CHAPTER 15

Ionic liquid based colloidal

nanoparticles: applications
in organic synthesis
Marium
1
Ishtiaq1, Mariya al-Rashida2, Rima D. Alharthy3 and Abdul Hameed1,2
H.E.J. Research Institute of Chemistry, International Center for Chemical and Biological Sciences, University of Karachi,
Karachi, Pakistan
2
Department of Chemistry, Forman Christian College (A Chartered University), Lahore, Pakistan
3
Department of Chemistry, Science and Arts College, Rabigh Campus, King Abdulaziz University, Jeddah, Saudi Arabia

Contents
15.1 Introduction 280
15.2 Classes of ionic liquids 282
15.2.1 1,2,3-Triazolium ionic liquids 282
15.2.2 Thiazolium ionic liquids 284
15.2.3 Ionic liquids from (Meth) acrylic compounds 284
15.2.4 Glycoside-based ionic liquids 285
15.3 Nanoparticles 286
15.4 Classification of nanoparticles 286
15.4.1 Carbon-based nanoparticles 287
15.4.2 Metal nanoparticles 287
15.4.3 Semiconductor nanoparticles 288
15.4.4 Polymeric nanoparticles 288
15.4.5 Lipid-based nanoparticles 288
15.5 Synthesis of nanoparticles 289
15.5.1 Synthesis of nanoparticles via ionic liquids 289
15.5.2 Solvent-exchange method 291
15.5.3 From natural iron oxide (Fe2O3) and dichalcogenide 291
15.5.4 UV-based photoreduction 292
15.5.5 Photoinduced reduction 292
15.5.6 Bio-based methods 293
15.6 Conclusion 295
References 296

Metal Nanoparticles for Drug Delivery and Diagnostic Applications r 2020 Elsevier Inc.
DOI: https://doi.org/10.1016/B978-0-12-816960-5.00015-X All rights reserved. 279
280 Metal Nanoparticles for Drug Delivery and Diagnostic Applications

15.1 Introduction
The term “ionic liquid” (IL) is used for organic salts having melting point lower
than 100 C, however, some room-temperature ILs (RTILs) are liquid even at room
temperature (Welton, 1999; Wasserscheid and Welton, 2008; Hallett and Welton,
2011; Plechkova and Seddon, 2008; Rogers et al., 2012). The concept of ILs first
emerged in the early 1900s when electrochemists were trying to prepare ideal elec-
trolytes for use in batteries. The first known IL was ethyl ammonium nitrate
[EtNH3][NO3], reported in 1914 by Walden (Walden, 1914; Welton, 1999). It was
prepared by simple reaction of ethylamine with concentrated nitric acid
(Niedermeyer et al., 2012; Hallett and Welton, 2011). The earliest synthesized 1,3-
dialkylimidazolium ILs were very reactive, even toward water and other organic
compounds, this severely limited any useful application of these ILs. Later in 1992
Wilkes and Zaworotko were credited with discovering water-stable IL, 1-ethyl-3-
methylimidazolium. This opened up new avenues for the synthesis of various other
ILs and thus began exploration of their versatile applications in organic syntheses
(Wilkes, 2002). Although there are limitless possibilities for the design of ILs, some
common classes of ILs are given in Fig. 15.1.
In general, the ILs possess certain unique physicochemical properties that render
them useful in many task-specific applications where conventional solvents are
ineffective or nonapplicable. ILs not only provide an efficient medium for carrying
out reactions but also can act as a catalyst, reagent, electrolyte, and dispersion
medium for colloids and nanoparticles (NPs). ILs also play a crucial role in

Figure 15.1 Some known cations and anions of ionic liquids (Welton, 1999; Freemantle, 2010;
Wasserscheid and Welton, 2008; Plechkova and Seddon, 2008).
 Ionic liquid based colloidal nanoparticles: applications in organic synthesis 281

analytics, biotechnology, catalysis, electrochemistry, extraction, etc. (Egorova et al.,

