Role of Nanomaterials For Forensic Investigation and Latent Fingerprinting - A Review
Role of Nanomaterials For Forensic Investigation and Latent Fingerprinting - A Review
Role of Nanomaterials For Forensic Investigation and Latent Fingerprinting - A Review
doi: 10.1111/1556-4029.14172
CRITICAL REVIEW Available online at: onlinelibrary.wiley.com
CRIMINALISTICS
Vandana Prasad,1 M.Sc.; Sally Lukose,2 Ph.D.; Prashant Agarwal,1 Ph.D.; and Lalit Prasad,3 Ph.D.
ABSTRACT: The imminent nanotechnology and progressive instrumentations together have vast applications in the field of forensic science.
Few prominent examples are gold nanoparticles for improvising the efficiency of polymerase chain reaction and atomic force microscopy for
examining ink and bloodstains. Characteristics like distinct ridge details of fingerprints could be obtained by applying different nanoparticles
such as silver, zinc oxide, silicon dioxide, aluminum oxide, gold (with silver physical developer), europium, fluorescent carbon, and amphiphi-
lic silica on a range of object surfaces, and among all, gold is most commonly used. Fingerprint is considered noteworthy evidence in any
crime scene, and nano-based techniques hold immense future potential in fingerprint investigations. Therefore, this paper focuses on the appli-
cations of nanoparticles in developing and detecting the latent fingerprints.
KEYWORDS: forensic science, forensic investigation, latent fingerprint, nano-techniques, nano-forensics, nano-fingerprinting
Nanotechnology is the field of science that deals with the Considering the progress of nanotechnology in forensic inves-
study of materials in the nanometer scale (1). Additionally, the tigation, some of the major roles of nanotechnology and its
domain can also be defined as the synthesis of matter on an applications in various fields of forensic science are summarized
atomic level, with sizes ranging from 1 to 100 nm. in Fig. 1.
The use of nanoscience and nanotechnology has been known Since nanotechnology is advancing with time, the instrumenta-
since the 4thcentury. Gold was the first introduced nanoparticle, tions which were earlier used in other fields to study nanomateri-
which was applied as a coating agent on the Lycurgus cup als have also been upgraded to suit the needs of forensic
developed by the Roman workers. Currently, nanotechnology science. Atomic force microscopy (AFM) has been updated in
has vast applications in different fields including electronics, this manner. The instrument has provided a valuable contribution
drug development/analysis, and construction. Products as diverse to the field over the recent years. Therefore, nanotechnology pro-
as nano-coated waterproof shirts and nanotransistors on com- vides a new perspective in the field of forensic science for
puter chips have been developed (2). From ancient to the recent examining the evidences in any crime scene (1,3).
times, it has been perceived that nanoscience plays an important This paper presents a literature review on the major role of
role in different areas of science. Thus, in the present era, nano- nanotechnology in the development and detection of latent fin-
materials have fueled a boom in many aspects of science and gerprints. Besides, it gives an overview on the applications of
technology. nano-based materials in the development of latent fingerprints
In addition to its vital applications in several other fields, nan- along with numerous techniques and instrumentations applied in
otechnology also has a significant impact on forensic science. forensic analysis by nanoscience. The paper also discusses the
This field is referred to as nano-forensics and is the latest inno- future aspects of nano-based techniques in the field of forensic
vation in the field of forensic science. The evolution of nano- science.
sensors and nano-devices for identifying anonymous evidences
which are challenging to identify by using the current techniques
Forensic Applications of Nanotechnology
is one of novel applications.
Forensic applications of nanotechnology have been discussed
in the following major headings:
1
Forensic Science Department, School of Basic and Applied Sciences, Gal-
gotias University, Greater Noida, Uttar Pradesh, India. Nanotechnology and Questioned Documents
2
Forensic Science Department, College of Traffic Management, IRTE,
Faridabad, Haryana, India. To study the forensic materials, a new advanced AFM which
3
Chemistry Department, School of Basic and Applied Sciences, Galgotias works at the nanoscale was introduced in forensics (1). This
University, Greater Noida, Uttar Pradesh, India.
Corresponding author: Lalit Prasad, Ph.D. E-mail: [email protected] instrument is a type of microscope which can analyze ink cross-
Received 11 April 2019; and in revised form 30 May 2019, 25 July 2019; ing by scanning the surface of documents through which the pat-
accepted 26 July 2019. tern of pen strokes and 3-D surface morphology can be
FIG. 2––(A) The optical micrograph of ink passage scan area. (B) The 3D height image shows deposition of the two inks: first by the red stamp ink and sec-
ond by the blue ballpoint ink. (C) The scan area height, Z-sensor, amplitude, and phase images (1).
