Trends in Analytical Chemistry 120 (2019) 115661

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Trends in Analytical Chemistry

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Functionalized nanomaterial for forensic sample analysis

Deepak Rawtani a, Maithri Tharmavaram a, Gaurav Pandey a,
Chaudhery Mustansar Hussain b, *
a
Institute of Research & Development, Gujarat Forensic Sciences University, Sector-9, Gandhinagar, Gujarat 382007, India
b
Department of Chemistry and Environmental Science, New Jersey Institute of Technology, Newark, NJ 07102, USA

a r t i c l e i n f o a b s t r a c t

Article history: Nanomaterials, over the years have found applications in nanomedicine, environmental remediation, and
Available online 13 September 2019 other catalytic applications due to their small size, large surface area and enhanced reactivity. Func-
tionalization of these nanomaterials allows the incorporation of a myriad of functional groups that not
Keywords: only enhance the existing properties of the nanomaterials but also impart additional properties. Due to
Forensic science this, the applicability of these functionalized nanomaterials significantly increases and are therefore
Nanotechnology
highly suitable for use in forensic science. Lately, such functionalized nanoscale materials have assisted in
Nanomaterial
the detection of fingerprints, explosives, chemical and biological warfare agents and unlawful drugs. This
Fingerprinting
Explosive
review discusses about the classification of functionalized nanomaterials, their fabrication, and their
application in different fields of forensic science. It also offers insights into the prospects and challenges
of bringing the functionalized nanomaterial-based technology to the end user in the forensic science
laboratories.
© 2019 Elsevier B.V. All rights reserved.

1. Introduction science such as detection of fingerprints, biological fluids, DNA,

Nanotechnology is an ever-expanding field whose tentacles are
gripping almost every field of science. The crux of nanotechnology
lies in the application of nanosized materials in different fields.
Over the years, nanomaterials have found applications in envi-
ronmental remediation, nanomedicine, biotechnology, food pack-
aging and in the development of biosensors [1e13]. Nanomaterials
due to their size have widely tunable electrical, optical and me-
chanical properties. Their size also allows them to have a large
surface area and excellent reactivity [14]. This reactivity offers the
nanomaterials the potential to be modified by a myriad of func-
tional agents. Functionalization or modification of the nano-
materials enhances the ever-existing properties of the
nanomaterial along with the addition of some desired properties.
Forensic science is a field where errors cannot be tolerated due
to their significance in the deliverance of justice. Areas of forensic
* Corresponding author. Department of Chemistry and Environmental Science,
New Jersey Institute of Technology, 161 Warren St., University Heights, Newark, NJ
07102, USA.
E-mail addresses: rawtanid@gmail.com (D. Rawtani), tmaithri@gmail.com
(M. Tharmavaram), gauravpandey226005@gmail.com (G. Pandey), chaudhery.m.
hussain@njit.edu (C.M. Hussain).
narcotics and poisons demand high precision with the least room
for errors. The sensing and specificity of detection of target mole-
cule gets enhanced by functionalized nanomaterials (FNMs).
Forensic sample analysis has been usually done through cumber-
some analytical techniques which require significant expertise
[15,16]. The nanoscale size, high reactivity, along with other various
properties of these nanomaterials assist in selective binding with
the target group. The most widely applicable properties of the
FNMs are luminescence and electrochemical conductivity, which
allow them to be used directly on the crime scene such as in the
case of fingerprint detection or in the development of a biosensor
for detection of drugs, poisons or alcohol.
The current article elucidates about the different routes for
fabrication and functionalization of various nanoscale materials.
Furthermore, the applications of such functionalized nano-
materials in areas of forensic science such as detection of fin-
gerprints, explosives, illicit drugs, DNA analysis, counterfeiting
and homeland security have also been discussed. Also, insight
has been given in the future prospects of the FNMs in forensic
science and the challenges that may be encountered in its
practical applications.

https://doi.org/10.1016/j.trac.2019.115661
0165-9936/© 2019 Elsevier B.V. All rights reserved.
