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Nanoparticles: Properties, Applications and Toxicities: Arabian Journal of Chemistry

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Arabian Journal of Chemistry (2019) 12, 908–931

King Saud University

Arabian Journal of Chemistry


www.ksu.edu.sa
www.sciencedirect.com

REVIEW

Nanoparticles: Properties, applications and


toxicities
Ibrahim Khan a,*, Khalid Saeed b, Idrees Khan c

a
Center of Research Excellence in Nanotechnology (CENT), King Fahd University of Petroleum and Minerals (KFUPM),
Saudi Arabia
b
Department of Chemistry, Bacha Khan University, Charsadda, Pakistan
c
Department of Chemistry, University of Malakand, Chakdara, Pakistan

Received 18 March 2017; accepted 10 May 2017


Available online 18 May 2017

KEYWORDS Abstract This review is provided a detailed overview of the synthesis, properties and applications
Nanoparticles; of nanoparticles (NPs) exist in different forms. NPs are tiny materials having size ranges from 1 to
Fullerenes; 100 nm. They can be classified into different classes based on their properties, shapes or sizes. The
Optical; different groups include fullerenes, metal NPs, ceramic NPs, and polymeric NPs. NPs possess
Plasmonic; unique physical and chemical properties due to their high surface area and nanoscale size. Their
Toxicity optical properties are reported to be dependent on the size, which imparts different colors due to
absorption in the visible region. Their reactivity, toughness and other properties are also dependent
on their unique size, shape and structure. Due to these characteristics, they are suitable candidates
for various commercial and domestic applications, which include catalysis, imaging, medical appli-
cations, energy-based research, and environmental applications. Heavy metal NPs of lead, mercury
and tin are reported to be so rigid and stable that their degradation is not easily achievable, which
can lead to many environmental toxicities.
Ó 2017 The Authors. Production and hosting by Elsevier B.V. on behalf of King Saud University. This is
an open access article under the CC BY-NC-ND license (http://creativecommons.org/licenses/by-nc-nd/4.0/).

Contents

1. Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 909
2. Classification of NPs . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 909
2.1. Carbon-based NPs . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 909

* Corresponding author.
E-mail address: ebraheem.chemist@gmail.com (I. Khan).
Peer review under responsibility of King Saud University.

Production and hosting by Elsevier

http://dx.doi.org/10.1016/j.arabjc.2017.05.011
1878-5352 Ó 2017 The Authors. Production and hosting by Elsevier B.V. on behalf of King Saud University.
This is an open access article under the CC BY-NC-ND license (http://creativecommons.org/licenses/by-nc-nd/4.0/).
Nanoparticles 909

2.2. Metal NPs . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 910


2.3. Ceramics NPs. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 910
2.4. Semiconductor NPs. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 910
2.5. Polymeric NPs . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 910
2.6. Lipid-based NPs . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 911
3. Synthesis of nanoparticles . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 912
3.1. Top-down syntheses . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 912
3.2. Bottom-up syntheses . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 913
4. Characterization of NPs. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 915
4.1. Morphological characterizations. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 915
4.2. Structural characterizations . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 916
4.3. Particle size and surface area characterization . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 918
4.4. Optical characterizations . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 919
5. Physicochemical properties of NPs . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 921
5.1. Electronic and optical properties . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 921
5.2. Magnetic properties . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 922
5.3. Mechanical properties . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 922
5.4. Thermal properties . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 923
6. Applications of NPs . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 924
6.1. Applications in drugs and medications . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 924
6.2. Applications in manufacturing and materials. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 924
6.3. Applications in the environment. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 925
6.4. Applications in electronics . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 925
6.5. Applications in energy harvesting . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 925
6.6. Applications in mechanical industries . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 926
7. Toxicity of NP . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 926
8. Conclusion . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 927
9. Recommendations . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 927
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 927

1. Introduction such exceptional characteristics, these materials got immense interest


of researchers in multidisciplinary fields. Fig. 2 shows scanning elec-
Nanotechnology is a known field of research since last century. Since tron microscopy (SEM) and transmittance electron microscope
‘‘nanotechnology” was presented by Nobel laureate Richard P. Feyn- (TEM) images of mesoporous and nonporous methacrylate-
man during his well famous 1959 lecture ‘‘There’s Plenty of Room at functionalized silica (MA-SiO2). Mesoporousity imparts additional
the Bottom” (Feynman, 1960), there have been made various revolu- characteristics in NPs. The NPs can be employed for drug delivery
tionary developments in the field of nanotechnology. Nanotechnology (Lee et al., 2011), chemical and biological sensing (Barrak et al.,
produced materials of various types at nanoscale level. Nanoparticles 2016), gas sensing (Mansha et al., 2016; Rawal and Kaur, 2013;
(NPs) are wide class of materials that include particulate substances, Ullah et al., 2017), CO2 capturing (Ganesh et al., 2017;
which have one dimension less than 100 nm at least (Laurent et al., Ramacharyulu et al., 2015) and other related applications (Shaalan
2010). Depending on the overall shape these materials can be 0D, et al., 2016).
1D, 2D or 3D (Tiwari et al., 2012). The importance of these materials In this review article, we provide a general overview on the different
realized when researchers found that size can influence the physio- types, synthesis methods, characterizations, properties and applica-
chemical properties of a substance e.g. the optical properties. A 20- tions of NPs. The last section is also provided with the future aspects
nm gold (Au), platinum (Pt), silver (Ag), and palladium (Pd) NPs have and recommendations.
characteristic wine red color, yellowish gray, black and dark black col-
ors, respectively. Fig. 1 shows an example of this illustration, in which 2. Classification of NPs
Au NPs synthesized with different sizes. These NPs showed character-
istic colors and properties with the variation of size and shape, which
can be utilized in bioimaging applications (Dreaden et al., 2012). As NPs are broadly divided into various categories depending on
Fig. 1 indicates, the color of the solution changes due to variation in their morphology, size and chemical properties. Based on
aspect ratio, nanoshell thickness and % gold concentration. The alter- physical and chemical characteristics, some of the well-
ation of any of the above discussed factor influences the absorption known classes of NPs are given as below.
properties of the NPs and hence different absorption colors are
observed. 2.1. Carbon-based NPs
NPs are not simple molecules itself and therefore composed of
three layers i.e. (a) The surface layer, which may be functionalized with
a variety of small molecules, metal ions, surfactants and polymers. (b) Fullerenes and carbon nanotubes (CNTs) represent two major
The shell layer, which is chemically different material from the core in classes of carbon-based NPs. Fullerenes contain nanomaterial
all aspects, and (c) The core, which is essentially the central portion of that are made of globular hollow cage such as allotropic forms
the NP and usually refers the NP itself (Shin et al., 2016). Owing to of carbon. They have created noteworthy commercial interest
910 I. Khan et al.

also in nanocomposites for many commercial applications


such as fillers (Saeed and Khan, 2016, 2014), efficient gas
adsorbents for environmental remediation (Ngoy et al.,
2014), and as support medium for different inorganic and
organic catalysts (Mabena et al., 2011).