2017). Some characteristics of ILs that make them ideal for use in diverse applica-
tions are as follows:
• Ease of preparation
• Environmentally benign procedure to follow
• Low toxicity
• Low-cost reagents
• Tunable viscosity
• Nonflammable
• Thermal stability
• Facile recovery and reuse
The physical and chemical properties of ILs are highly dependent upon their struc-
ture, the interplay of molecular interactions such as hydrogen bonds, van der Waals
inductive and dispersion interactions. Coulombic interactions are also known to have
a profound effect on the properties of ILs (Andrzejewska et al., 2017). In fact, certain
properties of ILs can be “fine-tuned” for highly specialized applications; hence, ILs are
also dubbed as “designer liquids.”
Interestingly ILs are also biologically active, although their activity is highly
dependent on the nature of organism or type of cell as well. Retention of water
content has also been known to be an important factor contributing in their bio-
logical activity. Antimicrobial activity of ILs is well documented and can in gen-
eral be attributed to the interaction of ionic components of ILs with the
microorganism’s cell membrane causing its disruption. Anticancer activity for few
ILs has also been reported, again this is possibly due to the ability of ILs to disrupt
lipid bilayer of cell membrane; however, exact mechanism of anticancer action
varies (understandably) with the nature of IL and largely remains elusive;
and hence, this is an area demanding further exploration and investigation
(Egorova et al., 2017).
Nowadays, ILs have gained much popularity in chemistry, especially in the field of
green chemistry. Since the last decade, a dramatic increase in research papers related to
ILs has been seen. A variety of new ILs have been synthesized and utilized to test their
scope in the chemical synthesis. An estimate from SciFinder Scholar showed more
than 8000 publications on this subject from 2001. So far, around 1 million ILs have
been synthesized by simply varying the combinations of different cations and anions.
About 300 ILs are now commercially available from renowned commercial sources
(Welton, 1999; Freemantle, 2010; Wasserscheid and Welton, 2008; Plechkova and
Seddon, 2008) (Fig. 15.2).
282 Metal Nanoparticles for Drug Delivery and Diagnostic Applications

Figure 15.2 Time line for the development ionic liquids (Freemantle, 2010; Wasserscheid and
Welton, 2008; Plechkova and Seddon, 2008).

15.2 Classes of ionic liquids

Many different ILs have been synthesized and classified on the basis of their struc-
ture. Some of the important classes of ILs are briefly described in the following
sections.

15.2.1 1,2,3-Triazolium ionic liquids

There are many classes of ILs reported containing N-heterocyclic cations, among
these 1,2,3-triazolium salts are the most eminent. Some of these cations are commer-
cially available because of their extensive use in catalysis and organic synthesis.
However, a variety of these compounds can easily be synthesized by relatively
simple means. The synthesis of 1,2,3-triazolium-based ILs consists of two major steps:
(1) construction of 1,2,3-triazole ring system, and (2) its N-alkylation as shown in
Scheme 15.1.
Since ILs can be used both as a catalyst and as a medium for reaction, an interesting
approach is the design and use of ILs that are structurally endowed with the
 Ionic liquid based colloidal nanoparticles: applications in organic synthesis 283

organocatalyst moiety. Hence, chiral ILs containing α,α-diarylprolinol moieties have

been synthesized, which serve the dual purpose of IL as well as a catalyst. Scheme 15.1
shows synthesis of α,α-diarylprolinol-derived chiral IL containing 1,2,3-triazolium cat-
ion (Maltsev et al., 2010).

Scheme 15.1 Synthesis of α,α-diarylprolinol-derived chiral IL containing 1,2,3-triazolium cation

(Maltsev et al., 2010). IL, Ionic liquid. r2010. Reproduced with permission from the Elsevier Science Ltd.

1-Amino-1,2,3-triazoles can easily be obtained by the oxidation of glyoxal bishy-

drazones (Kaplan et al., 2005). 1,4-Disubstituted 1,2,3-triazole compounds are synthe-
sized by [3 1 2] cyclo-addition reactions between terminal alkynes and azides, as
shown in Scheme 15.2. These salts are relatively stable. When employed as a catalyst
and/or reaction medium for nucleophilic displacement reactions, these ILs cause
deprotonation of the substrate. In inorganic syntheses, triazolium ILs are also used for
the formation of transition metal complexes, whereby often the triazolium IL itself can
act as a ligand-forming coordination complexes with the added metal ions (Zekarias
and Jürgen, 2011).
284 Metal Nanoparticles for Drug Delivery and Diagnostic Applications

Scheme 15.2 Schematic representation of IL formation using Cu(I) (Zekarias and Jürgen, 2011). IL,
Ionic liquid.