2 D. Rawtani et al. / Trends in Analytical Chemistry 120 (2019) 115661
2. Types and fabrication of functionalized nanomaterials
2.1. Types of functionalized nanomaterials
As discussed earlier, a functionalized nanomaterial (FNM) can be
defined as a nanomaterial which has been processed post its
fabrication either through chemical or physical route in order to
bestow unique properties, which are not exhibited by their bulk
counterpart. These FNMs are of several types and can be classified
on the basis of: (a) composition of nanomaterial; and (b) func-
tionalization agent, as shown in Fig. 1.
2.1.1. Classification on the basis of composition of nanomaterial
Synthesis of nanomaterials highly depends on the precursor
used. However, the type of precursor used does not limit the
morphologies of the nanomaterials as they come in different
shapes such as nanoparticles, nanowires, nanotubes, nanorods,
nanosheets on the basis of their dimension [17]. The type of pre-
cursor used determines the composition of the consequential
nanomaterial is decided. Some of the common compositions of
nanomaterials include metallic, bimetallic, metal oxide, carbon-
based, and silicon-based. Metallic nanomaterials are usually pre-
pared using noble metals viz. silver (Ag) [18], gold (Au) [19],
palladium (Pd) [20] and platinum (Pt) [21]; as well as using tran-
sition metals such as copper (Cu) [22] iron (Fe) and zinc (Zn). The
properties of such monometallic nanomaterials are solely governed
by the type of metal atom used. Such nanomaterials have found
applications in electronics, catalysis, and antimicrobial agents [23].
Bimetallic nanomaterials, which are derived by the combination of
atoms from two different metals at the nanoscale level [24], have
also attracted the attention of researchers in various fields. The
combination of two different metals synergistically develops very
discrete, remarkable and captivating properties in the nanomaterial
[25]. These bimetallic nanomaterials serve as an excellent tool for
applications related to biosensing, since they allow us to optimize
the Plasmin absorption band energy for the bimetallic mixture.
Some of the common bimetallic nanomaterials include nano-
materials of PteCu, AuePt, CueNi, FeeCu, PdeAg, AueAg, AuePd
[23]. Metal oxide nanomaterials have also been widely applied in
many areas, usually because of their superconducting properties.
The unique and effective photocatalytic activity of these nano-
materials comes from their superconducting nature, which has
been widely used by scientific and technological community the
Fig. 1. Classification of functionalized nanomaterials.
sensing and remediation of agrochemicals such as pesticides. Metal
oxide nanomaterials of silicon dioxide (SiO2), titanium dioxide
(TiO2), zinc oxide (ZnO) and iron oxide (Fe2O3/Fe3O4) have been
used for the aforementioned purposes [24]. Past decades have also
witnessed an upsurge in the use of carbon-based nanomaterials,
which are exclusively composed of sp2 hybridized atoms of carbon.
These nanomaterials can be zero, one or two-dimensional. Such
carbon-based nanostructures are chemically stable and possess
excellent thermal and electrical conductivity along with improved
mechanical and optical properties. Some of the commonly used
carbon-based nanomaterials include fullerenes, carbon nanotubes,
graphene and azobenzene [26]. Several silicon-based nano-
materials have also been used for various purposes by researchers.
Upon bringing the size of silicon to nanoscale, various unique and
size dependent optical properties emerge in the nanomaterial. Such
properties have been harnessed especially in applications related to
fluorescence, in the fields spanning from physics to biomedicine.
Some of the common Si-based nanomaterials include Si nano-
particles and Si nanorods [27].
