qdata set and D) showing the classification percentage for several
44 subsets of the array. 161
45
46
47 forms suitable for MEMS due to their high ing the resonance shifts in PEG–DA on absorp-
48 sensitivity, small size and low cost of manu- tion of IR radiation. IR-active analytes present
49 facture. Different coatings can be applied to on the microcantilever causes a reduction in
50
51 microcantilevers to achieve chemical, physical the natural resonance frequency of the micro-
52 and biochemical characterisation data. 169 Re- cantilever, thus providing a molecular ‘finger-
53 cently, polyethyleneglycol diacrylate (PEGDA) print’. Detection limits of 600 ng/cm2 and 40
54 was used to fabricate microcantilevers for the ng/cm2 were achieved, for RDX and PETN,
55 detection of PETN, TNT and RDX. Detection respectively. 170 Selectivity in microcantilever-
56
57 was achieved using photothermal cantilever res- MEMS can be achieved by incorporating trans-
58 onance spectroscopy (PCRS), through exploit- ducing elements with selective binding for ana-
59
15
lytes of interest. Palaparthy et.al reports an E-

1
2 nose with piezo-resistive micro-cantilever sen-
3 sors coated with mercaptobenzoic acid, methyl
4 benzene thiol and amino thiol phenol for se-
5 lective detection of TNT, RDX, and PETN
6
at ppb levels. 171 Holthoff et. al demon-
7
8 strated selective detection of 2,4-dinitrotoluene
9 (DNT) down to 500 parts-per-trillion (ppt) us-
Figure 12: Scanning electron micrographs of
10 ing microcantilevers functionalized with molec-
11
the micro-capacitor sensor. (A) a pair of capac-
ular imprinted polymers (MIPs). 172 Udara et.
12 itors forming the differential sensor. (B) close-
al showed coating a silicon substrate microcan-
13 up detail of the comb-structure. 175 Reproduced
tilever with polyvinylpyrrlidone led to enhanced
14 from ref. 175 Copyright 2017 MDPI.
15 detection of ammonium nitrate. 173 An electro-
16 chemical MIP sensor for TATP was developed
17 by Kassahun et. al, reporting detection limits Ion mobility spectrometry
18
of 26.9 µg/L. 174 Strle et. al reports a mul-
19 IMS remains one of the most popular tech-
20 tichannel E-nose which uses SiO2 MEMS ca-
21 pacitors for multiple analyte detection. The niques used in security and is the preferred an-
22 comb-shaped capacitors (Figure 12) were func- alytical method for explosives detection world-
23 tionalised with different silane molecules and se- wide. 180 IMS is also used in the detection of
24 illicit drugs 181 and chemical warfare agents 182
25
lective adsorption of target analytes which re-
sulted in a change in capacitance. Detection of and in many areas outside of the security sec-
26
27 TNT was possible at 3.5 ppt, within 1 second at tor. Systems can exist as hand-held or desktop
28 room temperature. 175 Chemical selectivity was variants and can sample both particulates and
29 further improved using machine learning. 176 vapours. In-field devices are portable, have low
30 detection limits and are easy to use. Another
31
Zandieh et. al report the detection of RDX
and PETN using a multi-modal sensor. The major advantage of IMS when compared with
32
33 system consists of a microcantilever, micro- other techniques is the ability to screen samples
34 heater/micro-thermometer device with an IR in seconds. This is particularly beneficial in op-
35 laser. Identification of RDX, PETN and binary erational environments such as airports, where
36 fast screening methodologies are needed to pro-
37
mixtures of each material was achieved, with
LOD for RDX and PETN reported as 31 pg cess large passenger numbers and minimise de-
38
39 and 49 pg, respectively. 177 Analyte interroga- lays.
40 tion through use of opto-calorimetric IR spectra The setup of most commercial IMS systems
41 and micro-differential thermal analysis enabled consists of four main components: a sample
42 collection and introduction methodology, an
43
selectivity and sensitivity of the system. Sim-
ilarly, detection of TNT, RDX and DNT 178,179 ionisation chamber, a drift tube and detector
44
45 has been achieved using heat absorption moni- (Figure 13). IMS functions by analysing ions
46 toring (HAM) sensors, with selectivity achieved from vaporised samples. Sample collection can
47 through monitoring temperature variation dur- be achieved using swabs or directly sampling
48 vapour. Collected samples are thermally des-
49 ing the melting process. Quantities of TNT and
RDX at 1 ppm and DNT at 20 ppb were de- orbed into a chamber and ionised. 3 H, 241 Am
50
51 tected. A graphene-oxide HAM device was also and 63 Ni can be used as ionisation sources 183
52 developed with chemical selectivity for DNT but the latter is more commonly found in com-
53 and an LOD of 4.6 ppb. 134 mercial devices. Due to safety concerns and
54 stringent rules for transporting radioactive ma-
55
terials, there is now an increasing move towards
56
57 the use of non-radioactive ionisation sources.
58 Examples include; photoionisation, 184 corona
59
16
discharge 185,186 and helium plasma ionisation systems. 202 The research is promising for detec-
1
2 (HEPI). 187 Table 2 outlines some of the com- tion of materials with low vapour pressures and
3 mercial systems currently in use and Table 3 also for the development of new swab materials,
4 shows recent advances in IMS for ETD. as realised in the form of a patented Naiform
5 swab. 203 Laster et. al compared the collec-
6
Recent developments tion efficiency of modified polypyrrole films
7
8 and commercial swabs for TNT. Polypyrrole
9 Traditional methods for mimicking human and polypyrrole-poly[pyrrole-N-propionic acid]
10 wipe-sampling involved the use of a TL- films were found to show greater interaction
11 slip/peel tester or similar devices where pres- with TNT (Figure 14). 204 Dopants can be used
12 sure, speed and direction are controlled param- to generate reactant ions to improve the se-
13
14 eters. Such devices offered limited automation lectivity of product ions. Recently, Jiang et.
15 capability and suffered from human error asso- al. reported detection of HMTD and TATP
16 ciated with manual loading unloading of sam- using dopant assisted positive ionisation IMS
17 ples. A robotic variant of the TL-slip/peel (DAPPI-IMS) in the presence of complex ma-
18 tester was developed by Robinson et al., with trices. 205 Acetone was used to improve the res-
19
20 the main advantage the ability to investigate olution of product ion peaks and detection lim-
21 multidirectional swiping with constant pressure its for TATP and HMTD were reported to be
22 and speed, as well as minimising human er- 23.3 ng and 0.2 ng, respectively. An improved
23 rors. 198 Choi et al. report the use of different thermal desorber capable of activation within
24
hydrophilic surfaces as smear matrices, in con- 0.8 seconds of sample input is also reported
25
26 junction with a stainless steel roller to manually which would benefit the short lifetimes of per-
27 collect particulate trace explosives for detection oxide explosives. The technology could also be
28 with IMS. Detection of RDX and TNT were re- used for drug detection which favour electropos-
29 ported to be at several hundred nanograms. 199 itive ionisation. Tsai et al. also report the use
30
Although these values are much higher than of chemical modifiers to improve the detection
31
32 what is currently achieved in field instruments, of AN and UN. Detection was achieved using
33 the study provides important fundamental data crown ethers and sugars to form adducts with
34 useful for characterising explosives on surfaces the cationic and anionic constituents, respec-
35 which may lead to the development of better tively, for each explosive. Modified ions gen-
36
swabs or collection methodologies. The effect erated were identified using electrospray ion-
37
38 of swab re-use on the collection efficiency was isation mass spectrometry (ESI-MS) and ESI
39 studied by DeGreeff who characterised wear us- high performance IMS mass spectrometry (ESI-
40 ing GC-MS and silhouette microscopy. Com- HPIMS-MS). 206
41 paring two widely used materials, Nomex and Fundamental errors and experimental drift
42
teflon-coated fibreglass, collection efficiency was associated with determining reference K 0 val-
43
44 found to increase with re-use due to increased ues can lead to wide threshold windows in de-
45 surface roughness. 200 tection equipment and impair the accuracy of
46 Various methods of chemical modification detection equipment. For operational equip-
47 have been reported to improve IMS detection of ment, these values are rarely disclosed, however
48
49
exlosives. Chouyyok et al. modified swabs us- 1-2 % is reported by some manufacturers, 207 . 208
50 ing phenyl-functionalised fibreglass to improve Hauck et al. report an IMS design with a her-
51 the collection efficiency of explosives. The en- metically sealed drift tube to improve the accu-
52 hanced swabs showed better performance com- racy of calculated K 0 values and overcome the
53 pared to muslin, a commercially available swab effect of pressure on K 0 drift. An accuracy of
54
55
material. 201 Kelley et al. showed the addition 0.1 % was achieved for a device using a 63 Ni
56 of sulphuric acid to chlorate and perchlorate ionisation source. 209
57 salts improved the availability of product ions The sensitivity of IMS can be enhanced
58 in both thermal desorption MS and IMS-MS through incorporating separation technologies
59
17
Detector (faraday
Gas outlet
1 plate and
2 Direction of electric field aperture grid)
3
4
5
Sample
6
7
8
9
10 Gas inlet
11
12
13
14 Ionisation Drift region
region
15
16 Ion shutter
17
Reactant Sample Product Direction
18 of carrier
ions molecules ions
19 gas flow
20
21
22
Figure 13: Typical set-up of an ion mobility spectrometer.
23
24 Table 2: Examples of IMS ETD devices currently in use
25
Manufacturer Model Sample Type Swab Type Ionisation Method Reference
26
27 Bruker Daltonik GmbH DE-tector Particulate Teflon® -coated (PTFE) fiberglass HEPI 188
Bruker Daltonik GmbH RoadRunner Particulate, Teflon® -coated (PTFE) fiberglass HEPI 189
28 vapour
29 L3 Technologies QS-B220 Particulate Teflon® -coated (PTFE) fiberglass Photo ionisation 190
30 Rapiscan Systems ITEMISER 4DX Particulate Teflon® d-coated (PTFE) fiber- Corona discharge 191
31 glass
Rapiscan Systems ITEMISER DX Particulate Teflon® -coated (PTFE) fiberglass 63 Ni 192
32 63 Ni 193
Nuctech TR2000DB-A Particulate Swab
33 Smiths Detection IONSCAN 500DT Particulate Cotton, Nomex® 63 Ni 194
34 Smiths Detection IONSCAN 600 Particulate Nomex® Corona discharge 195
63 Ni 196
35 Smiths Detection Multi-Mode Particulate, Cotton
36 Threat Detec- vapour, liquids
tor (MMTD)
37 Thermo Fisher Scientific EGIS Defender Particulate, Teflon® -coated (PTFE) fiberglass 63 Ni 197
38 vapour
39
40
41 such as High-Field Asymmetric Waveform Ion peaks obtained for PETN and erythritol tetran-
42 Mobility Spectrometry (FAIMS), mass spec- itrate (ETN) using IMS-MS corresponded with
43
trometry (MS) and tandem mass spectrometry peaks seen in a commercial IMS system. Stud-
44
45 (MS/MS). IMS-MS and IMS-MS/MS for explo- ies conducted using ETN synthesised under dif-
46 sives detection is well reported in literature and ferent methods showed discrimination of ana-
47 can detect both military and home-made ex- lyte and impurity peaks, indicating the possi-
48 plosives. 210–214 ESI can be integrated with an bility of the technique being used to forensically
49
IMS system to provide high resolution data and identify sources of HMEs. 217 Another modifica-
50
51 analysis of liquid phase samples. The Excellims tion of traditional IMS instruments is the use
52 GA2100 and GA2200 are examples of commer- of lasers to achieve concurrent desorption and
53 cial ESI-IMS systems with the ability to detect ionisation. Akmalov et. al compared the de-
54 10 explosives, including thermally labile TATP tection ability of this approach using pulsed and
55
and PETN. 215,216 Recently, IMS was coupled continuous wave lasers. Several nitro explosives
56
57 to an orbitrap MS to produce a high resolu- were successfully detected, with analyte disso-
58 tion accurate mass (HRAM) device. Analyte ciation neglible in affecting detection. 218 Sub-
59
18
sequent studies by the same group report the