2.2. Metal NPs

Metal NPs are purely made of the metals precursors. Due to


well-known localized surface plasmon resonance (LSPR) char-
acteristics, these NPs possess unique optoelectrical properties.
NPs of the alkali and noble metals i.e. Cu, Ag and Au have a
broad absorption band in the visible zone of the electromag-
netic solar spectrum. The facet, size and shape controlled syn-
thesis of metal NPs is important in present day cutting-edge
materials (Dreaden et al., 2012). Due to their advanced optical
properties, metal NPs find applications in many research areas.
Gold NPs coating is widely used for the sampling of SEM, to
enhance the electronic stream, which helps in obtaining high
quality SEM images (Fig. 1). There are many other applica-
tions, which are deeply discussed in applications section of this
review.

2.3. Ceramics NPs

Ceramics NPs are inorganic nonmetallic solids, synthesized via


heat and successive cooling. They can be found in amorphous,
polycrystalline, dense, porous or hollow forms (Sigmund et al.,
2006). Therefore, these NPs are getting great attention of
researchers due to their use in applications such as catalysis,
photocatalysis, photodegradation of dyes, and imaging appli-
cations. (Thomas et al., 2015).

2.4. Semiconductor NPs

Semiconductor materials possess properties between metals


Figure 1 Color dependence of Au NPs on size and shape
and nonmetals and therefore they found various applications
(Dreaden et al., 2012).
in the literature due to this property (Ali et al., 2017; Khan
et al., 2017a). Semiconductor NPs possess wide bandgaps
and therefore showed significant alteration in their properties
due to their electrical conductivity, high strength, structure, with bandgap tuning. Therefore, they are very important mate-
electron affinity, and versatility (Astefanei et al., 2015). These rials in photocatalysis, photo optics and electronic devices
materials possess arranged pentagonal and hexagonal carbon (Sun, 2000). As an example, variety of semiconductor NPs
units, while each carbon is sp2 hybridized. Fig. 3 shows some are found exceptionally efficient in water splitting applications,
of the well-known fullerenes consisting of C60 and C70 with due to their suitable bandgap and bandedge positions
the diameter of 7.114 and 7.648 nm, respectively. (Hisatomi et al., 2014).
CNTs are elongated, tubular structure, 1–2 nm in diameter
(Ibrahim, 2013). These can be predicted as metallic or semicon- 2.5. Polymeric NPs
ducting reliant on their diameter telicity (Aqel et al., 2012).
These are structurally resembling to graphite sheet rolling These are normally organic based NPs and in the literature a
upon itself (Fig. 4). The rolled sheets can be single, double special term polymer nanoparticle (PNP) collective used for
or many walls and therefore they named as single-walled it. They are mostly nanospheres or nanocapsular shaped
(SWNTs), double-walled (DWNTs) or multi-walled carbon (Mansha et al., 2017). The former are matrix particles whose
nanotubes (MWNTs), respectively. They are widely synthe- overall mass is generally solid and the other molecules are
sized by deposition of carbon precursors especially the atomic adsorbed at the outer boundary of the spherical surface. In
carbons, vaporized from graphite by laser or by electric arc on the latter case the solid mass is encapsulated within the particle
to metal particles. Lately, they have been synthesized via chem- completely (Rao and Geckeler, 2011). The PNPs are readily
ical vapor deposition (CVD) technique (Elliott et al., 2013). functionalize and thus find bundles of applications in the liter-
Due to their unique physical, chemical and mechanical charac- ature (Abd Ellah and Abouelmagd, 2016; Abouelmagd et al.,
teristics, these materials are not only used in pristine form but 2016).
Nanoparticles 911

Figure 2 FE-SEM micrographs of (a) nonporous MA-SiO2 NPs, (b) mesoporous MA-SiO2 NPs. TEM images of (c) nonporous MA-
SiO2 NPs and (d) mesoporous MA-SiO2 NPs (Lee et al., 2011).

Figure 3 Different form of Fullerenes/buck balls (A) C60 and (B) C70.

2.6. Lipid-based NPs cally spherical with diameter ranging from 10 to 1000 nm. Like
polymeric NPs, lipid NPs possess a solid core made of lipid
These NPs contain lipid moieties and effectively using in many and a matrix contains soluble lipophilic molecules. Surfactants
biomedical applications. Generally, a lipid NP is characteristi- or emulsifiers stabilized the external core of these NPs (Rawat
912 I. Khan et al.

Figure 4 Rolling of graphite layer into single-walled and multi-walled CNTs.

et al., 2011). Lipid nanotechnology (Mashaghi et al., 2013) is a i.e. (1) Bottom-up approach and (2) Top-down approach
special field, which focus the designing and synthesis of lipid (Wang and Xia, 2004) as shown in Scheme 1 (Iravani, 2011).
NPs for various applications such as drug carriers and delivery These approaches further divide into various subclasses based
(Puri et al., 2009) and RNA release in cancer therapy (Gujrati on the operation, reaction condition and adopted protocols.
et al., 2014).
3.1. Top-down syntheses
3. Synthesis of nanoparticles
In this method, destructive approach is employed. Starting
Various methods can be employed for the synthesis of NPs, from larger molecule, which decomposed into smaller units
but these methods are broadly divided into two main classes and then these units are converted into suitable NPs. Examples

Scheme 1 Typical synthetic methods for NPs for the (a) top-down and (b) bottom-up approaches.
Nanoparticles 913

Figure 5 SEM images of (a) The untreated carbon black, (b) and (c) 10 min and 1 h ultrasonication in POM solution (Garrigue et al.,
2004).

of this method are grinding/milling, CVD, physical vapor size of the carbon particles become smaller with sonication
deposition (PVD) and other decomposition techniques time. A series of transition-metal dichalcogenide nanodots
(Iravani, 2011). This approach is used to synthesized coconut (TMD-NDs) were synthesized by combination of grinding
shell (CS) NPs. The milling method was employed for this pur- and sonication top-down techniques from their bulk crystals.
pose and the raw CS powders were finely milled for different It was revealed that almost all the TMD-NDs with sizes
interval of times, with the help of ceramic balls and a well- <10 nm show an excellent dispersion due to narrow size distri-
known planetary mill. They showed the effect of milling time bution (Zhang et al., 2015). Lately, highly photoactive active
on the overall size of the NPs through different characteriza- Co3O4 NPs were prepared via top-down laser fragmentation,
tion techniques. It was determined that with the time increases which is a top-down process. The powerful laser irradiations
the NPs crystallite size decreases, as calculated by Scherer generate well-uniform NPs having good oxygen vacancies
equation. They also realized that with each hour increment (Zhou et al., 2016). The average size of the Co3O4 was deter-
the brownish color faded away due to size decrease of the mined to be in the range of 5.8 nm ± 1.1 nm.
NPs. The SEM results were also in an agreement with the X-
ray pattern, which also indicated the particle size decreases
with time (Bello et al., 2015). 3.2. Bottom-up syntheses
One study revealed the spherical magnetite NPs synthesis
from natural iron oxide (Fe2O3) ore by top-down destructive This approach is employed in reverse as NPs are formed from
approach with a particle size varies from 20 to 50 nm in relatively simpler substances, therefore this approach is also
the presence of organic oleic acid (Priyadarshana et al., called building up approach. Examples of this case are sedi-
2015). A simple top-down route was employed to synthesize mentation and reduction techniques. It includes sol gel, green
colloidal carbon spherical particles with control size. The syn- synthesis, spinning, and biochemical synthesis. (Iravani,
thesis technique was based on the continuous chemical adsorp- 2011). Mogilevsky et al. synthesized TiO2 anatase NPs with
tion of polyoxometalates (POM) on the carbon interfacial graphene domains through this technique (Mogilevsky et al.,
surface. Adsorption made the carbon black aggregates into rel- 2014). They used alizarin and titanium isopropoxide precur-
atively smaller spherical particles, with high dispersion capac- sors to synthesize the photoactive composite for photocatalytic
ity and narrow size distribution as shown in Fig. 5 (Garrigue degradation of methylene blue. Alizarin was selected as it
et al., 2004). It also revealed from the micrographs, that the offers strong binding capacity with TiO2 through their axial
914 I. Khan et al.