2.1.2. Classification on the basis of functionalization agent
The surface of nanomaterials has been functionalized with a
number of agents of chemical and biological origin. Chemical route
is the most common strategy applied for such surface functionali-
zation [17]. Some of the common types of functionalization agents
used include organosilanes, polymers and biopolymers, surfactants
and chemicals of biological origin. Over the years, organosilanes
have been used for the modification of surfaces of minerals and
glass fibers. The silicon atom in the monomeric organosilane shares
bond with and organic and an inorganic functional group. The
alkoxy group of organosilane reacts with the surface of nano-
material [17]. Organosilanes such as 3-aminopropyltriethoxysilane
(APTES) [28], 2-aminoethyl-3-aminopropyltrimethoxysilane (APS)
[29], 3-mercaptopropyltrimethoxysilane (MPTS) [30] have been
used by researchers for various applications. Various types of
polymers and biopolymers have also attracted the attention over
the years for functionalizing the nanomaterial's surface with
different functional groups. Among polymers, polyvinyl alcohol
(PVA) [31], polyvinyl pyrrolidone (PVP) [32], poly-
ethylenedioxythiophene (PEDOT) [33] have remained common,
while as far as biopolymers are concerned, polyaniline [34], poly
lactic acid [35], chitosan [36], and DNA [37] have remained at the
top in the priority list of researchers. Surfactants such as oleic acid
 D. Rawtani et al. / Trends in Analytical Chemistry 120 (2019) 115661
[38] and cetrimonium bromide (CTAB) [39] have also been utilized
to functionalize the surface of different nanomaterials. Chemicals of
biological origin have started gaining attention in recent times,
mainly because of their non-toxicity and biocompatibility. Among
them, tannic acid based surface functionalization has been widely
practiced [40,41].
These different kinds of functionalization agents modify the
nanomaterial's surface with myriad functional groups. This created
functional moieties on nanomaterial play a major role in attaching
different kinds of guest molecules on the nanomaterial, depending
upon the desired area of application.
2.2. Fabrication of functionalized nanomaterials
In general, nanomaterials can be fabricated via 2 approaches: (a)
top-down; and (b) bottom-up, as shown in Fig. 2. Top-down
approach can be referred to at the breaking down of bulk mate-
rials up to nanoscale level, while bottom-up approach deals with
the arrangement of atoms in a particular shape, reaching up to the
nanoscale level.
Various chemical and physical routes are employed for the
functionalization of nanomaterials, chemical routes being the more
common among the two. Physical route such as ball milling is
usually applied during top down approach, or post fabrication of
nanomaterial. The functionalization agent, usually in the powder
form is mixed with the nanomaterial powder, and ball milled for
some time for functionalization. In a previous study, this strategy
was utilized to functionalize the nano-diamonds with amine
groups. Ammonium bicarbonate, sodium chloride and sucrose
were used as milling media during the process [42]. Chemical
routes for surface functionalization are usually applied during
bottom-up approach. In some cases, functionalization agent is
added in the already prepared suspension of nanomaterial and
allowed to react with the nanomaterial's surface under optimum
conditions of pH, temperature, pressure and time. In a recent
research, halloysite nanotubes were functionalized with amino-
propyl group, which provided a net positive charge to the surface of
negatively charged nanotubes. This surface modification was car-
ried out with APTES at high temperature, atmospheric pressure
under constant mechanical stirring using toluene as solvent [43]. In
another approach, multi-walled carbon nanotubes were function-
alized with H2SO4:HNO3 mixture in the ratio of 3:1. The function-
alization took place through sonication at high temperature under
reflux [44]. Using the similar chemical route for surface function-
alization, some of the recent works include the functionalization of
carbon nano-onions were with mercaptophenyl methacrylate
(MPMA) [45] and nano-Fe3O4 with pyrene [46].
Both the routes for the fabrication of functionalized nano-
materials have their own merits and demerits. The physical route is
Fig. 2. Approaches for the fabrication of nanomaterials.
Adapted with permission from Pandey et al., 2016.
3
fast and generally non-toxic, but is less efficient and non-specific,
hence not preferred by many. On the other hand, chemical route
is slow and involves use of toxic chemicals many times but has very
high efficiency for surface functionalization. The criteria for
selecting either of the approach ultimately depend on the appli-
cation of the functionalized nanomaterial.
3. Applications of functionalized nanomaterials in forensic
science
3.1. Fingerprint identification
Fingerprints are crucial for the identification of a suspect or a
victim in a crime scene. Conventionally, techniques such as dye
reagents, iodine fuming, powder dusting, Ninhydrin and DFO (1,8-
diazafluoren-9-one) reagents, physical developer and superglue
fuming have been used for the development of fingerprints [47].