1
2 detection threshold of TNT to be 10-14 g/cm3 ,
3 for a laser IMS system 219 and improved sensi-
4 tivity for the detection of TNT using dopants,
5 for a laser FAIMS system. 220
6
7
8
9
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
32
33
34
35
36
37
38
39
40
41
42
43
44
45
46
47
48
49
50
51
52
53
54
55
56
57
58
59
19
1
2
3
4
5
6
7
8
9
10
11
12
13
14
15 Figure 14: Study by Laster et. al into the effect of surface morphology on adhesion of TNT
16
17
molecules. a-c) Microscopy images of PAPy films, d) Average collection of TNT by PAPy films
18 with different surface roughness. 204 Reproduced from ref. 204 Copyright 2018 Elsevier.
19
20 Table 3: Recent developments involving IMS detection of explosives
21
22 Ionisation source Carrier gas Dopant Materials detected LOD Reference
23 266 nm Nd3+ :YAG laser Air None TNT, RDX 2 ppt (TNT), 5 ppt 219
(RDX)
24
Secondary electrospray ionisation N2 KCl TNT 1 µg L-1 221
25 (SESI)
26 Thermal ionisation Air CCl4 TNT, RDX , PETN 0.15 ng (TNT re- 222
27 ported)
Ni63 Air CCl4 NG, RDX, TNT, Not reported 223
28 PETN
29 X-ray with Rhodium target Air - Ammonia 30-7500 ppt 224
30 SESI N2 - RDX, PETN, NG, Ppq 225
31 EGDN, TNT
32
33
34 Colorimetric kits ployment of colorimetric kits for security, are
35 provided by Kangas 60 and Meaney. 229
36 Colorimetry describes techniques which use
37 colour change to determine the presence of an-
38 alytes in solution, usually through indicating
Recent developments
39
the presence of specific functional groups. A Colorimetric kits exploit luminescence, ab-
40
41 wide range of applications exists for colorimet- sorbance and fluorescence phenomena to elicit
42 ric kits 226–228 and examples of commercially colour changes. Fluorescence quenching meth-
43 available kits for ETD are listed in Table 4. ods remain the most popular technique and an
44 Such kits are easy to use, exists in different in-depth review can be found by Sun et. al . 235
45
forms i.e. sprays, swabs and pens and pro- Such methods can be achieved through a va-
46
47 vides results in seconds. Thus, colorimetric kits riety of materials including; small molecules,
48 are very useful as a diagnostic tool. As with metal organic frameworks (MOFs), polymers
49 colorimetric arrays discussed previously, tech- and functionalised nanoparticles. The ba-
50 nological advances have seen the integration of sis of many nitroaromatic detection mecha-
51
52
colorimetric kits with digital sensors for better nisms exploit the electron withdrawing prop-
53 colour discrimination. Many commercial sys- erty of the -NO2 group, which deactivates
54 tems exist as electronic portable devices which the aromatic ring. As such, this makes ni-
55 benefit from data storage, automated detection troaromatic compounds good electron accep-
56 and ruggedness capability. Recent reviews cov- tors and charge transfer interactions between
57
58
ering luminescent approaches, design and de- nucleophiles generally leads to the formation
59
20
Table 4: Examples of commercially available colorimetric kits