15.2.2 Thiazolium ionic liquids

Thiazole is a structurally and biologically important scaffold. The thiamine moiety in
vitamin B1 is a naturally occurring substituted thiazolium salt. By introducing modifica-
tions in the Hanztch’s thiazole synthesis, thiazolium salts can be easily obtained in good
yields. This method is especially suitable for such thiazolium compounds (e.g., N-het-
eroaryl or N-aryl substituted thiazolium salts) where the substituent on the ring nitro-
gen cannot be introduced by direct N-alkylation. The general schematic representation
of synthesis of thiazolium salts is given in Scheme 15.3 (Munawar and Nadeem, 2011).

Scheme 15.3 Reaction of N-monosubstituted thioamides with α-halocarbonyl to give thiazolium

salts (Munawar and Nadeem, 2011).

15.2.3 Ionic liquids from (Meth) acrylic compounds

Acrylic compounds provide vast opportunities to access structurally diverse ILs. In a
typical procedure, an ionic part is introduced on two different sites either by Michael
addition on the double bond (route-2) or by nucleophilic substitution at the end of
ester chain (route-1) (Scheme 15.4) (Sindt et al., 2011).

Scheme 15.4 General scheme for the synthesis of meth acrylic compounds (Sindt et al., 2011).
 Ionic liquid based colloidal nanoparticles: applications in organic synthesis 285

For the synthesis of N-alkylimidazolium IL the two-step synthesis results in the

formation of desired product by Michael addition. In the first step the counter ion is
introduced by the protonation of N-alkylimidazole by acids such as para-toluenesulfo-
nic acid, or tetrafluoroboric acid. The second step involves the addition of N-proton-
ated alkylimidazole on an unsaturated compound such as methyl acrylate, or methyl
vinyl ketone. The schematic representation of this type of IL is shown in Scheme 15.5
(Sindt et al., 2011; Xu et al., 2007)

Scheme 15.5 General procedure for one-pot synthesis of imidazolium IL (Sindt et al., 2011; Xu
et al., 2007).

15.2.4 Glycoside-based ionic liquids

In literature, glycoside-based ILs have been reported with imidazolium, ammonium,
pyridinium, and sulfonium cations. This represents an interesting, new class of ILs,
with relatively less explored applications.
A simple nucleophilic substitution reaction is used to introduce cationic moieties
onto simple sugar molecules. A typical reaction involves selective tosylation of primary
hydroxyl groups of glycoside moiety followed by its replacement by a tertiary amine
scaffold, resulting in quaternary nitrogen-based cation with a counter anion. Thus a
wide range of different quaternary ammonium salts derived from carbohydrate precur-
sors has been prepared and investigated in this way. Structures of some of the polyca-
tionic and cationic derivatives of methyl-D-glucopyranoside are illustrated in Fig. 15.3
(Engel, 2011).

Figure 15.3 Cationic methyl-D-glucopyranoside derivatives of (i) 4-dimethylaminopyridine, (ii) N-

methylimidazole, (iii) N-methylpyrrolidine, and (iv) 4-benzyl-1-aza-4-azoniabicyclo[2.2.2]octane
(Engel, 2011).
286 Metal Nanoparticles for Drug Delivery and Diagnostic Applications

Figure 15.4 Glucose-linked triazolium ILs (v vii) (Jha and Jain, 2013). IL, Ionic liquid. r2013.
Reproduced with permission from the Elsevier Science Ltd.