PRASAD ET AL. . FORENSIC SCIENCE, LATENT FINGERPRINT, NANOTECHNIQUES 3
important evidences found at the crime scene is fingerprints citrate ion were applied on the fingerprint before the treatment
since they are recognized as generalized proofs of human iden- with Ag-PD solution (13,14) as shown in Fig. 3 (15). A brief
tity (7–9). description of the comparative work is given in Table 1.
Fingerprints may be latent, patent, or plastic in nature.
• Patent fingerprints are those that are easily visible to the Gold Nanoparticles (AuNPs)
naked eye and can be developed on the object by foreign
substances such as blood, paint, and grease. Gold nanoparticles (AuNPs) play a significant role in the
• Plastic fingerprints are those that are formed by the pressure development of latent fingerprints because of their inert nature,
of skin friction on soft objects such as soap, clay, putty, wax, high selectivity and sensitivity, and attributes, which enable the
and glue. storage of the developed fingerprints for a prolonged period of
• Latent fingerprints are those that are not visible to the naked time (16). Owing to these properties, the gold nanoparticles were
eye and are transferred to the surface through bodily secre- used to enhance the visibility of the latent fingerprints by multi-
tions and contaminants found on the fingers. These are the metal deposition (MMD) which involves a two-step sol–gel
preeminent forms of fingerprint evidence encountered in the method. The fingerprint-bearing surface was immersed in the
crime scene; yet, they are the most challenging ones to iden- solution of gold nanoparticles (stabilized in citrate ion medium)
tify (7,10). followed by the addition of silver physical developer (Ag-PD)
solution (7,16). Characterization was done by using UV-Vis
Fingerprints contain bodily secretions and contaminations
spectrophotometer as shown in Fig. 4 (17). The gold nanoparti-
from the surroundings (7,11). Secretions from the three types of
cles bind to the fingerprint residue and catalyze the precipitation
sweat glands, namely eccrine, apocrine, and sebaceous, may be
of silver ions to metallic silver (8,15,17). Thus, a silver image of
present in latent fingerprints (7). The choice of technique for
the latent fingerprint is obtained because of the electrostatic
latent fingerprint development depends on the content of the
interaction between the negatively charged gold nanoparticles
latent fingerprint as well as on the nature of the surface.
and the positive charged fingerprint residue as shown in Fig. 5
Currently, a myriad of techniques, such as iodine fuming, nin-
(18).
hydrin, silver nitrate, and cyanoacrylate, are being used to
However, the application of the MMD method is limited
develop the latent fingerprints (7). However, in the case of addi-
because it requires the object bearing the fingerprints to be
tionally aged prints, the environment might have contaminated
bathed in an aqueous solution of the gold nanoparticles. There-
them. In such situations, the fingerprints may suffer from
fore, the method is not suitable for developing the prints on sur-
reduced reactivity to detection from the above-mentioned meth-
faces such as walls and floors at the scene of crime or for any
ods (12). Therefore, over the past few generations, nano-tech-
object too large to be soaked in a desktop bath. The details of
niques have been chiefly used for the development of latent
the comparative work are furnished in Table 1.
fingerprints in order to better identify them (1,19). Furthermore,
the method offers the opportunity to develop new fingerprint
techniques with superior properties including enhanced selectiv- Zinc Oxide Nanoparticles (ZnO-NPs)
ity, improved contrast with the background, and increased sensi-
According to literature survey, ZnO has amazing properties
tivity.
such as wide band gap (3.37 eV), high excitation binding energy
The different types of nanoparticles and their applications in
(60 MeV), which allows its transition even at room temperature,
the identification of latent fingerprints are discussed in the fol-
and an additional adhesive property that facilitates interaction
lowing sections.