1
2 Manufacturer Product name Explosives detected Test time Detection mode Reference
3 Morphix® TraceX® Nitroaromatics, nitramines/nitrate < 3 minutes Naked eye 230
4 esters, inorganic nitrates, chlo-

rates/bromates, peroxides, acids and
5
bases
6 ChemSee Portable explosive Nitroaromatics, nitramines, in- 20-60 seconds Naked eye 231
7 test kit organic nitrates, peroxides, chlo-

8 rates/perchlorates
DetectaChem SEEKERe Nitroaromatics, nitramines/nitrate Seconds Digital 232
9 esters, inorganic nitrates, chlo-
10 rates/perchlorates, peroxides
11 BBI Detection Dry Explosive De- Nitroaromatics, nitroamines/nitrate 3-6 minutes Naked eye 233
12 tection Test Kit esters, nitrates, chlorates/bromates,

(DETK) hydrogen peroxide
13 BBI Detection Liquid Explosive Nitromethane, hydrazine, nitro- 1-2 minutes Naked eye 233
14 Test Kit (LETK) glycerine, fuels, and precursor solvents,
15 peroxides, acids and bases
Mistral Secu- DropEx TNT, Nitroaromatics, ni- 5 seconds Naked eye 234
16
rity Inc. troamines/nitrate esters, inorganic
17 nitrates, perchlorates, peroxides,
18 inorganic oxidants, nitromethane
19
20
21 of brightly coloured Meisenheimer complexes. troscopy, with the latter showing increasing
22 Amines are commonly used and an example is fluorescence quenching with respect to TNT
23 shown in Figure 15 from the interaction of TNT and TNP concentration. Choodum et. al
24
25 and cysteine to produce a red Meisenheimer developed several test kits for TNT by trap-
26 complex. ping different colorimetric reagents (tetram-
27 ethylammonium hydroxide, ethylenediamine
28 and potassium hydroxide) in polyvinyl alco-
29
hol or polyvinyl chloride hydrogels. 57–59 Each
30
31 test kit is portable, low cost and can be frozen
32 for storage. Quantitative data from the re-
33 sultant coloured meisenheimer complexes is
34 provided through a conventional smartphone
35
camera. The UN–1 kit exploits the acidic
36 Figure 15: Example of a TNT-meisenheimer
37 nature of UN to achieve selectivity against
complex formed on interaction between TNT urea. The reaction proceeds under neutral con-
38
39 and cysteine. 236 Reproduced from ref. 236 Copy- ditions using p-dimethylaminocinnamaldehyde
40 right 2013 RSC. (p-DMAC), forming a red pigment within 60
41
seconds. The test can exist as a swab test with
42 The Griess test is another traditional ap-
43 liquid reagent or as a spray, with detection lim-
44
proach used to detect nitrate ester, nitramine its of 100 µg/cm2 . 238 Zhao et. al developed a
45 and nitrate explosives such as AN and UN. Dif- sensor array for the simultaneous detection of
46 ferent mechanisms are used, including; alkali 10 explosives. The authors used time-resolved
47 hydrolysis, α-elimination, β-elimination and re- reduction of indigo carmine by dithiothreitol
48 duction of nitrates to produce nitrite ions. 6
49 and discrimination was achieved by simultane-
50
Zhang et al. report the development of a ously monitoring 6 absorption peaks to produce
51 chemosensor for TNT and 2,4,6-trinitrophenol a ‘colorimetric fingerprint’. The limit of detec-
52 (TNP). The sensor probe features a Schiff tion was 1.5 µM. This approach was also ef-
53 base, naphthalene, which forms a red meisen-
54
fective when tested against contaminated water
heimer complex in the presence of TNT. TNP samples. 239
55
56 undergoes deprotonation and forms a yellow Peroxide-based explosives are generally de-
57 product. 237 The reactions can also be ob- tected through indirect means, after undergo-
58 served using UV–VIS and fluorescence spec- ing decomposition to hydrogen peroxide. Var-
59
21
A 2-azidoterephthalate 5-azidoterephthalate
B C
1
2
3
4
5
6
7
8 D E
9
10
11
12
13
14 Figure 16: MOF-based fluorescent probes for detection of TNP using dysprosium centres A)
15 Schematic showing formation of MOFs derived from two carboxylate ligands, 2-azidoterephthalate
16
17 (2N3 -TPA) and 5-azidoterephthalate (5N3 -IPA), producing MOFs 1 and 2, respectively. Fluores-
18 cence quenching experiments in the presence of TNP and other nitro explosives to aqueous suspen-
19 sions of B) MOF 1 and C) MOF 2. Optical images of aqueous dispersion of MOFs on addition of
20 various nitro explosives under UV light for D) 1 and E) 2. 240
21
22
23 ious approaches can be used, involving en- porosity, structure, topology and the variety
24
zyme catalysed reactions. The ‘Acro-P.E.T’ of mechanisms with which to elicit responses.
25
26 is a 2–step field kit which involves liberation Several authors report the development of
27 of hydrogen peroxide through acid hydroly- MOF materials capable of multi-target de-
28 sis of suspect materials, followed by oxidation tection. Wang et. al incorporated a cationic
29 of a chromogenic substrate, 2,2’-Azino-bis(3- dye, (E)–4–(4–(dimethylamino)styryl)–1–
30
ethylbenzthiazoline-6-sulfonic acid) diammo- methylpyridin–1–ium (DMASM), into a
31
32 nium salt in the presence of horseradish peroxi- Zn-MOF, (Zn8 (Ad)4 (BPDC)6 O·2Me2 NH2 ,
33 dase to produce a blue-green colour. 241 Hydro- Ad=adeninate; BPDC=biphenyldicarboxylate).
34 gen peroxide present in detergents, cosmetics The resultant probe enables two fluorescence
35 and cleaning products can lead to false posi- quenching approaches, allowing differentia-
36
tive results. Schulte-Ladbeck et al. overcame tion between nitroaromatic, nitramide and
37
38 this by using catalase to remove trace hydrogen nitrate esters explosives, including the tag-
39 peroxide in samples prior to testing, followed gant DMNB. 245 In a similar study, Fu et. al
40 by decomposition of explosive material through incorporated an anionic dye, 8–hydroxy–1,3,6–
41 UV photolysis and detection of the resul- pyrenetrisulfonicacid (HPTS), into a Zn–MOF,
42
tant hydrogen peroxide using 2,2’-azino-bis(3- [Zn(TIPA)(NO3 - )2 ]·5H2 O (TIPA=(tri(4–
43
44 ethylbenzothiazoline)-6-sulfonate (ABTS) and imidazolylphenyl)amine)). Using ratiometric
45 p-hydroxyphenylacetic acid (pHPAA) in the fluorescence, the authors show detection of
46 presence of horseradish peroxidase. 242 Several RDX is possible down to 39 ppm. 246 Both
47 thin film sensors were developed by Fan et. MOF constructs are reusable. Jurcic et. al
48
49
al using fluorenylboronate esters. Detection of report the development of a MOF array for the
50 TATP vapour was achieved through the gen- differentiation between TNT, tetryl, RDX and
51 eration of H2 O2 using Amberlyst-15. A de- PETN with limits of detection down to ppm. 247
52 tection limit of 40 ppb within 60 seconds was Various signal transduction approaches have
53 achieved, with the speed of detection enhanced been adopted to enhance the sensitivity of
54
55
through blending the boronate ester mixtures MOF materials. Recently, a Cu–MOF was
56 with tetra-n-butylammonium hydroxide. 243 linked to an optical fibre Fabry–Pérot inter-
57 MOFs have received a lot of interest due ferometer (FPI) to achieve real-time detection
58 to their many tunable properties such as; of nitrobenzene. 248 Integration of a europium-
59
22
A B C D
1
2
3
4
5
6
7
8
9
10
11
12 Figure 17: AIE hyperbranched poly(silylenephenylene) (hb-PSP) for the detection of trinitrophenol
13 (picric acid, PA). A) Structure of hb-PSP with repeat units tri-phenylbenzene. B) In-solution and