A novel glucose-tethered triazolium IL has been prepared and successfully applied

for copper-catalyzed amination of bromo, chloro, and iodobenzene by using aqueous
ammonia as an amine source. One of the advantages of using 1,4-disubstituted triazo-
lium ILs containing sugars, as catalysts and reaction medium, is their ready availability/
preparation from easily accessible low-cost starting materials. Furthermore, these ILs
can be easily recovered and reused. The structure of these IL is shown in Fig. 15.4
(Engel, 2011; Jha and Jain, 2013).

15.3 Nanoparticles
NPs encompass a diverse array of “nanoscale” materials, which are typically less than
100 nm in size. These NPs have varying shapes or structures such as (1) nanotubes
(Xia et al., 2010), (2) nanobelts (Li et al., 2010), (3) nanorods (Okada et al., 2005)
(Fig. 15.5), (4) nanoribbons (Park et al., 2010), and (5) hierarchical nanostructures
(Cao et al., 2007). Nanomaterials are gaining much importance day by day in various
fields owing to their unique functional properties that can be customized and specifi-
cally tailored to cater for particular needs and applications. There are numerous shapes
or structures possible for NPs, some of these are shown in Fig. 15.5 (Tiwari et al.,
2012; Kinnear et al., 2017).

15.4 Classification of nanoparticles

NPs have been extensively categorized on the basis of their size, shape, and chemical
properties. Any type of alteration in the structure and/or size of NPs greatly influences
 Ionic liquid based colloidal nanoparticles: applications in organic synthesis 287

Figure 15.5 SEM images of structures of some nanomaterials: (A) nanotubes (Xia et al., 2010) and
(B) nanobelts (Li et al., 2010; Tiwari et al., 2012). SEM, Scanning electron microscope. (A) r2010.
Reproduced with permission from the Elsevier Science Ltd. (B) r2010. American Chemical Society
publishers.

their absorption properties, resulting in different absorption spectra and colors

(Jeevanandam et al., 2018; Khan et al., 2017).
On the basis of elementary chemical and physical characteristics, the important
classes of NPs are briefly described in the following sections.

15.4.1 Carbon-based nanoparticles

The carbon-based NPs have been classified into two major classes: (1) carbon nano-
tubes and (2) fullerenes. The fullerene is considered as an allotropic form of carbon
and has a hollow cage-like structure. There is a significant interest in the NPs because
of their various commercial applications, such as their use as fillers, a support for vari-
ous inorganic and organic catalysts, and effective gas adsorbents for various environ-
mental applications (Saeed and Khan, 2016; Mabena et al., 2011; Ngoy et al., 2014).

15.4.2 Metal nanoparticles

The metal-based NPs are typically prepared from metallic precursors, they can either be
nanosized metals, or nanosized metal oxides, metal sulfides, metal phosphates, etc.
Because of their renowned localized surface plasmon resonance characteristics (the ability
of outer electron cloud/density of NPs to oscillate in response to external electromag-
netic field), such NPs bear unique optoelectrical properties. The NPs derived from alkali
metals, and noble metals show wide absorption band in the visible region of the electro-
magnetic spectrum. Such metal NPs have extensive applications in paints, pigments, and
in preparation of new generation of advanced materials with versatile electrical and
optical properties. The shape and size of these metal NPs is crucial to modulating their
physiochemical properties for use in cutting-edge new and advanced materials (Dreaden
et al., 2012; Fedlheim and Foss, 2001). Hence, much of the research is focused on
finding synthetic strategies to control the size and shape of these metal NPs.
288 Metal Nanoparticles for Drug Delivery and Diagnostic Applications

15.4.3 Semiconductor nanoparticles

Semiconductor NPs are semiconductor materials at nanoscale. These semiconductor
NPs exhibit unique optoelectronic and magnetic properties due to their extremely
small size (1 20 nm), high surface area, and quantum size effects. These are also
known as quantum dots and have interesting applications in a wide array of areas such
as LEDs, diodes, transistors, lasers, solar cells, medical imaging, and quantum comput-
ing. The characteristic properties of these semiconductor NPs or quantum dots are
highly dependent on their size and shape (Ali et al., 2017b). Because of their
extremely small size, they are often considered as “artificial atoms,” since they have
unique, discrete, and definitive electronic states as can be seen for the naturally occur-
ring atoms/molecules. Moreover, a range of semiconductor NPs have been employed
in water-splitting applications as they have appropriate bandgap and band-edge
positions (Hisatomi et al., 2014).