However, these techniques have limitations such as toxicity,
destructive nature of visual image, less preservation time, low
sensitivity, selectivity and contrast [48].
Over the years, nanomaterials have found widespread use in the
visualization of the fingerprints. This is mainly due to their small
size which allows them to have a higher surface area and higher
reactivity. These properties can be further enhanced through
functionalization. The small size of the nanomaterials allows them
to bind efficiently to the minute ridge details present on the fin-
gerprints which further causes superior imaging of the ridge details
along with the sweat pores. This is a major advantage over con-
ventional techniques in which the ridge details are usually not
clearly visible due to excessive treatment with the reagents [48].
Quantum dots (QD) and rare earth fluorescence materials such as
YVO4:Eu and LaPo4:Ce, Tb [49] have gained significant attention
due to their small size, excellent fluorescent intensity, good
chemical and photostability.
Latent fingerprints have been developed using fluorescent, metal,
metal oxide, and metal sulphide nanomaterials. These nanoparticles
have either been used in a solution form or in a powder form. Metal
nanoparticles in solution form have been used to detect fingerprints
either through multi-metal deposition or a single metal deposition.
These techniques involve the use of gold nanoparticles (AuNP) along
with the SPR or physical developer. Functionalized metal oxide
nanoparticles such as TiO2 and ZnO NPs and metal sulphide nano-
particles such as Molybdenum disulphide (MoS2) have been used for
this purpose [50] Metal alloy nanoparticles such as GdAlO3:Ce3þ and
CdSe NPs have also been developed for enhanced development of
fingerprints, ease in fixation of the nanocomposite on the finger-
prints and minimisation in the time for development [51,52]. SiNPs
functionalized by organosilanes and conjugated by fluorescent dyes
and SiO2 nanocomposites modified with Europium and sensitising
4 D. Rawtani et al. / Trends in Analytical Chemistry 120 (2019) 115661
ligand have also been used for the development of latent fingerprints
[53,54]. The functionalization allowed the exhibition of a very strong
luminescence with less imaging time. Careful control of the size of
SiNPs also provides them with photonic crystal-like behaviour and
therefore can provide luminescence easily [55]. Fluorescent carbon
nanoparticles (fCNPs) which despite their biocompatibility and low
toxicity have low luminescence can that can be overcome through
nitrogen doping and have been successfully used for the develop-
ment of fingerprints [56]. Bloody fingerprints are prone to smearing
and contamination due to which the ridge details can be easily
destroyed. To overcome this limitation, nanoparticles such as QDs
have been used due to their fluorescence properties. Any limitation
of QD such as background interference and toxicity can be overcome
through functionalization with up-conversion nanoparticles made
from lanthanide doped rare earth materials for their high sensitivity
and strong fluorescence such as NaYF4:Yb, Er, upconversion nano-
materials [57].
3.2. Explosives detection
Explosives are widely used in military conflicts and terrorist
attacks. Explosives such as bombs, grenades, improvised explosive
devices are known to cause widespread mass destruction. A major
drawback with conventional techniques of explosive detection
such as mass spectrometry (MS), gas chromatography (GC), ion
mobility spectrometry (IM) is that they require expertise, are
expensive and time consuming. Over the years, various sensing
methods have been developed. Sensing of explosives usually takes
place either through qualitative (canines and electronic noses) or
quantitative methods (Bioassays) [58]. Sensing using nanomaterials
is usually done either electrochemically or through luminescence.
Most of the explosives are based on nitroamines which have redox
properties that allows them to be electrochemically detected.