Scheme 2 Synthesis of TiO2 via bottom-up technique. SEM images showing the TiO2 NPs (Mogilevsky et al., 2014).

hydroxyl terminal groups. The anatase form was confirmed by ± 2.6 nm of Au nanospheres (red column Fig. 6e) and 72
XRD pattern. The SEM images taken for different samples ± 3.1 in edge length of Au octahedra per particle (blue column
with reaction scheme are provided in scheme 2. SEM indicates Fig. 6f).
that with temperature elevation, the size of NPs also increases More recently, solvent-exchange method is used to achieve
(Mogilevsky et al., 2014). limit sized low density lipoprotein (LDL) NPs for medical can-
Well-uniform spherical shaped Au nanospheres with cer drug delivery purpose by Needham et al. In this method
monocrystalline have been synthesized via laser irradiation nucleation is the bottom approach followed by growth which
top-down technique (Liu et al., 2015a, 2015b). Liu et al. selec- is the up approach. The LDL NPs were obtained without using
tively transform the octahedra morphology to spherical shape phospholipid and possessed high hydrophobicity, which is
by controlling the laser treatment time and other reaction essential for drug delivery applications (Needham et al., 2016).
parameters. Fig. 6 provides the SEM and TEM of the prepared The monodispersed spherical bismuth (Bi) NPs were syn-
Au nanospheres, which showed average diameter of 75 thesized by both top-down and bottom-up approaches
Nanoparticles 915

Figure 6 SEM for Au nanospheres (a) top view, (b) tilted view, (c) TEM image of Au nanospheres (d) SAED pattern (inset: TEM of
single Au particle), (e) and (f) size distribution spectra of spherical and octahedral Au NPs (Liu et al., 2015a, 2015b).

(Wang and Xia, 2004). These NPs have excellent colloidal bottom-up techniques with general remarks (Biswas et al.,
properties. In the bottom-up approach bismuth acetate was 2012).
boiled within ethylene glycol, while in top-down approach
the bismuth was converted into molten form and then the mol- 4. Characterization of NPs
ten drop was emulsified within the boiled diethylene glycol to
produce the NPs. The size of the NPs obtained by both meth- Different characterization techniques have been practiced for
ods was varied from 100 nm to 500 nm (Wang and Xia, 2004). the analysis of various physicochemical properties of NPs.
The details of this study are provided in Scheme 3. Green and These include techniques such as X-ray diffraction (XRD),
biogenic bottom-up synthesis attracting many researchers due X-ray photoelectron spectroscopy (XPS), infrared (IR),
to the feasibility and less toxic nature of processes. These pro- SEM, TEM, Brunauer–Emmett–Teller (BET), and particle size
cesses are cost-effective and environmental friendly, where syn- analysis.
thesis of NPs is accomplished via biological systems such as
using plant extracts. Bacteria, yeast, fungi, Aloe vera, tamarind 4.1. Morphological characterizations
and even human cells are used for the synthesis of NPs. Au
NPs have been synthesis from the biomass of wheat and oat
(Parveen et al., 2016) and using the microorganism and plant The morphological features of NPs always attain great interest
extracts as reducing agent (Ahmed et al., 2016). Table 1 pro- since morphology always influences most of the properties of
vides the merits and demerits of various top-down and the NPs. There are different characterization techniques for
916 I. Khan et al.

Scheme 3 (A) Bottom-up approach: A molecular precursor is disintegrated to simpler metal atoms that grow into colloids. (B) Top-
down approach: Large drops of a metal broken into smaller drops (Wang and Xia, 2004).

morphological studies, but microscopic techniques such as ject material. XRD, energy dispersive X-ray (EDX), XPS, IR,
polarized optical microscopy (POM), SEM and TEM are the Raman, BET, and Zieta size analyzer are the common tech-
most important of these. niques used to study structural properties of NPs.
SEM technique is based on electron scanning principle, and XRD is one of the most important characterization tech-
it provides all available information about the NPs at nanos- niques to reveal the structural properties of NPs. It gives
cale level. Wide literature is available, where people used this enough information about the crystallinity and phase of
technique to study not only the morphology of their nanoma- NPs. It also provides rough idea about the particle size
terials, but also the dispersion of NPs in the bulk or matrix. through Debye Scherer formula (Khan et al., 2017b, 2017c;
The dispersion of SWNTs in the polymer matrix poly(buty- Ullah et al., 2017). This technique worked well in both single
lene) terephthalate (PBT) and nylon-6 revealed through this and multiphase NPs identification (Emery et al., 2016). Never-
technique (Saeed and Khan, 2016, 2014). The same group also theless, in the case of smaller NPs having size less than hun-
provides POM study of their materials, which showed star-like dreds of atoms, the acquisition and correct measurement of
spherulites of the formed materials, whose size was decreased structural and other parameters may be difficult. Moreover,
with the incremental filling of SWNTs. The morphological fea- NPs having more amorphous characteristics with varied inter
tures of ZnO modified metal organic frameworks (MOFs) were atomic lengths can influence the XRD diffractogram. In that
studied through SEM technique, which indicates the ZnO NPs case, proper comparison of the diffractograms of bimetallic
dispersion and morphologies of MOFs at different reaction NPs with those of the corresponding monometallic NPs and
conditions (Fig. 7) (Mirzadeh and Akhbari, 2016). their physical mixtures is required to obtain accurate informa-
Similarly, TEM is based on electron transmittance princi- tion. Comparison of computer simulated structural model of
ple, so it can provide information of the bulk material from bimetallic NPs with observed XRD spectra is the best way
very low to higher magnification. The different morphologies to get good contrast (Ingham, 2015). EDX, which is normally
of gold NPs are studied via this technique. Fig. 8 provides fixed with field emission scanning electron miscopy (FE-SEM)
some TEM micrographs showing various morphologies of or TEM device is widely used to know about the elemental
gold NPs, prepared via different methods (Khlebtsov and composition with a rough idea of % wt. The electron beam
Dykman, 2011, 2010a, 2010b). TEM also provides essential focused over a single NP by SEM or TEM through the pro-
information about two or more layer materials, such as the gram functions, to acquire the insight information from the
quadrupolar hollow shell structure of Co3O4 NPs observed NP under observation. NP comprises of constituent elements
through TEM. These NPs founded to be exceptionally active and each of them emits characteristics energy X-rays by elec-
as anode in Li-ion batteries (Fig. 9). Porous multishell struc- tron beam irradiation. The intensity of specific X-ray is directly
ture induces shorter Li+ diffusion path length with adequate proportional to the concentration of the explicit element in the
annulled space to buffer the volume expansion, good cycling particle. This technique is widely used by researchers to give
performance, greater rate capacity, and specific capacity as support to SEM and other techniques for the confirmation
well (Wang et al., 2013). of their elements in prepared materials (Avasare et al., 2015;
Iqbal et al., 2016). The EDX technique used to determine
4.2. Structural characterizations the elemental composition of ultra-sonochemically synthesized
pseudo-flower shaped BiVO4 NPs (Khan et al., 2017b). Simi-
The structural characteristics are of the primary importance to larly, by utilizing similar technique the elemental confirmation
study the composition and nature of bonding materials. It pro- and graphene impregnation of In2O3/graphene heterostructure
vides diverse information about the bulk properties of the sub- NPs was carried out, which showed C, In and O as contribut-
Nanoparticles 917