with the lipids and proteins in the fingerprint residue at ambient
temperatures (8,19,20). ZnO nanoparticles were used in the form
of a nano-powder for developing the aged latent fingerprints on
Silver Nanoparticles
nonporous surfaces. The developed fingerprint exhibited distin-
As per literature, metallic silver has an affinity for the organic guishable ridge details which fluoresced under UV light as por-
constituents of the fingerprint residue. Based on this concept, sil- trayed in Fig. 6 (22). Researchers from the Sydney University
ver nanoparticles have been used as a reagent in the silver physi- recently reported that ZnO nano-powders (20 nm) not only pro-
cal developer (Ag-PD) method since 1970 for the visualization duce clear prints but also naturally fluoresce in UV light under
of latent fingerprints on porous paper surfaces. The Ag-PD wet conditions (21). Other researchers have also documented that
method involves an oxidation–reduction couple in which an iron nanostructured zinc oxide produces a good fluorescent image of
salt reduces an aqueous solution of silver nitrate to metallic sil- the latent fingerprints when illuminated by long-wave UV light
ver. The silver nanoparticles (1–200 nm) formed during the reac- (22,23). A new combination of nano-powder consisting of ZnO-
tion interact with the organic constituents of the fingerprint SiO2 has been found to be effective in developing the latent fin-
residue and enable the visualization of the impression as a dark gerprints on various nonporous surfaces (8,20). Information on
gray or black silver image on the paper surface. The fingerprint the comparative work is given in Table 1.
development is due to the presence of electrostatic force of
attraction between the positively charged fingerprint residues and
Silica Nanoparticles (SiO2-NPs)
negatively charged silver colloids (12,13). Other researchers
have also reported that Ag-PD method is suitable for the identifi- The use of silica nanoparticles (SiO2-NPs) serves as a novel
cation of latent fingerprints on porous items, especially when method of improving the detection of latent fingerprints because
visualization on articles which have been deliberately or acciden- of their ease of synthesis and their ability to coat dyes, which
tally moistened is involved (13) Table 1. prevents photo-decomposition (10). Owing to their coating abil-
Nonetheless, the method has one drawback, that is, the Ag- ity, the nanoparticles were functionalized with dye particles to
PD solution alone yields poor visibility of the fingerprints. To recognize the fingerprint residues, where the outer shell of SiO2-
overcome this problem, gold nanoparticles stabilized with a NPs was functionalized to create interaction with organic
4 JOURNAL OF FORENSIC SCIENCES
compounds of latent fingerprints such as amino acids and pro- fingerprints by gold nanoparticles by the multimetal deposition
teins to enhance the latent fingerprint image on a wide range of method. To determine the electrostatic mechanism, the finger-
object surfaces (23). print-bearing object surface (aluminum foil) was immersed in a
A study has reported the electrostatic mechanism between the solution of carboxyl-functionalized silica nanoparticles. The neg-
silica nanoparticles and the fingerprint residue, which is similar atively charged silica nanoparticles interacted with the positively
to the interaction taking place during the detection of latent charged amine groups of the fingerprint residue and formed an
PRASAD ET AL. . FORENSIC SCIENCE, LATENT FINGERPRINT, NANOTECHNIQUES 5
FIG. 5––(a) Optical laser scanner image of the latent fingerprint on glass surface enhanced by the MMD technique. The black and white lines represent the
ridges and furrows. (b) A high-resolution scanning electrochemical microscopy (SECM) image (3–2 mm) of the sample with a scan rate of 300 mm/sec. The
SECM image area corresponds approximately to the rectangle region marked (inside black line) in (b), and the brown and white lines represent the ridges and
furrows (18).
6 JOURNAL OF FORENSIC SCIENCES
FIG. 8––Results obtained after application of SiO2-COOH NPs at pH 6. For the right half, EDC/NHS is used to mediate the reaction. On the right shows the
bond formation between -COOHl groups present on SiO2 NPs surface and amine groups found in the fingerprint secretion. The amide linkage is mediated by
the use of EDC/NHS (24).
PRASAD ET AL. . FORENSIC SCIENCE, LATENT FINGERPRINT, NANOTECHNIQUES 7
FIG. 11––Synthesis of 1 and 2. (a) CH3CN, 85°C, 18 h, N2. (b) CH2Cl2, SOCl2, reflux. (c) CH2Cl2, RT. (d) Toluene, 24-h stirring, RT. TOAB, tetraoctylam-
monium bromide (30).
8 JOURNAL OF FORENSIC SCIENCES
paper, and the gold nanoparticles lead to the development of ordinary luminescent powders owing to its intense luminescence
latent prints as shown in Figs 12 and 13 (30). A brief sketch of property (32). A brief scheme of the comparative work is given
the comparative work could be found in Table 1. in Table 1.