14 aggregate forms of hb-PSP in the presence of explosive. C) Detection of trinitrophenol using hb-
15 PSP in tetrahydrofuran (THF) and D) THF-water mixture. Inset image shows the active hb-PSP
16
17
and fluorescence quenching of hb-PSP on addition of 0.12 mM trinitrophenol. 244 Reproduced from
18 ref. 244 Copyright 2010 RSC.
19
20
21 MOF with a hydrogel optical fibre was also and 1.1 × 10-6 M, respectively. 263 Recent de-
22 shown to be an effective sensor for TNP. 249 velopments in conjugated polymers has seen the
23 Mukherjee et. al synthesised MOFs using use of aggregation-induced emission (AIE) ma-
24 dysprosium incorporated into two carboxylate terials, whereby polymer fluorophores exhibit
25
26
ligands for the detection of TNP, achieving lim- low emission in a dissolved state but strong
27 its of detection in the µM range (Figure 16). 240 emission on aggregation. The effect is re-
28 Additional metal centres which have been alised through free vibrational and rotational
29 used in MOFs for explosives detection include; intramolecular motions which dissipate exciton
30 sodium, 250 indium, 251 cadmium, 252 zinc 253 energy of the polymer in solution. Aggrega-
31
32 and lanthanide elements; europium 254,255 and tion of polymer molecules leads to conforma-
33 terbium. 256,257 tional changes (i.e. π-π stacking), which re-
34 Conjugated polymers are effective candidates stricts these intramolecular motions, enabling
35 for the detection of nitroaromatic explosives be- radiative decay of exciton energy and emis-
36 cause they are excellent electron donors. One sion. 264 To date, a number of branched and lin-
37
38 mechanism exploited for ETD is the ‘molecu- ear AIE polymers have been reported for many
39 lar wire’ effect, which allows for the conduc- nitroaromatic explosives. 265 An example of a
40 tive quenching of connected polymer molecules hyperbranched AIE polymer was reported by
41 on adsorption of a target analyte. 258 Significant Liu et.al using poly(silylenephenylene) for the
42
enhancement over molecule-based fluorophores detection of TNP. 244 The polymer’s globular
43
44 can be achieved 259 and this effect has been structure with numerous cavities results in high
45 used to develop ‘Amplifying fluorescent poly- surface area for the binding of TNP molecules
46 mers (AFP)’, as seen in the commercially avail- as well as improving exciton migration (Figure
47 able Fido explosives detectors which have de- 17). Wu et. al used triphenylamine-based ma-
48
tection limits down to ppt levels. 260–262 Ma et.al terials with dimethyl sulfoxide/water-mediated
49
50 utilised the molecular wire effect through a hy- AIE to detect TNP. 266
51 drophillic polymer consisting of a carbazole- Carbazole-based nanostructures developed by
52 based backbone and diethanolamine-based side the Zhao group have shown successful identifi-
53 groups. The presence of hydroxyl groups on the cation between classes of explosives, using dif-
54
polymer facilitated H-bonding with nitroaro- ferent fluorescence quenching mechanisms. A
55
56 matic explosives and signal amplification. The two-member construct made up of nanofibres
57 authors report selective detection of DNT and and nanoribbons was used by Zhu et. al. By
58 TNT with detection limits of 7.4 × 10-7 M proportioning the fluorescence quenching ratios
59
23
between each sensor, nitroaromatic, nitramine, a DNA-based assay for the detection of TNT
1
2 nitrate esters and ammonium nitrate explo- which uses a dual-identification approach.
3 sives were identified at ng-levels. 267 Using the The DNA construct is capped at one end
4 same carbazole nanofibres by Zhu, along with with an aptamer specific for TNT and with
5 a Co2+ –coordinated analogue, Xiong et. al de- copper nanoparticles (CuNPs) at the other
6
veloped a binary polymer able to discriminate end. Exploiting the fluorescence properties of
7
8 between six classes of explosives. Peroxide ex- the CuNPs and with use of inductively coupled
9 plosives were detected indirectly through active plasma mass spectrometry (ICPMS), identifi-
10 decomposition to produce H2 O2 ,and reduction cation was achieved with high selectivity and
11 of Co+ . Conversely, detection of nitroaromatic, detection limits of 0.17 ng/mL and 0.32 pg/mL
12
nitramine, nitrate esters and black powder is were achieved using fluorimetry and ICPMS,
13
14 achieved through electron transfer between the respectively. 274 An electrochemical aptamer
15 nanofibre network and explosive. The resultant sensor specific for detection of TNT was also
16 fluorescence quenching by different parts of the developed by Roushani et. al, consisting of
17 same molecule enables selectivity and detection gold nanoparticles deposited on fullerene (C60)
18
in the ng range. 268 Self-assembling carbazole and with a detection limit of 0.17 fM. 275 Table
19
20 nanospheres were developed by Ma et al. for 5 shows recent developments in colorimetric
21 the detection of TNP in solution, with a detec- approaches to ETD.
22 tion limit of 120 nM. 269
23 Due to their unique optical, catalytic and
24
25
electronic properties, there is continuing inter-
26 est in the use of nanoparticles to improve the
27 speed, sensitivity and selectivity of colorimet-
28 ric approaches. Au-Ag nanoparticles function-
29 alised with β–cysteamine were developed by Ar-
30
31
shad et. al and incorporated onto a paper sen-
32 sor for the detection of TNT. 270 The addition
33 of cetyltrimethylammonium bromide surfactant
34 (CTAB) enhanced the rate of reaction and se-
35 lectivity was shown against TNP, DNT and NB
36
37
explosives. Idros et. al used 3-aminopropyl-
38 triethoxysilane (APTES) to produce amine-
39 functionalised SiO2 nanoparticles for the detec-
40 tion of TNT. A red-green colour change on for-
41 mation of NH3 -TNT meisenheimer complexes is
42
43
observed and discrimination between DNT was
44 achieved by measuring the change in reflective
45 properties of the self-assembling film. 271 Taw-
46 fik et. al used polythiophene coated CdTe QDs
47 to detect TNP. The amphiphilic sensors were
48
49 coupled with a smartphone to facilitate on–site
50 detection with LOD being 0.56×10-9 M. 272
51 A fluorescence sensor using 4,5–
52 di(hetero)arylpyrimidine dyes has been
53 developed, with ability to screen for a range of
54
55 nitroaromatic explosives with detection limits
56 between 10-4 –10-6 M. The sensor has been
57 subsequently realised in the form a commercial
58 device called ‘Nitrosensor’. 273 Hu et. al report
59
24
1
2
3
4
5
6 Table 5: Colorimetric approaches to ETD - recent developments for MOF’s, polymers, function-
7
8 alised nanomaterials and fluorescent molecules. Physical parameters used for detection and LOD’s
9 are reported. 1 MOF formula given.
10
Type Agent λAbs max Emission λ Excitation Analyte LOD Ref.
11 (nm) (nm) λ (nm)
12 Cu nanoclusters capped with – 480 330 TNT 0.05 nM 276
13 polyethylene imine
Functionalised Ag nanoparticles modified with 4– Not re- – – TNP 0.13 nM 277
14
nanoparticles amino–3–hydrazino–5–mercapto– ported
15 1,2,4–triazole
16 Mercaptoethylamine–capped Au – 540 – TNT 21.9 nmol L-1 278
17 nanopaticles and mercaptopropi-