Table 1 Top-down and bottom-up synthetic techniques with merits, demerits and general remarks (Biswas et al., 2012).
Top–down Merits Demerits General remarks
method
Optical Long-standing, established Tradeoff between resist process The 193 nm lithography infrastructure
lithography micro/nanofabrication tool especially sensitivity and resolution, involves already reached a certain level of
for chip production, sufficient level of state-of-the-art expensive clean room maturity and sophistication, and the
resolution at high throughputs based complex operations approach could be extended to extreme
ultraviolet (EUV) sources to shrink the
dimension. Also, future developments
need to address the growing cost of a
mask set
E-beam Popular in research environments, an Expensive, low throughput and a slow E-beam lithography beats the
lithography extremely accurate method and effective process (serial writing process), difficult diffraction limit of light, capable of
nanofabrication tool for <20 nm for <5 nm nanofabrication making periodic nanostructure features.
nanostructure fabrication with desired In the future, multiple electron beam
shape approaches to lithography would be
required to increase the throughput and
degree of parallelism
Soft and Pattern transfer based simple, effective Difficult for large-scale production of Self-assembled nanostructures could be
nanoimprint nanofabrication tool for fabricating densely packed nanostructures, also a viable solution to the problem of
lithography ultra-small features (<10 nm) dependent on other lithography complex and costly template
techniques to generate the template, generation, and for templates of
and usually not cost-effective periodic patterns of <10 nm
Block co- A high-throughput, low-cost method, Difficult to make self-assembled Use of triblock copolymers is promising
polymer suitable for large-scale densely packed nanopatterns with variable periodicity to generate more exotic nanopattern
lithography nanostructures, diverse shapes of required for many functional geometries. Also, functionalization of
nanostructures, including spheres, applications, usually high defect parts of the block copolymer could be
cylinders, lamellae possible to fabricate densities in block copolymer self- done to achieve hierarchy of
including parallel assembly assembled patterns nanopatterning in a single step
nanofabrication process
Scanning probe High resolution chemical, molecular Limited for high throughput Scanning probe lithography can be
lithography and mechanical nanopatterning applications and manufacturing, an leveraged for advanced
capabilities, accurately controlled expensive process, particularly in the bionanofabrication that involves
nanopatterns in resists for transfer to case of ultra-high-vacuum based fabrication of highly periodic
silicon, ability to manipulate big scanning probe lithography biomolecular nanostructures
molecules and individual atoms

Bottom–up Merits Demerits General remarks


method
Atomic layer Allows digital thickness control to the Usually a slow process, also an Although a slow process, it is not
deposition atomic level precision by depositing one expensive method due to the detrimental for the fabrication of future
atomic layer at a time, pin-hole free involvement of vacuum components, generation ultra-thin ICs. The stringent
nanostructured films over large areas, difficult to deposit certain metals, requirements for the metal barriers
good reproducibility and adhesion due multicomponent oxides, certain (pure; dense; conductive; conformal;
to the formation of chemical bonds at technologically important thin) that are employed in modern Cu-
the first atomic layer semiconductors (Si, Ge, etc.) in a cost- based chips can be fulfilled by atomic
effective way layer deposition
Sol gel A low-cost chemical synthesis process Not easily scalable, usually difficult to A versatile nanofabrication method
nanofabrication based method, fabrication of a wide control synthesis and the subsequent that can be made scalable with further
variety of nanomaterials including drying steps advances in the synthesis steps
multicomponent materials (glass,
ceramic, film, fiber, composite
materials)
Molecular self- Allows self-assembly of deep molecular Difficult to design and fabricate Molecular self-assembly of multiple
assembly nanopatterns of width less than 20 nm nanosystems unlike mechanically materials may be an useful approach in
and with the large pattern stretches, directed assembly developing multifunctional
generates atomically precise nanosystems and devices
nanosystems
Physical and Versatile nanofabrication tools for Not cost-effective because of the It provides unique opportunity of
chemical vapor- fabrication of nanomaterials including expensive vacuum components, high- nanofabrication of highly complex
phase complex multicomponent nanosystems temperature process and toxic and nanostructures made of distinctly
deposition (e.g. nanocomposites), controlled corrosive gases particularly in the case different materials with different
simultaneous deposition of several of chemical vapor deposition properties that are not possible to
(continued on next page)
918 I. Khan et al.

Table 1 (continued)
Bottom–up Merits Demerits General remarks
method
materials including metal, ceramics, accomplish using most of the other
semiconductors, insulators and nanofabrication techniques. New
polymers, high purity nanofilms, a advances in chemical vapor deposition
scalable process, possibility to deposit such as ‘initiated chemical vapor
porous nanofilms deposition’ (i-CVD) provide
unprecedented opportunities of
depositing polymers without reduction
in the molecular weights
DNA- Allows high-precision assembling of Many issues need to explore, such as Very early stage. Ultimate success
scaffolding nanoscale components into novel unit and integration processes, depends on the willingness of the
programmable arrangements with compatibility with CMOS fabrication, semiconductor industry in terms of
much smaller dimensions (less than line edge roughness, throughput and need, infrastructural capital investment,
10 nm in half-pitch) cost yield and manufacturing cost