15.4.4 Polymeric nanoparticles

The polymer NPs (PNPs) are typically in the form of nanospheres or nanocapsules
(Mansha et al., 2017). PNPs have diverse applications, but majority are in drug deliv-
ery. For drug-delivery applications, typically a drug molecule is entrapped or encapsu-
lated in a PNP. The nanosize of drug-PNP helps in increasing the stability of the drug
and also in cell permeation thereby ensuring effective drug action with minimum con-
centration/dose of the drug. The earlier trend in preparation of PNPs involved matrix
particles (or nanospheres) with central solid mass, having alternate molecules of differ-
ent types (according to specific need/application) adsorbed onto the outer surface of
these nanosphere. In recent studies the central solid mass has been encapsulated within
the particle completely to employ them for various applications (Abd ellah and
Abouelmagd 2017; Rao and Geckeler, 2011).

15.4.5 Lipid-based nanoparticles

The lipid-based NPs (LNPs) comprise lipids, usually as phospholipid bilayer vesicles.
Since they are mostly made from naturally occurring lipids, they are not toxic, have
high biological tolerance, and are easily biodegradable. They can easily solubilize lipo-
philic molecules and have numerous biomedical applications. Once inside the biological
system, they can be hydrolyzed by lipase enzymes. Hence, for stabilization of the exter-
nal core of these NPs, surfactants or emulsifiers are often used (Rawat et al., 2011).
In the modern era of research, lipid nanotechnology is a distinctive field, which
focuses on the usage of LNPs as carriers and delivery vehicles (Mashaghi et al., 2013).
LNPs are also being studied as vehicles for RNA release, as potential treatment for cancer
therapy. A schematic representation of the formation of small interfering RNA (siRNA)
by electrostatic interaction with a peptide is shown in Fig. 15.6 (Gujrati et al., 2014).
 Ionic liquid based colloidal nanoparticles: applications in organic synthesis 289

Figure 15.6 siRNA formation via electrostatic interaction b/w anionic siRNA and cationic head
group, disulfide bridge formation by autooxidation of thiol groups of cysteine residues, and hydro-
phobic interactions of lipid tail group (Gujrati et al., 2014). siRNA, Small interfering RNA. r2014.
Reproduced with permission from the American Chemical Society.

15.5 Synthesis of nanoparticles

Research and applications in the realm of NPs and nanotechnology is ever expanding,
with new frontiers being explored and reported routinely. A vast amount of literature
is available on the synthesis of these NPs under different conditions (Wang and
Herron, 1991; Mansur et al., 1995), which are briefly described in the following
sections.

15.5.1 Synthesis of nanoparticles via ionic liquids

Synthesis of NPs using RTILs is gaining much attention. The reason for extensive use
of ILs in synthesis is because of the potential of ILs as recyclable alternative to the
traditional organic solvents. Hence, ILs are also regarded as “green solvents.” They are
nonvolatile and provide polar environment for chemical synthesis (Hallett and
Welton, 2011; Dupont et al., 2002; Wasserscheid and Keim, 2000). A comprehensive
literature is available for the synthesis of NPs.
The IL-assisted synthesis of many different types of NPs has been carried out. The
synthesis of imidazolium-based gold NPs (Fig. 15.7) (Itoh et al., 2004) has been
reported. Similarly, magnetic NP (MNP) supported imidazolium-ILs (MNP-1)
(Zheng et al., 2009) were used to form cyclic carbonate from carbon dioxide
(Schaffner et al., 2010). The use of ILs in synthesis has increased because of their high
ionic conductivity, high thermal stability, negligible vapor pressure, and the ability to
dissolve in a variety of materials (Lin and Dehnen, 2011).
290 Metal Nanoparticles for Drug Delivery and Diagnostic Applications

Figure 15.7 Ionic liquid based gold nanoparticles (Itoh et al., 2004). r2004. Reproduced with per-
mission from the American Chemical Society.