18 onic acid-capped CdSe quantum
dots
19 N,N–Dimethyl–p– 554 – – TATP 0.47 mg L-1 279
20 phenylenediamine with Fe3 O4
21 nanoparticles
ZnCr2 O4 nanoparticles 410 – – TNP 0.1 µM 280
22 -1 281
Ag nanoparticles and 3,3’,5,5’– 655 – – TATP 0.31 mg L
23 tetramethylbenzidine (TMB)
24 [Zn3 (L)2 (bipy)(µ3 -OH)2 ]·3H2 O - 363 281 DNT, TNP 400 µM 282
25 Ag@Zn(TA)·(H2 O)·(DMF) 652 – – TATP 0.1 mg L-1 283
[(CH3 )2 NH2 ][Eu3 (µ3 –OH)(1,4– 263 617 263 Tetryl, 20–140 mg/mL 284
26 MOF’s1
BDC)3 (HCOO)3 ] TNP, TNT
27 [Zn4 L(H2 O)4 ·(solvent)]n – 348 315 RDX, ppm 247
28 PETN,
29 TNT,
DNT,
30 Tetryl
31 [Dy(2N3 - – 437, 673 333 TNP 0.04 µM 240
32 TPA)2 (H2 O)(CH3 OH)]∞

33 [Zn(PBPCA)(H2 O)2 ]Q[6]·21H2 O – 346 290 TNP 3.20 ×10-7 M 285
Pyrenyl–fluorene copolymers – 461 – H2 O2 , 1.6 ppb (H2 O2 ) 286

34 TATP
35 Fluorene substituted silica micro- – 525 – PETN Not reported 287
Polymers
36 spheres
Polyfluorene probe, PF6-Boc – – 365 RDX 0.041 ppt 288
37 289
Carbazole and tetraphenylethylene – 515 – TNT 74 µM
38 copolymer
39 Glutaraldehyde and chitosan – 445 370 TNP 2.8 nM 290
40 copolymer
Dimethyl–5–(pyren–1– – 469 365 TNP 10 nM 291
41
ylmethyleneamino)isophthalate
42 2,4,6–triformyl phenol/amine sys- – 590 – TATP 0.2 ppb 292
43 tem
44 Fluorescent Azetidine derivative of naphthyldi- – 650 – TATP 0.5 µg mL-1 293
45 molecules imide
4–(dicyanomethylene)-2-methyl– – 620 – RDX, 1 pmol (RDX 294
46 6–(4–dimethylaminostyryl)–4H– HMX, and HMX),
47 pyran) PETN 1–10 pmol
48 (PETN)
Quinoline–benzimidazole conju- – 442 369 TNP 4.86 ppb 295
49 gate
50 Curcumin conjugate – 516 – TNP 11×10-8 M 296
51 Boronate ester quinoline – 520 365 H2 O2 150 ppt 297
Polyaromatic imine conjugates – 410, 492 308 NB 0.013 µM 298

52
53
54
55
56
57
58
59
25
Raman spectroscopy rods, 319 tubes, 320 wires, 321 prisms 322,323 and oc-
1
2 tahedra. 324 Additional examples of SERS sub-
3 Raman spectroscopy involves the collection and strates can be found in Table 7. The chem-
4 analysis of scattered photons to provide infor- ical enhancement is generally considered to
5 mation on molecular vibrations and hence sam- be due to charge transfer between analyte
6 ple identification and quantitation. The tech- and metallic nanoparticles. 325–327 Work towards
7
nique is widely used and advantages include; exploiting this effect for explosives detection
8
9 high selectivity, fast analysis times, minimal has led to the development of functionalised
10 sample preparation and the ability to analyse nanoparticles, with common linking agents be-
11 solid, liquid and gaseous samples. In addi- ing; APTES (3–aminopropyltriethoxysilane) 328
12 tion, analysis is carried out in a non-destructive DACH (trans–1,2–Diaminocyclohexane) 329 and
13
manner and the technique offers stand-off de- PATP (p–aminothiophenol (PATP). 330 As with
14
15 tection capabilities. As such, these features IMS devices, there is a need for convenient sam-
16 are of great interest in the counter-terrorism ple delivery and separation/pre–concentration
17 community and such applications have been of complex sample matrices for Raman–based
18 reviewed extensively for Raman 299,300 and its techniques. Piorek et al. developed a microflu-
19
most common variants; surface enhanced Ra- idic system with a SERS sensor and showed
20
21 man spectroscopy (SERS) 301–303 and spatially detection of 2,4–dinitrotoluene (DNT) down
22 offset Raman spectroscopy (SORS). 304,305 Ex- to 1 ppb of gaseous phase. 331 The system
23 amples of commercially available Raman sys- provides continuous, real-time sample analy-
24 tems are listed in Table 6. SERS overcomes the
25
sis. A large surface-to-volume is achieved us-
low sensitivity of conventional Raman through ing shallow channels of 4-40 µm, enabling pre-
26
27 adsorption of analyte molecules onto a rough- concentration of the sample and trace-level de-
28 ened metal surface, resulting in strong enhance- tection.
29 ment of the analyte’s Raman signals. Signif-
30 icant enhancement factors and the capability
31
32
for single–molecule detection using noble–metal
33 nanostructures 306,307 makes SERS a promising
34 approach for explosives detection. SORS allows
35 through–barrier analysis of opaque or semi–
36 transparent materials leaving samples intact.
37
38
This makes the technology desirable for liquid
39 screening and has been realised in the commer-
40 cially available Agilent Insight and RESOLVE
41 systems, widely used in UK airports.
42
43
44 Recent developments
45
46 SERS enhancement is attributed to both chemi-
47 cal and electromagnetic contributions. The lat-
48 ter process provides a much greater enhance-
49
ment effect and is most significant when the
50
51 surface plasmon frequency of the metal sur-
52 face is in resonance with incident radiation. 316
53 Surface plasmon resonance can be tuned by
54 changing the size, morphology and spatial po-
55
56
sitioning and identity of nanostructures. 317,318
57 As such, a range of nanostructures have been
58 developed for explosives detection, including;
59
26
Table 6: Examples of commercially available ETD Raman systems