Therefore, nanomaterials-based sensors are highly suitable for the
electrochemical detection of the explosives owing to their high
sensitivity and selectivity. The nanomaterials commonly used in
the detection of explosives include graphene [59], Carbon Nano-
tubes (CNT) [60], AuNPs [61], SiNPs [62], Si microspheres with SiO2
core [63], and hybrids of carbon-nanoparticles such as Platinum
nanoparticle-graphene nanosheets [64]. Another technique for the
detection of explosives is based on luminescence. Such a detection
in the presence of low or zero background along with a high-power
source offers very clear detection of the explosives. Explosives such
as Trinitro toluene (TNT), Dinitrobenzene (DNB) have been widely
tested on. While explosives as such do not have any inherent
luminescence properties, they can be combined with a reporter dye
which has excellent fluorescent properties. Organic fluorescent
dyes are commonly used, however a major drawback associated
with such dyes is that they have a limited quantum yield, high
toxicity, stability and labelling efficiency. Nanomaterials overcome
this drawback along with additional benefits such as enhanced
sensitivity, selectivity and contrast. Sensing of explosives has been
carried out through various types of nanomaterials such as non-
metal, metal and metal oxide NPs, QDs, nanomaterials based on
carbon, lanthanide doping and fluorescent dye, metal organic
frameworks, have been used for the detection of explosives [65].
3.3. DNA analysis
Much like fingerprint development, DNA analysis is crucial in
forensics for the deliverance of justice. While fingerprints are useful
in establishing the identity of an individual, DNA analysis helps in
establishing relationships. Conventional detection techniques
involve use of fluorophore labelling sensing systems or Polymerase
Chain Reaction assays. However, these techniques have several
limitations such as such huge costs, requirement of expertise and
time and therefore are difficult to be used in routine analysis. Using
nanomaterials for the detection of minute quantities of DNA at a
crime scene where the DNA samples are not free from contami-
nation and destruction will be highly useful. Several platforms for
the sensing of DNA have been developed which involve the use of
AuNPs for the high dependence of their optical and electrochemical
properties on their size. The changes in its properties in the pres-
ence of DNA are highly sensitive and therefore can accurately
determine the presence of DNA. Apart from AuNP, SiNP are also
useful in DNA detection due to their high stability, unique geo-
metric properties and tunable surface chemistry [66]. Carbon
nanostructures such as CNT and graphene have also been used [67].
Dendrimers, especially G4 PAMAM dendrimers have excellent
stability, surface functionality and geometric symmetry and an
abundance of amine groups and can therefore by functionalized by
myriad groups and enhance their ability to detect DNA [68].
Nanowires [69] and QDs [70] have also been used for the detection
of DNA [71]. Halloysite Nanotubes (HNT) which are clay-based
nanotubes have also been functionalized with AuNP and AgNP for
DNA detection through analysis through colorimetric techniques
[72,73]. The mechanisms generally employed by these nano-
materials can be either electrochemical which mainly employs the
redox reactions or optical which either involves the detection of
light by the fluorophores or through colorimetric techniques [74].
3.4. Sensing of illicit drugs
Illicit drugs especially narcotics play a major role in forensics as
they provide links for criminal profiling, drug trafficking, environ-
mental monitoring and even security surveillance. Several tech-
niques such as GC, high performance liquid chromatography
(HPLC), and mass spectrometry (MS) are used for this purpose. As
mentioned in previous sections, these techniques require expertise,
are time consuming, and cost ineffective. Therefore, alternative
sensing techniques using FNMs are necessary. Sensing using
nanomaterials usually takes place through electrochemical, color-
imetric, fluorescence, Surface Plasmon Resonance (SPR) and Sur-
face Enhanced Raman Spectroscopy (SERS). In the absence of
nanomaterials, electrochemical sensing can have decreased sensi-
tivity, as seen in the case of opioid alkalides [75]. Nanomaterials
such as Graphene oxide (GO) can differentiate between the vol-
tammograms of the drugs due to their high electrochemical con-
ductivity and sensitivity [75]. Apart from GO [75]; CNT electrodes
[76], Au nanoprobes [77] have also been used for the electro-
chemical detection of illicit drugs. These nanomaterials have also
been used in the detection of the drugs through SPR. AuNPs and
AgNPs have excellent SPR effect. SPR results in a red shift of the
wavelength and this shift is further affected by the presence of a
drug. Semiconductor NPs and QDs have also been used for
fluorescence-based sensing due to their excellent chemical stabil-
ity, biocompatibility and excellent quantum yield and fluorescence.