Table 15.1 Cu Zn nanoparticle size and size distribution (Schütte et al., 2014).
Entry Molar ratio mg(mmol) mg(mmol)
of Cu:Zn precursor {[Me(C(NiPr)2)]Cu}2 [Me(C(NiPr)2)]2Zn
In [BMIm][BF4]
1 1:1 16.1 (0.039) 26.5 (0.076)
2 3:1 24.2 (0.059) 13.3 (0.038)
In PC
3 1:1 16.1 (0.039) 26.5 (0.076)
4 3:1 24.2 (0.059) 13.3 (0.038)
PC, Propylene carbonate.
r2014. Reproduced with permission from the Royal Society of Chemistry.

Marquardt et al. used ILs 1-n-butyl-3-methyl-imidazolium tetrafluoroborate and

n-butyl-N-trimethyl-ammonium bis(trifluoromethylsulfonyl)imide, for the synthesis of
Pt NPs. The reaction did not require the use of any external stabilizing agents.
Furthermore, the Pt nanoparticle-IL dispersion was also found to be a highly effective
catalyst for synthesis of triethyl(2- and 1-phenylvinyl)silane from the reaction of triethyl-
silane and phenylacetylene (Marquardt et al., 2012; Salas et al., 2011; Gutel et al., 2007).
The main reason is that the steric and electrostatic properties of the [BMIm][BF4] IL
allow the stabilization of metal NPs (Marquardt and Janiak, 2013).
ILs have also been used for the synthesis of nanoalloys (Ferrando et al., 2008). The
two amidinates {[Me(C(NiPr)2)]Cu}2 (1) and [Me(C(NiPr)2)]2Zn (2) were suspended
together under nitrogen environment. Propylene carbonate or the IL, [BMIm][BF4]
was added in different ratios as shown in Table 15.1. The complete decomposition of
the targeted amidinates in the solvent took a total of 10 min by microwave irradiation,
using low power (50 W), the reaction temperature was 220 C (Schütte et al., 2014)
(Fig. 15.8).
 Ionic liquid based colloidal nanoparticles: applications in organic synthesis 291

Figure 15.8 (A) Microwave-assisted codecomposition of metal amidinates to Cu/Zn alloy, (B)
β-CuZn alloy NPs, (C) g-Cu3Zn alloy NPs (Schütte et al., 2014). r2014. Reproduced with permission
from the Royal Society of Chemistry.

15.5.2 Solvent-exchange method

Another important method for the synthesis of NPs is solvent-exchange method. This
method primarily involves nucleation, which is the bottom approach, it is then fol-
lowed by growth which is the up approach. Such methods offer advantages to prepare
limit size particles, such as the synthesis of low-density lipoprotein (LDL) NPs for anti-
cancer drug-delivery applications. These LDL NPs possess increased hydrophobicity
since they were obtained without using phospholipid, which is a desirable characteris-
tic for drug-delivery applications (Needham et al., 2016).

15.5.3 From natural iron oxide (Fe2O3) and dichalcogenide

The metal oxide NPs can be synthesized by the adsorption of polyoxometalates
(POMs) on carbon surface using ultrasonication. This causes the carbon black to
aggregate in to small spherical-shaped particles, with a narrow size distribution and
high dispersion capacity as shown in Fig. 15.9. It has been suggested via experimental
data that size of carbon particles became smaller with increased sonication time. The
size of NPs could be varied in range of 20 50 nm by using oleic acid (Garrigue et al.,
2004; Priyadarshana et al., 2015).
292 Metal Nanoparticles for Drug Delivery and Diagnostic Applications

Figure 15.9 (A) The untreated carbon black, (B) and (C) 10 min and 1 h ultrasonication in POM
solution (Garrigue et al., 2004). POM, Polyoxometalate. r2004. Reproduced with permission from the
American Chemical Society.

Various types of transition metal dichalcogenide nanodots (TMD-NDs) have been

synthesized by applying both sonication and grinding techniques. This method was
found to be very effective and showed eminent dispersion of NPs due to their narrow
size, which was ,10 nm (Zhang et al., 2015). Cobalt tetraoxide (Co3O4) NPs have
been prepared by laser fragmentation, which gave well-organized NPs. The average
size of these particles was found to be in range of 5.8 6 1.1 nm (Zhou et al., 2016).