1
2 Manufacturer Model Laser Excitation wavelength Technology Reference
3 Smiths Detection Inc. ACE-ID Diode 785 nm Raman 308
Nuctech RT1003 series Diode 830 nm Raman 309

4 310
Thermo Fisher Scientific Inc. FirstDefender RMX Diode 785 nm SORS
5 Thermo Fisher Scientific Inc. Gemini Analyzer Diode 785 nm IR and Raman 311
6 Agilent (formerly Cobalt Light Sys- Insight 100M and Diode 830 nm SORS 312
7 tems) 200M
Agilent (formerly Cobalt Light Sys- RESOLVE Diode 830 nm SORS 313
8
tems)
9 Real-Time Analyzers Inc. Portable SERS Ana- Diode 785 nm SERS 314
10 lyzer
11 Hamamatsu C13560 spectroscopic Diode 785 SERS 315
12 module
13
14
15 angular nanoprisms onto an APTES function-
16 alised glass coverslip followed by transfer onto
17 a flexible adhesive tape. The resulting sensor
18 showed detection of TNT down to 900 parts
19
per quadrillion (ppq) and 56 ppq for RDX and
20
21 PETN, using a commercial off the shelf Raman
22 system. 323 The ‘plasmonic patch’ developed by
23 Gupta et. al. is a transparent flexible PDMS
24 film decorated with gold nanorods which can
25
be added to different SERS substrates, lead-
26
27 ing to enhanced sensitivity 332 (Figure 18). Liu
28 et. al also report development of a flexible
29 Figure 18: SERS ‘plasmonic patch’ for the col- substrate, by immobilising silver nanoparticles
30 lection and analysis of explosives as described onto a composite sponge surface consisting of
31 in ref. 332 A) Schematic representing vapour de- polyurethane and polydopamine. Perchlorates,
32 tection of TNT via peptide-conjugated gold
33 chlorates and nitrates were detected at sub-
nanorods. B) Characterisation of bare and pep- nanogram quantities. 334
34
35 tide conjugated gold nanorods using UV-Vis Non-plasmonic substrates including graphene
36 spectroscopy. C) Raman data showing vapor- and semiconductor materials generally have low
37 phase detection of TNT. enhancement capabilities, however, their strong
38
39 charge transfer properties 335,336 have been used
40 Shi et al. report the development of a chem- effectively with noble nanoparticles for detec-
41 ically modified SERS substrate for the detection of many explosives. Examples include
42 tion of inorganic and organic explosives. Sil- ZnO, 337 graphene oxide 338,339 and TiO2 . 340 The
43 ver nanowires were manufactured with diethyl-
44
introduction of oxygen vacancies can improve
45 dithiocarbamate (DDTC) ligands to produce Raman enhancement of semiconductors and
46 a positively charged system. SERS detection this can be achieved through surface and atomic
47 was achieved using an excitation wavelength defects. 341 Ben–Jaber et al. report the use of
48 of 785 nm. The detection of perchlorates photo-induced SERS (PIERS) for the detection
49
(ClO4 - ), chlorates (ClO3 - ), nitrates (NO3 - ) and of TNT, DNT, RDX and PETN at concentra-
50
51 2,4–dinitrophenol were reported to be 2, 1.7, tions of 7 µg/L, 0.1 µg/L, 2.2 mg/L and 3.2
52 0.1, 45.8, and 36.6 ng, respectively. 333 The mg/L, respectively 342 (Figure 19). PIERS sig-
53 flexible substrate can be used as a swab and nals showed enhancement compared with SERS
54 this is a promising advancement of SERS as a for all explosives studied, with a 20-fold in-
55
ETD technique for use in operational screen- crease achieved for RDX. Substrate regenera-
56
57 ing. Other flexible substrates have also been tion was achieved using UV-light. Addition-
58 reported. Liyange et. al fabricated gold tri- ally, Glass et. al studied the surface oxygen va-
59
27
cancy states of different metal oxide substrates,

1
2 including TiO2 , ZnO and WO3 . 343 Differences
3 observed in vacancy formation and healing life-
4 times of these materials could help guide de-
5 velopment of PIERS substrates. Given the UV
6
pre-irradiation step is sample-independent and
7
8 the proven versatility of SERS in detecting a
9 range of organic and inorganic explosives, 344–346
10 development of a reusable multi-target sensor is
11 a possibility and would greatly benefit routine
12
screening in civilian and military environments.
13
14 These studies indicate potential further applica-
15 tions of established metal oxide SERS materials
16 as PIERS substrates.
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
32
33
34
35
36
37
38
39
40
41
42
43
44
45
46
47
48
49
50
51
52
53
54
55
56
57
58
59
28
1
2
3
4
5
6
7
8
9
10 Figure 19: Proposed PIERS mechanism. UV light is used to increase the availability of electrons in
11
the conduction band of the SERS substrate through the creation of vacancy defects. This results in
12
13 elevated levels of electron migration from substrate to nanoparticles upon Raman laser illumination.
14 (A) Creation of oxygen vacancies (VO ) in the TiO2 below the conduction band using ultraviolet
15 C light (UVC).(B) Sample deposition (DNT shown) followed by irradiation with 633 nm Raman
16 laser. This leads to photoexcitation of TiO2 and increase in charge on the nanoparticles. (C)
17
Charged nano particles lead to PIERS signal enhancement. VO are replenished upon exposure to
18
19 air. (D) The PIERS effect gradually disappears as the VO are completely replenished over time. The
20 substrate can then be cleaned and recharged through exposure to more UVC light absorption. 342
21 Reproduced from ref. 342 Copyright 2016 Nature.
22
23
24 A limitation of SERS is signal reproducibility, samples which are very thin i.e. white powders
25 which is affected by the shape and size, as well within envelopes or parcels. Cletus et. al used
26
27
as the separation, of the nanoparticles used in nanosecond time-resolved SORS to achieve de-
28 the substrate. Efforts to overcome these prob- tection of explosives through opaque containers
29 lems have resulted in some commercially avail- under ambient and fluorescent light. 353 By ex-
30 able substrates which include; QSERS, RAM- ploiting the time delay between laser excitation
31 SERS, KlariteTM and SERStrate, which have and detector activation, emitted photons due
32
33
recently been tested using commercial Raman to fluorescence can be excluded, thus suppress-
34 systems for contraband detection. 347–350 ing interference from ambient light. Using this
35 A limitation of SORS is the ability to probe approach, detection of DNT, hydrogen perox-
36 thin layers which are micrometers thick. This ide and nitromethane was achieved in different
37 is due to the wide Raman excitation beam and coloured HDPE containers. Another approach
38
39
collection area used, generally at the mm scale to reduce fluorescence interference is reported
40 or higher. 351 The use of SORS for subsurface by Hopkins et. al, which involved the use of
41 detection of analyte through thin turbid media a 1064 nm laser excitation source in combina-
42 was reported by Conti et al. Termed Micro- tion with an indium gallium arsenide (InGaAs)
43 SORS, the technique utilises a conventional Ra- detector. 354
44
45 man confocal microscope to perform two mea-
46 surements; with the sample in its original and
47 defocused positions. Spectral subtraction com-
48 bined with a scaling factor to cancel out resid-
49 ual surface layer Raman bands results in a Ra-
50
51 man signal for the sub-surface. Interrogation
52 of multi-layers can be achieved with additional
53 defocused positions and subtractions. 352 The
54 technique was used to interrogate painted lay-
55
ers on delicate artwork, but would also bene-
56
57 fit defence and security. Micro-SORS could be
58 used for non-invasive analysis of multi-layered
59
29
Table 7: SERS substrates for ETD - recent developments