The properties of these nanoparticles further get enhanced through
functionalization. For instance, QDs have been conjugated with
antimorphine for the development of CdSe/ZnS QDs morphine
biosensor. Apart from this, unique nanomaterials such as nano-
diamonds (ND) and nanocrystals have a myriad of electrode
properties and have been used for the sensing of codeine and
morphine respectively [78e80].
3.4.1. Antidoping
Doping refers to the use of illicit drugs such as anabolic steroids,
narcotics, stimulants and peptide hormones in order to enhance
athletic performance. However, this is illegal therefore it is neces-
sary to develop sensors that can test the presence of such drugs in
 D. Rawtani et al. / Trends in Analytical Chemistry 120 (2019) 115661
the biological fluids of the suspect. Metal NPs due to the phe-
nomena of Localised Surface Plasmon Resonance (LSPR), makes
them a suitable candidate for the fabrication of such biosensors
[80e82]. As mentioned in the previous section, the presence of any
illicit drugs causes a shift in the standard SPR signal of the nano-
particle. Therefore, LSPR which is a more localised phenomena al-
lows sensing in Near-infrared (NIR) and UVeVisible regions. Apart
from LSPR, fluorescence-based sensing is also performed by the
nanoparticles. LSPR enhances the fluorescence in the metal NPs
which can also be further enhanced through functionalization of
the nanoparticles with suitable fluorophores such as organic dyes.
Functionalization can also be done using antibodies or aptamers for
enhanced sensing [83e85].
3.5. Counterfeiting
Counterfeiting is a major hassle as they cause copyright
infringement and societal damage. Counterfeited notes can signif-
icantly damage the economy while counterfeit drugs put the public
health at significant risk. Conventionally, techniques such as
detection of holograms, water marks, metal threads, and Radio
Frequency Identification (RFID) have been used in order to increase
the security of materials and thereby help in identification of
counterfeit materials. Yoon et al., 2013 had very well summarised
about the modern techniques developed to improve the identifi-
cation of counterfeit materials. The methods involve SPR methods,
fluorometric approaches which include fluorescent nanostructures,
and QDs [86e88]. Imbibing these nanomaterials in the materials
which need to be protected will significantly increase its safety.
3.6. Homeland security
Identification of Weapons of Mass Destruction (WMD) is a major
part of homeland security as they are known to cause significant
damage to life and property. FNMs play a huge role in this field as
they are known to bind efficiently with the target compounds such
as toxic industrial chemicals, chemical and biological warfare
agents such as Sarin and Tabun [89]. Nanomaterials can serve as
chelating agents to remediate the agents or as sensing agents for
their detection. Nanomaterials can serve as platforms for the
immobilization of enzymes such as acetylcholinesterase [90] and
phosphotriesterase [91] that are known to lose their function in the
presence of an organophosphate nerve agent. The nanomaterials
Fig. 3. Applications of functionalized nanomaterials in forensic sample analysis.
5
can be easily functionalized with organosilanes for the immobili-
zation of the enzyme [43]. Apart from enzymes, Molecularly
Imprinted Polymers (MIP) are a popular way of sensing compounds
as they have the ability to take the shape of any compound that has
been imprinted in it and thereby increase its selectivity to bind to
the particular compound at any condition or location. Several co-
polymers have been found which have been functionalized with
lanthanide coordination complexes in order to bind to chemical
warfare agents [92,93]. These agents have also been detected using
AuNP based sensors [94,95]. An extraordinary method of their
detection is through the use of nanomotors which propel either
through the mechanism of bubble formation or through light
activation of the nanoparticles [92,96] (see Fig. 3, Table 1).