ing elements. This material was synthesized through conven- Pr, La, Gd, Lu and Er) (NPs) was synthesized by correlated
tional hydrothermal technique (Mansha et al., 2016). techniques. FT-IR and Raman spectra analysis exhibited that
XPS is considered to be the most sensitive technique and it the La2Hf2O7:5%Eu3+ and Pr2Hf2O7:5%Eu3+ possessed rela-
is widely used to determine the exact elemental ratio and exact tively ordered pyrochlore structure as compared to RE2Hf2-
bonding nature of the elements in NPs materials. It is surface O7:5%Eu3+ compositions (RE = Y, Er, and Lu), which
sensitive technique and can be used in depth profiling studies possess disordered fluorite structure. The stable structures
to know the overall composition and the compositional varia- were found thermodynamically stable until high temperature
tion with depth. XPS is based on the basic spectroscopic prin- of 1500 °C. However, a disordered–ordered cause instability
ciples and typical XPS spectrum is composed of the number of in the latter case, and thus thermodynamically unstable
electrons on Y-axis plot versus the binding energy (eV) of the (Pokhrel et al., 2016).
electrons on X-axis. Each element has their own fingerprint More recently surface enhanced Raman spectroscopy
binding energy value and thus gives specific set of XPS peaks. (SERS) is evolving as vibrational conformational tool due to
The peaks correspond come from electronic configuration, its signal enhanced capability via SPR phenomenon
e.g., 1s, 2s, 2p, and 3s. Lykhach et al. provide a depth electron (Muehlethaler et al., 2016). One study reported SERS tech-
transfer study through CeO2 supported Pt NPs using XPS nique to study the vibrational properties with phonons modes
technique with support to others. They determined that per in nanostructured and quantum dots NPS of TiO2, ZnO and
ten Pt atoms, only one electron is elated from the NPs to PbS. They concluded that the enhanced spectra can be attrib-
CeO2 support (Lykhach et al., 2015). The depth profile analy- uted to the plasmonic resonances in semiconductor systems
sis was provided to study the dispersion of boron NPs (10 nm (Ma et al., 2011).
size) during polyethylene glycol (PEG) functionalization. Ar+
ions were used at 1.4 keV and 20 nm; depth surface etching 4.3. Particle size and surface area characterization
was performed. It was revealed that the concentration of
NPs increases from 2 to 5% with depth. This provided good Different techniques can be used to estimate the size of the
evidence that boron NPs are dissolved effectively within the NPs. These include SEM, TEM, XRD, AFM, and dynamic
bulk of functionalized PEG (Oprea et al., 2015). In similar light scattering (DLS). SEM, TEM, XRD and AFM can give
study coreshell Au/Ag showed similar behavior through XPS better idea about the particle size (Kestens et al., 2016), but the
depth profiling. Wang et al. quantify the NPs coating with this zeta potential size analyzer/DLS can be used to find the NPs
technique through XPS and STEM spectroscopies by help of size at extremely low level. In one study Sikora et al. used
SESSA software (Wang et al., 2016). DLS technique to investigate the size variation of silica NPs
Vibrational characterization of nanoparticles is normally with absorption of proteins from serum. The results showed
studied via FT-IR and Raman spectroscopies. These tech- that size increased with acquisition of protein layer. However,
niques are the most developed and feasible as compared to in case of agglomeration and hydrophilicity, DLS might prove
other elemental analytical methods. The most important range incapable of accurate measurement, so in that case we should
for NPs is the fingerprint region, which provides signature rely on the high-resolution technique of differential centrifugal
information about the material. In one study, functionaliza- sedimentation (DCS) (Sikora et al., 2016). Beside DSC,
tion of Pt NPs (1.7 nm mean size) and its interaction with Alu- nanoparticle tracking analysis (NTA) is relatively newer and
mina substrate studied via FT-IR and XPS technique. FT-IR special technique, which can be helpful in case of biological
confirms the functionalization as it showed the signature vibra- systems such as proteins, and DNA. In NTA method, we
tional peaks of carboxylated C–O 2033 cm 1, respectively in can visualize and analyze the NPs in liquids media that relates
addition to a broader O–H peak at 3280 cm 1. The degree of the Brownian motion rate to particle size. This technique
functionalization was revealed from the red shift values of allows us to find the size distribution profile of NPs with diam-
FT-IR bands (Fig. 10) (Dablemont et al., 2008). eter ranging from 10 to 1000 nm in a liquid medium (Filipe
In another study, a series of 5 mol% Eu3+ – doped rare et al., 2010). This technique produced some good results as
earth metal (RE) hafnium oxide RE2Hf2O7 (where RE = Y,
Nanoparticles 919

Figure 7 SEM images of ZnO modified MOFs at different temperatures (Mirzadeh and Akhbari, 2016).

compared to DLS and found to be very precise for sizing desorption. It was discovered that N2 adsorption volume is
monodisperse as well as polydisperse samples, with substan- progressively increased with relative pressure until certain limit
tially better peak resolution. Gross et al. detected the particle signifying the availability of pores. The BET specific surface
size and concentration of different sized NPs in suspensions area for this material was 133–144 m2/g, while the total pore
of polymer and protein samples and provided an overview volume was 0.112–0.185 cm3/g. But after sulphidation process,
on the effect of experimental and data evaluation parameters the BET surface area reduced to 110 m2/mg and the pore vol-
(Gross et al., 2016). ume decreased to 0.096 cm3/g, respectively (Liu et al., 2016).
Large surface area of nanomaterials offers great room for
various applications and BET is the best technique to deter-
4.4. Optical characterizations
mine the surface area of NPs materials. This technique is based
on adsorption and desorption principle and Brunauer–Emme
tt–Teller (BET) theorem. Normally nitrogen gas is used for Optical properties are of great concerned in photocatalytic
this purpose. BET produces four types of isotherm specifically, applications and therefore, photo-chemists acquired good
which are labeled as Type-I, Type-II, Type-III and Type-IV knowledge of this technique to reveal the mechanism of their
(Fagerlund, 1973). The fresh 7Cu3Ce/ZSM-5 showed typical photochemical processes. These characterizations are based
features of Type-I isotherm obtain from nitrogen adsorption/ on the famous beer-lambert law and basic light principles
920 I. Khan et al.

Figure 8 TEM images of different form of gold NPs, synthesized by different techniques (Khlebtsov and Dykman, 2011, 2010a, 2010b).