1
2 Substrate Nanostructure Laser λ Material detected LOD Reference
3 (nm)
4 Borosilicate glass Au nanocubes 633 DNT, RDX 10-15 M (DNT), 10-9 M 355
(RDX)
5 Filter paper Aggregated Ag/Au nano- 800 TNP, DNT and 11.5 ng (TNP), 1.82 356
6 particles 3-nitro-1,2,4-triazol-5- ng (DNT) and 13.1 ng
7 one (NTO) (NTO)
Klarite - 785 TATP, TNT - 357
8 Chemically modified Au nanoparticles 785 TNT 3.0 µM 358
9 Klarite® containing MIPs
10 Au colloid - 633 TNT Millimolar 359
11 Polystyrene Au nanoparticles 785 TNT 10-5 M 360
Porous silicon photonic Ag nanoparticles 633 TNP 10-8 M 361

12 crystals
13 Silicon wafer Ag nanoparticles decorated 632 Ammonium Perchlo- 10 µM 321
14 with Si nanowires rate

Silicon Bimetallic Ag/Au and 785 DTN, TNP 1 µM (DNT) and 5 µM 362
15
Cu/Au nanoparticles (TNP)
16 Aluminium Ag nanoflowers 785 TNT 5 µg 363
17 Reduced graphene oxide Ag nanoparticles 532 DNT Nanomolar 364
18 Silicon Ag/Cu nanoparticles 632 Ammonium nitrate, 5 µM (ammonium ni- 365
19 TNP trate and TNP)

20 Graphene nanosheets with - 514 TNT 5.0 × 10-16 M 366
Ag nanoparticles
21 Au nanoparticles and - 785 TNP,DNT, NTO Micromolar 367
22 nanostructures
368
23 Porous alumina mem- Au nanorod and nanopar- 785 HMTD 3 ppm
24 branes ticle mixed clusters
Silicon Magnetic hybrid system 785 TNT 1 pM 369
25 - Fe3 O4 @mTiO2 /P-ATP-
26 TNT/Au@Ag
370
27 Microscope slide Cucurbit[7]uril and Au 633 DNT 1 µM
nanoparticles
28
29
30
31
Conclusions and future per-
32 spectives
33
34
35 Table 8 and Figure 20 provide a comparison of
36 each technology, with insight into their analyti-
37 cal performances. Note, a holistic approach has
38 been taken with consideration from literature
39 reviewed here in addition to subjective assess-
40
41 ments. Animals remain a benchmark for emerg-
42 ing technologies with key attributes being high
Figure 20: Visual comparison of ETD technolo-
43 selectivity, sensitivity, concurrent detection of
44 gies based on sampling time, sensitivity, molec-
multiple analytes and fast screening times. The
45 ular selectivity and cost.
majority of in-field systems have sampling times
46
47 within minutes and this has also been observed
48 in many emerging technologies reviewed here. information. Ions generated from benign ma-
49 IMS remains a key technology in the field of terials with similar mobilities to explosive ions
50 ETD due to having good overall sensitivity, se- can trigger false positive responses and such in-
51
lectivity and analysis times in seconds. terferences include oils, creams, perfumes and
52
53 However, current IMS systems lack molec- medication. Efforts to improve the selectiv-
54 ular selectivity compared with spectroscopic ity of IMS include; use of dopants, develop-
55 approaches such as Raman and absorp- ment of chemically modified swabs, understand-
56 tion/emission spectroscopy which can provide ing the ion chemistry of analytes and integra-
57
molecular fingerprinting and functional group tion of IMS with mass spectrometry techniques.
58
59
30
Table 8: Advantages and limitations of ETD technologies