4. Future perspectives and challenges
FNMs hold a great promise for applications in forensic science
due to their excellent sensitivity, selectivity and the ability to
significantly reduce the overall time of analysis. Research on using
FNMs has also been widespread in this field. However, this is still an
emerging field and there are large gaps in the research. For
instance, research on identification of blood stains and other bio-
logical evidence such as semen and saliva are still minimal. FNMs
can be used to develop complex nanoreactor systems which can
carry out reactions to confirm the presence of the biological evi-
dence. Also, the most crucial aspect of any crime scene with a
corpse is to estimate the time of death. Till date, prediction of time
of death is not precise due to various factors such as the tempera-
ture and environment of the crime scene involved in the post-
mortem conditions. FNMs can also be used to develop biosensors
that accurately determine the chemical changes that occur in body
post-mortem. Nanomaterials such as HNTs which are clay-based
naturally occurring nanotubes are prime targets for functionaliza-
tion due to the disparity in functional groups in their inner lumen
(Al2O3) and outer surface (SieOH) [97e101]. These nanomaterials
being non-toxic and cost-effective substitutes to current toxic
nanomaterials (eg. CNT), become well-suited for developing bio-
sensors. In addition, functionalized nanomaterials assist in mini-
mizing the counterfeiting area by playing the role of taggants for
validating the objects [102]. Apart from this, nanomaterials can be
used to develop on-site sensors for sensing explosives that are
being used illegally as well. For instance, In Columbia, explosives
are used illegally to mine gold. Explosives such as Indugel and
Table 1

6
Functionalized nanomaterials in forensic applications.

S. No. Nanomaterial Functionalization agent Functional group Functionalization method Application Target/product Detection method Reference

1 GdAlO3:Ce3þ Aluminium AlO3, Solution Fingerprint identification Latent Cyan blue luminescence [51]
nanophosphors nitrate Ce3þ ions Combustion method Fingerprint
nonahydrate
Cerium (III)
nitrate
hexahydrate
2 PR254@SiNP PVP Vinylpyrollidone Stober method Fingerprint identification Latent Fluorescence [53]
Fingerprint
3 Carbon NP Malic acid, N group Pyrolysis method Fingerprint identification Latent Fluorescence [56]
Ammonium oxalate Fingerprint
4 SiO2 NP Europium, Eu3þ Solegel method Fingerprint identification Latent Fluorescence [54]
1,10-Phenanothroline Fingerprint
5 CdSe NP Mercaptoacetic acid Sulphydryl group Reflux method Fingerprint identification Latent Fluorescence and white SPR [52]
Fingerprint
6 YVO4:Eu PEI eNH2 Hydrothermal method Fingerprint identification Latent Fluorescence [49]

D. Rawtani et al. / Trends in Analytical Chemistry 120 (2019) 115661

nanocrystals Fingerprint
7 LaPO4:Ce, Tb Ethylene glycol eOH Hydrothermal method Fingerprint identification Latent Fluorescence [49]
nanobelts Fingerprint
8 Graphene 2,6-Diamino pyridine Pyridinic Nitrogen SN2 reaction method Explosives detection Trinitrophenol FRET mechanism [59]
9 CNT MHTPP Porphyrin Electrolytic method Explosives detection DNB DPS voltammetry [60]
THTPP
10 AuNPs 2-Mercaptoethane Oligoaniline group, Wet synthesis method Explosives detection TNT Voltammetry [61]
sulfonate Aminothiophenol group
p-Aminothiophenol
11 SiNPs Polyguanine Guanine Wet synthesis method Explosives detection TNT Voltammetry [62]
12 Si nanoshells 3-APTS eNH2 Reflux hydrolysis Explosives detection TNT, TNB, DNT Voltammetry [63]
13 PNEGHNs PMMA Methacrylic acid Microwave-assisted Explosives detection TNT Electrochemical [64]
heating method
14 PAMAM Amino modified SS DNA Wet synthesis method DNA analysis DNA Electrochemical Impedance [68]
dendrimers probe DNA
15 Si nanowire Trimethoxysilane Methoxy group Reflux hydrolysis DNA analysis DNA Electrochemical [69]
aldehyde
16 Quantum dots Sulfhydryl-DNA DNA Ligand-exchange method DNA analysis DNA Fluorescence [70]
17 HNT Chloroauric acid AuNPs On-spot reduction method DNA analysis DNA Fluorescence [72]