(Swinehart, 1962). These techniques give information about absorption band from 400 to 620 nm, showing decrease in their
the absorption, reflectance, luminescence and phosphorescence bandgap. This property makes these catalysts considerable for
properties of NPs. It is widely known that NPs especially solar light driven photocatalysis (Peng et al., 2016).
metallic and semiconductor NPs possess different colors and In addition to UV, PL also considers valuable technique to
therefore, best harmonized for photo-related applications. study the optical properties of the photoactive NPs and other
So, it is always interesting to know the value of absorption nanomaterials. This technique offers additional information
and reflectance of these materials to understand the basic about the absorption or emission capacity of the materials
mechanism for each application. Ultraviolet–visible (UV– and their effect on the overall excitation time of photoexcitons.
Vis), photoluminescence (PL) and the null ellipsometer are Thus, it provides significant information about the charge
the well-known optical instruments, which can be used to recombination and half-life of the excited materials in their
study the optical properties of NPs materials. conductance band, which are useful for all photo related and
The UV/vis- diffuse reflectance spectrometer (DRS) is a imaging applications. The PL spectrum can be recorded as
fully equipped device which can be used to measure the optical emission or absorbance depending on the nature of study.
absorption, transmittance and reflectance. The former two are Fig. 11 shows a typical PL spectrum of pristine and modified
supplementary to each other while the latter (DRS) is a special ZnO NPs. It is evident from this figure that pristine ZnO
technique use for sold samples mostly. The method is excep- NPs show high PL intensity as compared to CdS modified
tionally acceptable for the determination of bandgaps of NPs ZnO NPs. The gold embedded CdS/Au/ZnO composite shows
and other nanomaterials. Bandgap of materials is very impor- the lowest intensity. This quenching from pure ZnO to CdS/
tant to conclude about the photoactivity and conductance of Au/ZnO can be attributed to the decrease in the rate of charge
the material. The carbon nanodot-carbon nitride (C3N4) was recombination and larger lifetime of photoexcitons in the latter
found to be a metal free water splitting photocatalyst. The case (Yu et al., 2013). In addition, this technique is successfully
photo ability of this material is directly correlated to the band- used to determine the thickness of layer (Lin et al., 2015), dop-
gap value of 2.74–2.77 eV, which was calculated using UV–Vis ing quantity of (Gupta et al., 2013; Pal et al., 2012) material
spectroscopy (Liu et al., 2015a, 2015b). Similarly, this tech- and defects/oxygen vacancies determination (Torchynska
nique also use to see the absorption shift in case of doping, et al., 2016) of NPs.
composite formation or heterostructure NPs materials. Peng Similarly, Wan et al. determined the values of refractive
et al. synthesis MMT, LaFeO3 and LaFeO3/MMT nanocom- index and extinction coefficient for hollow gold NPs (HG-
posites and studied variation in their electromagnetic radia- NPs) via spectroscopic ellipsometry. They prepared a series
tions absorption through UV–vis DRS to reconnoiter their of HG-NPs, with different morphologies and plasmonic prop-
optical characteristics. The strong red shift observed in case erties and the optical constants were calculated. The values
of nanocomposite as compared to pristine MMT and LaFeO3 were compared with the optical constant values of solid gold
NPs. LaFeO3 and LaFeO3/MMT displayed rather broad NPs, which gave good indication to use these materials in
Nanoparticles 921

Figure 9 SEM (a–c, h), TEM (d–f), XRD patterns (g) and HRTEM (i) images of double, triple and quadruple Co3O4 hollow shells
(Wang et al., 2013).

chemical sensing applications due to their sensitive nature as of the bulk metal. This excitation band results when the inci-
revealed from ellipsometric values (Wan et al., 2009). dent photon frequency is constant with the collective excitation
of the conduction electrons and is known as the localized sur-
5. Physicochemical properties of NPs face plasma resonance (LSPR). LSPR excitation results in the
wavelength selection absorption with extremely large molar
As discussed earlier, various physicochemical properties such excitation coefficient resonance Ray light scattering with effi-
as large surface area, mechanically strong, optically active ciency equivalent to that of ten fluorophores and enhanced
and chemically reactive make NPs unique and suitable appli- local electromagnetic fields near the surface of NPs that
cants for various applications. Some of their important prop- enhanced spectroscopies. It is well established that the peak
erties are discuss in the following section. wavelength of the LSPR spectrum is dependent upon the size,
shape and interparticle spacing of the NPs as well as its own
5.1. Electronic and optical properties dielectric properties and those of its local environment includ-
ing the substrate, solvents and adsorbates (Eustis and El-
Sayed, 2006). Gold colloidal NPs are accountable for the rusty
The optical and electronic properties of NPs are inter- colors seen in blemished glass door/windows, while Ag NPs
dependent to greater extent. For instance, noble metals NPs are typically yellow. Actually, the free electrons on the surface
have size dependent optical properties and exhibit a strong in these NPs (d electrons in Ag and gold) are freely trans-
UV–visible extinction band that is not present in the spectrum portable through the nanomaterial. The mean free path for
922 I. Khan et al.

Figure 10 FTIR spectra of platinum (1.7 nm) (a) extracted from polyol, (b) dodecanethiol coated Pt, and (c) MUDA coated Pt
(Dablemont et al., 2008).

these particle priceless and can be used in different applications


(Faivre and Bennet, 2016; Priyadarshana et al., 2015; Reiss
and Hütten, 2005; Zhu et al., 1994). The uneven electronic dis-
tribution in NPs leads to magnetic property. These properties
are also dependent on the synthetic protocol and various syn-
thetic methods such as solvothermal (Qi et al., 2016), co-
precipitation, micro-emulsion, thermal decomposition, and
flame spray synthesis can be used for their preparation (Wu
et al., 2008).

5.3. Mechanical properties

The distinct mechanical properties of NPs allow researchers to


look for novel applications in many important fields such as
Figure 11 Photoluminescence (PL) spectra of pristine ZnO,
tribology, surface engineering, nanofabrication and nanoman-
CdS/ZnO, and CdS/Au/ZnO measured with 270 nm excitation
ufacturing. Different mechanical parameters such as elastic
wavelength at normal temperature (Yu et al., 2013).
modulus, hardness, stress and strain, adhesion and friction
can be surveyed to know the exact mechanical nature of
NPs. Beside these parameters surface coating, coagulation,
Ag and gold is 50 nm, which is more than the NPs size of
and lubrication also aid to mechanical properties of NPs
these materials. Thus, no scattering is expected from the bulk,
(Guo et al., 2014) (see Scheme 4). NPs show dissimilar
upon light interaction, instead they set into a standing reso-
mechanical properties as compared to microparticles and their
nance conditions, which is responsible for LSPR in these
bulk materials. Moreover, in a lubricated or greased contact,
NPs (Fig. 12) (Khlebtsov and Dykman, 2010a, 2010b).
the contrast in the stiffness between NPs and the contacting
external surface controls whether the NPs are indented into
5.2. Magnetic properties
the plan surface or deformed when the pressure at contact is
significantly large. This important information could divulge
Magnetic NPs are of great curiosity for investigators from an how the NPs perform in the contact situation. Decent controls
eclectic range of disciplines, which include heterogenous and over mechanical features of NPs and their interactions with
homogenous catalysis, biomedicine, magnetic fluids, data stor- any kind of surface are vital for enlightening the surface qual-
age magnetic resonance imaging (MRI), and environmental ity and elevating material removal. Fruitful outcomes in these
remediation such as water decontamination. The literature fields generally need a deep insight into the basics of the
revealed that NPs perform best when the size is <critical value mechanical properties of NPs, such as elastic modulus and
i.e. 10–20 nm (Reiss and Hütten, 2005). At such low scale the hardness, movement law, friction and interfacial adhesion
magnetic properties of NPs dominated effectively, which make and their size dependent characteristics (Guo et al., 2014).
Nanoparticles 923

Figure 12 Graphical illustration exemplifying the localized surface plasmon (LSPR) on nanoparticle outer surface (Khlebtsov and
Dykman, 2010a, 2010b).

Scheme 4 Schematic view of the mechanical properties and their applications (Guo et al., 2014).