1
2 Techniques Advantages Limitations
3 Animals concurrent sampling in real-time, wide range of threat high training and maintenance costs, inconsistencies,
4 materials affected by the environment and surroundings, not al-
ways practical in civilian environments
5 IMS easy to use, dual vapour and particulate detection in expensive, radioactive ionisation source, affected by
6 some systems, can be integrated with mass spectrom- humidity, temperature and sample composition, de-
7 etry, library structive, requires rigorous sampling to maximise an-
8 alyte collection
Raman portability, non-destructive analysis, sampling interference from fluorescent or strongly absorbing ma-
9 through packaging, stand-off detection capability, terials, small scan area, cannot be used for metals or
10 sampling of solid, liquid and gasses alloys
11 Colorimetric easy to use, portability, inexpensive, integration with stability/shelf life, may require multiple tests, destruc-
12 kits smart phone technology, small footprint and power re- tive
quirements
13 Sensors portability, customisable, multi-modal capability largely untested in operational environments
14
15
16 Traditional colorimetric reagents are limited calorimetric, acoustic wave resonators and ther-
17 by specificity, sensitivity and toxicity of some mal analyzers, means that multi-mode detec-
18
19 materials. Development of sensor arrays and tion systems are likely to become the next gen-
20 use of ratiometric fluorescence approaches over- eration of ETD detector. Furthermore, the re-
21 comes these problems as they probe the chem- cent development of a MEMS vacuum pump 371
22 ical properties of analytes, leading to greater and 3D printed sensors introduces further ap-
23
selectivity and sensitivity. The use of mul- plications for ETD. 372
24
25 tiple sensor elements to give a combined re- Traditional methods of vapour sampling in-
26 sponse further improves analyte differentiation clude IMS and GC-MS. However, these systems
27 and selectivity. This has been largely possible are limited by their range, lack of real-time sam-
28 through the use of tunable nanomaterials such pling and cost, making air sampling of large ar-
29
as MOFs, nanoparticles, quantum dots and con- eas a challenge. MOx semiconductor gas sensors
30
31 jugated polymers. SERS is a promising ap- are promising alternatives due to their low cost,
32 proach with high sensitivity and can be used ease in which they can be set up and potential
33 with current desktop and portable Raman sys- for real time analysis. In addition, numerous
34 tems. However the technique has yet to be approaches now exist to improve selectivity. E-
35
adopted in operational environments. As the noses containing multiple gas sensors have also
36
37 number of SERS substrates continue to expand, been developed showing both high sensitivity
38 the need to develop standardised tests for as- and selectivity. Gas sensing and MEMS tech-
39 sessing detection capability and reproducibility nology already share many overlaps and with
40 is required. Work towards reproducible sub- advances in both fields, we are likely to see
41
strates at low cost for commercial use is also more examples of multi-modal systems. Fur-
42
43 important for SERS to be a viable option for ther advances will also likely see more sensors
44 operational screening. integrated with AI to improve detection. 373
45 Another emerging field for ETD is hyper-
46 spectral imaging, which allows rich datasets to
47 Emerging fields and possible new
be collected across very narrow spectral bands.
48 directions for ETD
49 The resultant image, a 3D hyperspectral data
50 Many nanomaterials have been successfully in- cube, can be probed pixel-by-pixel to interro-
51 tegrated into MEMS-based sensors and these gate reflection, emission and absorption data.
52 Concurrent spectral and spatial interrogation of
advances in miniaturised technologies have pro-
53
54 duced systems with favourable qualities such as; surfaces can be achieved and the technique can
55 multi-modal detection, portability, high selec- be used with a range of illumination sources, in-
56 tivity and sensitivity. The wide tunability of cluding; UV, 374,375 IR 376–378 and Raman, 379–381
57 many nanomaterials, combined with a variety all demonstrated for the detection of explosives.
58 Hyphenated techniques involve connecting
of MEMS-based sensors such as; piezoresistive,
59
31
two or more instruments together to improve tems become more complex, the use of machine
1
2 material characterisation. Successful integra- learning will likely become more prevalent to
3 tion of different technologies requires consider- handle large datasets. Also, as the number
4 ations such as; sample delivery, design of the of open source machine learning libraries (i.e.
5 interface and the sample phase for analysis by Caffe, TensorFlow® and PyTorch) increases,
6
each technology. In ETD, the most notable ex- this will facilitate entry into using AI to analyse
7
8 amples of hyphenated technologies are IMS sys- sensor data. However, a key challenge is inte-
9 tems combined with mass spectrometry. How- grating machine learning with multi-modal sys-
10 ever, hyphenated vibrational spectroscopy tech- tems which combine different characterisation
11 niques have received less attention. Whilst, IR data to achieve selectivity. The use of machine
12
and Raman can provide high specificity through learning can also benefit other ETD technolo-
13
14 generation of molecular fingerprint profiles and gies such as IMS and Raman. In Raman-based
15 functional group information, interpretation of approaches, complex mixtures produce spectra
16 mixtures can be difficult due to the complex- showing vibrational modes from each compo-
17 ity of the spectra. The combination of Ra- nent. Spectral profiles in SERS is complicated
18
man with separation technologies could over- further due to orientation effects of molecules
19
20 come these problems. Such a system could in- with respect to SERS substrates. However,
21 volve the use of a microextraction technique to machine learning can be used to identify spec-
22 isolate analytes of interest, 382 combined with tral features of analytes from Raman and SERS
23 an integrated Raman-mass spectrometry sys- data and many examples can be found in fields
24
25
tem for analysis, 383 all enabled through a mi- outside of ETD. 388
26 crofluidic delivery system. Whilst a number of
27 hyphenated Raman approaches have been re- Concluding remarks
28 ported, 384,385 none have been applied to ETD
29 and the area remains largely unexplored. It is likely that nanomaterials will play an im-
30 portant role in the development of future ETD
31 technologies. We have seen significant develop-
32 Artificial Intelligence (AI) ap-
33
ments made in gas sensing such as graphene and
34 proaches to ETD quantum dots, with some systems able to detect
35 multiple classes of explosives at low concentra-
36
Machine learning is a branch of artificial intelli-
tions. SERS also continues to be an active area,
37 gence which uses algorithms to extract patterns
through developments improving the properties
38 and features within data in order to make deci-
39 of plasmonic and non-plasmonic nanoparticles.
sions. Data from sensor arrays is often complex
40 Whilst sensitivity and selectivity remain impor-
and contains many features which are difficult
41 tant goals for ETD systems, consideration of
42
to visualise or interpret through linear regres-
the operational environment is also important
43 sion models. Chemometric approaches such as
for design of future systems as deployment is
44 linear discriminant analysis (LDA) and princi-
45 a balancing act of many considerations. These
pal component analysis (PCA) can reduce the
46 include, cost, sampling throughput, sampling
dimensionality of data enabling feature selec-
47 time, portability and ease of operation. Com-
48 tion and pattern recognition. 386 LDA and PCA
putational chemistry has not been discussed
49 have been applied to a range of data types
here but is one approach which could be used to
50 in the field of ETD, with many examples al-
51 develop rationally designed sensing materials.
ready covered in this review. 66,70,161,171 A num-
52 Other computational approaches beneficial for
ber of machine learning algorithms have been
53 ETD would be modelling explosive adsorption
54 successfully applied to E-nose systems to clas-
on surfaces and vapour plumes in confined ar-
55 sify sensor inputs, leading to improved chemi-
eas, to improve screening procedures and place-
56 cal selectivity. Examples include; random for-
57 ment of sensors.
est, 68,176 support vector machines 91,387 and ar-
58 Acknowledgement This work was carried
tificial neural networks. 107 As detection sys-
59
32
out under EPSRC grant no. EP/L015862/1 as meric Nanocomposites. RSC Adv. 2016,
1
2 part of the University College London Molecu- 6, 3680–3689.
3 lar Modelling and Materials Science Doctoral
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Review

tion. 48 In addition, rats have lower training,

7 nanoparticles on carbon fibre electrodes HMTD

9 TiO2 sensor contained within a quartz crystal NG 1-10 ppm 88

19 Electrochemiluminescence (ECL) resonance TNT 0.65 ppm 95

tion of host-guest binding, electrostatics, and π-

lytes of interest. Palaparthy et.al reports an E-

sequent studies by the same group report the

30 SESI N2 - RDX, PETN, NG, Ppq 225

Table 4: Examples of commercially available colorimetric kits

4 esters, inorganic nitrates, chlo-

7 test kit organic nitrates, peroxides, chlo-

12 tection Test Kit esters, nitrates, chlorates/bromates,

17 nanopaticles and mercaptopropi-

25 Ag@Zn(TA)·(H2 O)·(DMF) 652 – – TATP 0.1 mg L-1 283

32 TPA)2 (H2 O)(CH3 OH)]∞

Pyrenyl–fluorene copolymers – 461 – H2 O2 , 1.6 ppb (H2 O2 ) 286

51 Boronate ester quinoline – 520 365 H2 O2 150 ppt 297

Polyaromatic imine conjugates – 410, 492 308 NB 0.013 µM 298

Table 6: Examples of commercially available ETD Raman systems

Nuctech RT1003 series Diode 830 nm Raman 309

cancy states of different metal oxide substrates,

Table 7: SERS substrates for ETD - recent developments

11 Polystyrene Au nanoparticles 785 TNT 10-5 M 360

Porous silicon photonic Ag nanoparticles 633 TNP 10-8 M 361

14 with Si nanowires rate

18 Silicon Ag/Cu nanoparticles 632 Ammonium nitrate, 5 µM (ammonium ni- 365

19 TNP trate and TNP)

Table 8: Advantages and limitations of ETD technologies

Energetic Small Molecule to a Conduct- Triperoxide by Ion Mobility Spectrome-

orption of Organic Molecules from Sur- Traces of Explosives in Cargo at Concen-

Recognition within Self-Assembled Plas- 379. Huehnerhoff, J.; Lozo, J. A.;

Chemical and Biological Hazards. Chem.

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