18 HNT Silver nitrate AgNPs On-spot reduction method DNA analysis DNA Fluorescence [73]
19 Graphene PSS Sodium Hydrothermal reaction Illicit drug sensing Heroine, morphine, Voltammetric [75]
nanosheets 4-styrenesulfone noscapine
20 MB-AuNPs Cocaine aptamer, Complementary Wet synthesis method Illicit drug sensing Cocaine Chemiluminescence [77]
nanoprobes signal DNA, DNA strands
Barcode DNA
21 AuNP G4-PAMAM NH2 group Wet synthesis method Illicit drug sensing (anti-doping) Insulin SPR [84]
22 AuNP Secondary IgG Wet synthesis method Illicit drug sensing (anti-doping) Testosterone SPR [85]
antibody
23 Ag, AuNP MUA, DDAB Trans-azobenzene Wet synthesis method Counterfeiting Erasable inks Colorimetric [86]
Nano inks groups,
Dodecylamine
24 Fe3O4 CNC Silica layer SiO2 Wet synthesis method Counterfeiting e Optical detection [88]
25 AuNP Lanthanum La3þ Crosslinking method Homeland security Methyl parathion Colorimetric [93]
chloride
26 AuNP Ascorbic acid Ascorbic group Wet synthesis method Homeland security Dichlorvos Colorimetric [95]

PR254: allylated Pigment Red 254; PVP: polyvinylpyrrolidone; 3-APTS: (3-aminopropyl)triethoxysilane; MHTPP: 5-(4-hydroxyphenyl)-10,15,20-triphenylporphyrin, THTPP: (meso-tetrakis(4-hydroxyphenyl)porphyrin); DNB:
dinitrobenzene; TNT: trinitrotoluene; DNT: dinitrotoluene; PNEGHNs: Pt nanoparticle ensemble-on-graphene hybrid nanosheet; HNT: halloysite nanotubes; SS DNA: single stranded deoxyribose nucleic acid; PMMA: pol-
y(methacrylic acid sodium salt); PSS: poly(sodium 4-styrenesulfonate); MB: magnetic microbeads; PEI: polyethylene amine; CNC: colloidal nanocrystal clusters; MUA: (11-mercaptoundcanoxy)azobenzene; DDAB: didode-
cyldimethylammonium bromide; G4 PAMAM: polyamidoamine dendrimer; SPR: surface plasmon resonance.
 D. Rawtani et al. / Trends in Analytical Chemistry 120 (2019) 115661
‘Polvo Loco’ are widely used for this purpose [103], therefore rapid
onsite testing of such explosives using the functionalized nano-
materials based onsite sensor can be done. This will assist in con-
stant monitoring of the illegal use of explosives.
One of the key challenges of using FNMs for forensic science is
the translation aspect of the technology to the market. Commer-
cialization of the FNMs to be used in every-day life will be very
challenging part. One of the major hurdles in this journey will be
the ease of use and handling of the FNMs by the end users. It is
important that the applicability of such nanomaterials be known to
the end users who are working in various forensic science labora-
tories across the world. Also, it is imperative that the technology
involving the nanomaterials be cost-effective in order to obtain
widespread usage in countries with high crime rate.
5. Conclusion
This review has attempted to discuss in brief about FNMs, the
different routes of functionalization, their unique optical, elec-
trical and mechanical properties and their applications in forensic
science. Nanomaterials such as QDs, CNT, GO, metal, metal oxide,
metal alloy and polymeric nanoparticles have been functionalized
with a myriad of functionalization agents such as organosilanes,
polymers, biopolymers, surfactants and compounds of biological
origin. Functionalization allows the introduction of guest groups
that not only impart additional properties to the nanomaterials
but also enhances their existing properties. They have been
applied in the detection of fingerprints, explosives, illicit drugs
and even counterfeiting and homeland security. The most widely
used properties of the nanomaterials are their luminescence and
electrochemistry due to which the nanomaterials can be used
either directly or incorporated in biosensors. These nanomaterials
can not only increase the sensitivity and selectivity of sensing but
can also be eco-friendly. The use of FNMs in forensic science holds
a lot of promise and hopefully this review raises awareness of the
implications of FNMs in the forensic science. Optimistically, in due
time the practical applications of the various FNMs-based tech-
nologies soon reach the end users in the forensic laboratories
across the world.
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