FIG. 12––Development of latent fingerprint by bifunctional reagent fol- FIG. 13––A fresh sebaceous fingerprint (after immersion in water for
lowed by Ag-PD (30). 5 min and drying under air) developed by treatment with 2(above fig), fol-
lowed by Ag-PD (30).
PRASAD ET AL. . FORENSIC SCIENCE, LATENT FINGERPRINT, NANOTECHNIQUES 9
nanoparticles was proposed for latent fingerprint detection. For sensing of the cocaine metabolites. A cocaine-specific DNA
developing latent fingerprints, amphiphilic silica nanoparticle aptamer was cut into two pieces and attached to different
powders were made using 4-(chloromethyl) phenyltrichlorosi- AuNPs. The DFM images of cocaine-loaded latent fingerprints
lane. The synthesized powder was characterized by SEM, FTIR depicted true-green to red color changes owing to the surface
spectrometer, X-ray photoelectron spectra (XPS), and X-ray plasmon resonance of the gold nanoparticles. Thus, a quantita-
powder diffraction (XRD). It was inferred that the material has tive method was exploited to identify the cocaine loading in
affinity toward the amino acids present in the fingerprint residue latent fingerprints. Subsequently, for the visualization of latent
owing to its amphiphilic nature, which results in a clear visibility fingerprints, 10 lL solution of cocaine was drop-casted on the
of the fingerprint on the nonporous surface ((43,37)). Details of fingerprint and air-dried. The dried latent fingerprint cast was
the comparative study are provided in Table 1. collected and incubated with the aptamer-bound AuNPs. The
DFM image of the latent fingerprint revealed second- and third-
level ridge characteristics (38). Details of the comparative study
Nanoplasmic Imaging of Latent Fingerprints and
are provided in Table 1.
Identification of Cocaine Metabolites using Gold
Nanoparticles
Evolution of Nanoparticles in the Field of Forensic
A novel nanoplasmonic spectroscopic method was demon-
Fingerprinting
strated for imaging latent fingerprints and identifying cocaine
metabolites in latent fingerprints by using gold nanoparticles as In the early 1970s, some information was available on the
a probe. Dark-field microscopy (DFM) was employed for high- detection of latent fingerprints with nanoparticles. During the
resolution imaging of the latent fingerprints and the cocaine 1980s, nanoparticles such as silver and gold were used in the
metabolites. The method comprised of two steps. Cocaine identi- common silver physical developer technique for the visualization
fication in the latent fingerprints was initially done for which of latent fingerprints on porous paper surfaces. However, during
gold nanoparticles were used as a probe for the aptamer-based these two decades, the nanoparticles were not utilized much for
10 JOURNAL OF FORENSIC SCIENCES
development on paper – a remedy to the variation in sweat composition. 35. Qin G, Zhang M, Zhang Y, Zhu Y, Liu S, Wu W, et al. Visualizing
Angew Chem Int Ed 2012;51(49):12224–7. latent fingerprints by electrodeposition of metal nanoparticles. J Elec-
31. Becue A, Champod C, Marot P. Use of gold nanoparticles as molecular troanal Chem 2013;693:122–6.
intermediate for the detection of fingermarks. Forensic Sci Int 2007;168 36. Lombardo D, Kiselev MA, Magazu S, Calandra P. Review article:
(2–3):169–76. amphiphiles self- assembly: basic concepts and future perspectives
32. Das A, Sharma V. Synthesis and characterization of Eu+3 doped a- of supramolecular approaches. Adv Cond Matter Phys 2015;2015:
Al2O3 nanocrystalline powder for novel application in latent fingerprint 151683.
development, research article. Adv Mater Lett 2016;7(4):302–6. 37. Huang W, Li X, Wang H, Xu X, Liu H, Wang G. Synthesis of amphi-
33. Li H, Guo X, Liu J, Li F. A synthesis of fluorescent starch based on philic silica nanoparticles for latent fingerprint detection. Anal Lett
carbon nanoparticles for fingerprints detection. Opt Mater 2016;60:404– 2015;48:1524–35.
10. 38. Li K, Qin W, Li F, Zhao X, Jiang B, Wang K, et al. Nanoplasmonic
34. Avilez HVR, Casadiego DAC, Avila ALV, Perez OJP, Almodovar J. imagining of latent fingerprints and identification of cocaine. Angew
Production of chitosan coatings on metal and ceramic biomaterials. Chi- Chem Int Ed 2013;52(44):11542–5.
tosan Based Biomater 2017;1:255–93.