5.4. Thermal properties (Al2O3) have thermal conductivity higher than that of water.
Therefore, the fluids containing suspended solid particles are
It is well-known fact that metals NPs have thermal conductiv- expected to display significantly enhanced thermal conductivi-
ities higher than those of fluids in solid form. For example, the ties relative to those of conventional heat transfer fluids.
thermal conductivity of copper at room temperature is about Nanofluids are produced by dispersing the nanometric scales
700 times greater than that of water and about 3000 times solid particles into liquid such as water, ethylene glycol or oils.
greater than that of engine oil. Even oxides such as alumina Nanofluids are expected to exhibit superior properties relative
924 I. Khan et al.

to those of conventional heat transfer fluids and fluids contain- of pharmacologically active drugs to the precise action site at
ing microscopic sized particles. Because the heat transfer takes the therapeutically optimum degree and dose regimen has been
place at the surface of the particles, it is desirable to use the a major goal in designing such devices.
particles with large total surface area. The large total surface Liposomes have been used as a potential drug carrier
area also increases the stability suspension (Lee et al., 1999). instead of conventional dosage forms because of their unique
Recently it has been demonstrated that the nanofluids consist- advantages which include ability to protect drugs from degra-
ing of CuO or Al2O3 NPs in water or ethylene exhibit advance dation, target to the site of action and reduce the noxiousness
thermal conductivity (Cao, 2002). and other side effects. However developmental work on lipo-
some drugs has been restricted due to inherent health issues
6. Applications of NPs such as squat encapsulation efficiency, rapid water leakage in
the commodity of blood components and very poor storage,
Considering the unique properties discussed in Section 5, NPs and stability. On the other hand, polymeric NPs promise some
can be used in variety of applications. Some important of these critical advantages over these materials i.e. liposomes. For
are given below. instance, NPs help to increase the ratability of drugs or prob-
lems and possess convenient controlled drug release properties.
Most of the semiconductor and metallic NPs have immense
6.1. Applications in drugs and medications
potential for cancer diagnosis and therapy on account of their
surface plasmon resonance (SPR) enhanced light scattering
Nano-sized inorganic particles of either simple or complex nat- and absorption. Au NPs efficiently convert the strong
ure, display unique, physical and chemical properties and rep- absorbed light into localized heat which can be exploited for
resent an increasingly important material in the development the selective laser photo thermal therapy of cancer (Prashant
of novel nanodevices which can be used in numerous physical, et al., 2007). Beside this the antineoplastic effect of NPs is also
biological, biomedical and pharmaceutical applications effectively employed to inhibit the tumor growth. The multihy-
(Loureiro et al., 2016; Martis et al., 2012; Nikalje, 2015). droxylated [Gd@C82(OH)22]n NPs showed antineoplastic
NPs have drawn increasing interest from every branch of activity with good efficiency and lower toxicity (Chen et al.,
medicine for their ability to deliver drugs in the optimum 2005). Ag NPs are being used increasingly in wound dressings,
dosage range often resulting in increased therapeutic efficiency catheters and various households’ products due to their
of the drugs, weakened side effects and improved patient com- antimicrobial activity (AshaRani et al., 2009). Antimicrobial
pliance (Alexis et al., 2008). Iron oxide particles such as mag- agents are extremely vital in textile, medicine, water disinfec-
netite (Fe3O4) or its oxidized form maghemite (Fe2O3) are the tion and food packaging. Therefore, the antimicrobial charac-
most commonly employed for biomedical applications (Ali teristics of inorganic NPs add more potency to this important
et al., 2016). The selection of NPs for achieving efficient con- aspect, as compared to organic compounds, which are rela-
trast for biological and cell imaging applications as well as tively toxic to the biological systems (Hajipour et al., 2012).
for photo thermal therapeutic applications is based on the These NPs are functionalized with various groups to overcome
optical properties of NPs. Mie theory and discrete dipole the microbial species selectively. TiO2, ZnO, BiVO4, Cu- and
approximation method can be used to calculate absorption Ni-based NPs have been utilized for this purpose due to their
and scattering efficiencies and optical resonance wavelength suitable antibacterial efficacies (Akhavan et al., 2011; Pant
for the commonly used classes of NPs i.e. Au NPs, silica-Au et al., 2013; Qu et al., 2016; Yin et al., 2016).
NPs and Au nanorods (Jain et al., 2006). The development
of hydrophilic NPs as drug carrier has represented over the last 6.2. Applications in manufacturing and materials
few years an important challenge. Among the different
approaches, polyethylene oxide (PEO) and polylactic acid
(PLA) NPs have been revealed as very promising system for Nanocrystalline materials provide very interesting substances
the intravenous administration of drugs (Calvo et al., 1997). for material science since their properties deviate from respec-
Superparamagnetic iron oxide NPs with appropriate surface tive bulk material in a size dependent manner. Manufacture
chemistry can be used for numerous in vivo applications such NPs display physicochemical characteristics that induce
as MRI contrast enhancement, tissue repair, and immunoas- unique electrical, mechanical, optical and imaging properties
say, detoxification of biological fluids hyperthermia, drugs that are extremely looked-for in certain applications within
delivery and cell separation. All of these biomedical applica- the medical, commercial, and ecological sectors (Dong et al.,
tions require that the NPs have high magnetization value, a 2014; Ma, 2003; Todescato et al., 2016). NPs focus on the
size smaller than 100 nm and a narrow particle size distribu- characterization, designing and engineering of biological as
tion (Laurent et al., 2010). The detection of analytes in tissue well as non-biological structures < than 100 nm, which show
sections can be accomplished through antigen-antibody inter- unique and novel functional properties. The potential benefits
actions using antibodies labeled with fluorescent dyes, of nanotechnology have been documented by many manufac-
enzymes, radioactive compounds or colloidal Au (Khlebtsov turer at high and low level and marketable products are
and Dykman, 2010b). already being mass-produced such as microelectronics, aero-
Over past few decades these has been considerable interest space and pharmaceutical industries (Weiss et al., 2006).
in developing biodegradable NPs as effective drug delivery Among the nanotechnology consumer products to date, health
devices (Zhang and Saltzman, 2013). Various polymers have fitness products from the largest category, followed by the elec-
been used in drug delivery research as they can effectively deli- tronic and computer category as well as home and garden cat-
ver the drugs to the target site thus increases the therapeutic egory. Nanotechnology has been touted as the next revolution
benefit, while minimizing side effects. The controlled release in many industries including food processing and packing.
Nanoparticles 925

Resonant energy transfer (RET) system consisting of organic high surface area of NPs due to very small size (<10 nm),
dye molecules and noble metals NPs have recently gamed con- facilitated the efficient photodegradation reaction (Rogozea
siderable interest in bio photonics as well as in material science et al., 2017). The same group has reported the synthesis of
(Lei et al., 2015). The presence of NPs in commercially avail- variety of NPs and reported their optical, florescence and
able products is becoming more common. degradation applications (Olteanu et al., 2016a, 2016b;
Metals NPs such as noble metals, including Au and Ag Rogozea et al., 2016).
have many colors in the visible region based on plasmon reso-
nance, which is due to collective oscillations of the electrons at 6.4. Applications in electronics
the surface of NPs (Khlebtsov and Dykman, 2010a, 2010b;
Unser et al., 2015). The resonance wavelength strong depends There has been growing interest in the development of printed
on size and shape of NPs, the interparticle distance, and the electronics in last few years because printed electronics offer
dielectric property of the surrounding medium. The unique attractive to traditional silicon techniques and the potential
plasmon absorbance features of these noble metals NPs have for low cost, large area electronics for flexible displays, sensors.
been exploited for a wide variety of applications including Printed electronics with various functional inks containing
chemical sensors and biosensors (Unser et al., 2015). NPs such as metallic NPs, organic electronic molecules, CNTs
and ceramics NPs have been expected to flow rapidly as a mass
6.3. Applications in the environment production process for new types of electronic equipment
(Kosmala et al., 2011).
The increasing area of engineered NPs in industrial and house- Unique structural, optical and electrical properties of one
hold applications leads to the release of such materials into the dimensional semiconductor and metals make them the key
environment. Assessing the risk of these NPs in the environ- structural block for a new generation of electronic, sensors
ment requires on understanding of their mobility, reactivity, and photonic materials (Holzinger et al., 2014; Millstone
Eco toxicity and persistency (Ripp and Henry, 2011; Zhuang et al., 2010; Shaalan et al., 2016).
and Gentry, 2011). The engineering material applications can The good example of the synergism between scientific dis-
increase the concentration of NPs in groundwater and soil covery and technological development is the electronic indus-
which presents the most significant exposure avenues for try, where discoveries of new semiconducting materials
assessing environmental risks (Golobič et al., 2012; resulted in the revolution from vacuumed tubes to diodes
Masciangioli and Zhang, 2003). Due to high surface to mass and transistors, and eventually to miniature chips (Cushing
ratio natural NPs play an important role in the solid/water et al., 2004).
partitioning of contaminants can be absorbed to the surface The important characteristics of NPs are facile manipula-
of NPs, co-precipitated during the formation of natural NPs tion and reversible assembly which allow for the possibility
or trapped by aggregation of NPs which had contaminants of incorporation of NPs in electric, electronic or optical
adsorbed to their surface. The interaction of contaminants devices such as ‘‘bottom up” or ‘‘self-assembly” approaches
with NPs is dependent on the NPs characteristics, such as size, are the bench mark of nanotechnology (O’Brien et al., 2001).
composition, morphology, porosity, aggregation/disaggrega-
tion and aggregate structure. The luminophores are not safe 6.5. Applications in energy harvesting
in the environment and are protected from the environmental
oxygen when they are doped inside the silica network Recent studies warned us about the limitations and scarcity
(Swadeshmukul et al., 2001). of fossil fuels in coming years due to their nonrenewable nat-
Most of environmental applications of nanotechnology fall ure. Therefore, scientists shifting their research strategies to
into three categories: generate renewable energies from easily available resources
at cheap cost. They found that NPs are the best candidate
1. Environmentally benign sustainable products (e.g. green for this purpose due to their, large surface area, optical
chemistry or pollution prevention). behavior and catalytic nature. Especially in photocatalytic
2. Remediation of materials contaminated with hazardous applications, NPs are widely used to generate energy from
substances and photoelectrochemical (PEC) and electrochemical water split-
3. Sensors for environmental stages (Tratnyek and Johnson, ting (Avasare et al., 2015; Mueller and Nowack, 2008; Ning
2006). et al., 2016). Beside water splitting, electrochemical CO2
reduction to fuels precursors, solar cells and piezoelectric gen-
The removal of heavy metals such as mercury, lead, thal- erators also offered advance options to generate energy (Fang
lium, cadmium and arsenic from natural water has attracted et al., 2013; Gawande et al., 2016; Lei et al., 2015; Li et al.,
considerable attention because of their adverse effects on envi- 2016; Nagarajan et al., 2014; Sagadevan, 2015; Young et al.,
ronmental and human health. Superparamagnetic iron oxide 2012; Zhou et al., 2016). NPs also use in energy storage
NPs are an effective sorbent material for this toxic soft mate- applications to reserve the energy into different forms at
rial. So, for no measurements of engineered NPs in the envi- nanoscale level (Greeley and Markovic, 2012; Liu et al.,
ronment have been available due to the absence of analytical 2015a, 2015b; Sagadevan, 2015; Wang and Su, 2014).
methods, able to quantify trace concentration of NPs Recently, nanogenerators are created, which can convert the
(Mueller and Nowack, 2008). Photodegradation by NPs is also mechanical energy into electricity using piezoelectric, which
very common practice and many nanomaterials are utilized for is an unconventional approach to generate energy (Wang
this purpose. Rogozea et al. used NiO/ZnO NPs modified sil- et al., 2015). Fig. 13 shows some energy generating devices,
ica in the tandem fashion for photodegradation purpose. The and uses NPs.
926 I. Khan et al.

Figure 13 Energy generation approaches from (A) Piezoelectrics actuators (B) Water splitting (C) CO2 reduction.

6.6. Applications in mechanical industries to various mechanically strong characteristics, as it improves


toughness and wear resistance. Alumina, Titania and carbon
As revealed from their mechanical properties through excellent based NPs successfully demonstrated to get the desirable
young modulus, stress and strain properties, NPs can offer mechanical properties in coatings (Kot et al., 2016;
many applications in mechanical industries especially in coat- Mallakpour and Sirous, 2015; Shao et al., 2012).
ing, lubricants and adhesive applications. Besides, this prop-
erty can be useful to achieve mechanically stronger 7. Toxicity of NP
nanodevices for various purposes. Tribological properties
can be controlled at nanoscale level by embedding NPs in Beside many industrial and medical applications, there are cer-
the metal and polymer matrix to increase their mechanical tain toxicities which are associated with NPs and other nano-
strengths. It is because, the rolling mode of NPs in the lubri- materials (Bahadar et al., 2016; Ibrahim, 2013; Khlebtsov and
cated contact area could provide very low friction and wear. Dykman, 2011, 2010b) and basic knowledge is required for
In addition, NPs offer good sliding and delamination proper- these toxic effects to encounter them properly. NPs surrepti-
ties, which could also effect in low friction and wear, and hence tiously enter the environment through water, soil, and air dur-
increase lubrication effect (Guo et al., 2014). Coating can lead ing various human activities. However, the application of NPs
Nanoparticles 927

for environmental treatment deliberately injects or dumps 9. Recommendations


engineered NPs into the soil or aquatic systems. This has resul-
tantly attracted increasing concern from all stakeholders. The Our recommendation for future work is that different reaction
advantages of magnetic NPs such as their small size, high reac- parameters such as temperature, pressure, time, and pH. can
tivity and great capacity, could become potential lethal factors play important role in controlling the shape and morphology
by inducing adverse cellular toxic and harmful effects, unusual of the NPs materials, so that should be optimize for achieving
in micron-sized counter parts. Studies also illustrated that NPs specific characteristic product. Beside this for good implica-
can enter organisms during ingestion or inhalation and can tions and properties study specific characterization techniques
translocate within the body to various organs and tissues should be used. More importantly environmental issued
where the NPs have the possibility to exert the reactivity being should be taken into account before using these materials for
toxicology effects. Although some studies have also addressed any applications, especially in case of heavy metals, which
the toxicological effects of NPs on animal cells and plant cells are prone to environmental hazards and can also affect the liv-
the toxicological studies with magnetic NPs on plants to date ings as well.
are still limited. The uses of Ag NPs in numerous consumer
products lead them to their release to the aquatic environment
and become a source of dissolved Ag and thus exert toxic References
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