15.5.4 UV-based photoreduction

This is a simple and effective method. This method is most commonly reported for
the synthesis of silver NPs in the presence of collagen, citrate, polyvinylpyrrolidone,
and polyacrylic acid. Relatively large size of silver NPs was observed when irradiated
for 3 h under UV. By extending the integration of UV irradiation, the size of NPs
got smaller, and a relatively stable size and size distribution could be obtained
(Huang and Yang, 2008). Silver NPs, including nanospheres, nanowires, and den-
drites, have been synthesized using UV irradiation photoreduction technique at
room temperature using poly vinyl alcohol (PVA) as a protecting and stabilizing
agent. The concentration of both silver nitrate and PVA plays an important role in
growth of dendrites and nanorods (Zhou et al., 1999). In a very recent approach the
size of the silver NPs was optimized using different concentrations of PVA. The
concentration at which PVA stabilizes the Ag NPs was 2 g/100 mL. The Ag NPs/
PVA sample prepared in the absence of UV light had a larger particle size than the
irradiated ones (Ali et al., 2017a).

15.5.5 Photoinduced reduction

Another method used for the synthesis of NPs is photoinduced reduction, or photoca-
talytic reduction method. Using this method, the NPs synthesized had an average size
of 8 nm. Different stabilizing agents such as poly styrene sulfonate and polyallylamine
 Ionic liquid based colloidal nanoparticles: applications in organic synthesis 293

Figure 15.10 Carnation flower-like ZnO@AgI hierarchical nanostructures (Huang et al., 2017).
r2017. Reproduced with permission from the Elsevier Science Ltd.

hydrochloride can be used. The growth/size of NPs was controlled using dual-beam
illumination of NPs (Ferrando et al., 2008). This is a clean processing that possesses a
high spatial resolution and affords great versatility. It allows fabrication of NPs in vari-
ous mediums such as emulsions, cells, surfactant micelles, and glasses.
Highly coherent visible light driven catalysts are required for the effective photo-
degradation of organic pollutants. In this regard, ZnO@AgI carnation like hierarchi-
cal nanostructures (Fig. 15.10) have been prepared at room temperature (Huang et al.,
2017). The results indicated high efficiency of ZnO@AgI nanostructures under visible
light radiation at the optimized concentration of ZnO@AgI 5% sample. The forma-
tion of ZnO@AgI nanostructures is illustrated in Fig. 15.11.
RTILs have been explored as reaction medium and as capping agents. Anisotropic
gold NPs have been synthesized in the presence of IL, 1-butyl-3-methylimidazolium
tetrafluoroborate ([BMIM][BF4]) as reaction medium without any capping agents. The
morphology of NPs can be controlled by use of appropriate IL ([BMIM][BF4]) and by
changing reagent concentrations (Fig. 15.12) (Zhu et al., 2007).

15.5.6 Bio-based methods

These methods are often regarded as economical and environmental friendly processes
because they do not make use of toxic chemicals for the synthesis. The organisms that
tend to be most frequently used (as biological reducing agents) for the NP synthesis
range from prokaryotes to eukaryotic fungi and plants (Mohanpuria et al., 2008). The
examples of NPs produced via bacteria include silver, gold, zinc, cadmium, and iron
NPs. The literature reports use of algae and fungi for gold, cadmium, and silver NPs;
yeasts for lead, cadmium, and silver NPs; and use of plants and plant extracts for the
294 Metal Nanoparticles for Drug Delivery and Diagnostic Applications

Figure 15.11 Schematic representation of (A) formation of ZnO hierarchical nanostructures and (B)
the deposition of AgI NPs on ZnO nanosheets (Huang et al., 2017). NP, Nanoparticle. r2017.
Reproduced with permission from the Elsevier Science Ltd.

Figure 15.12 Preparation of gold sheets in ionic liquid [BMIM][BF4] (Zhu et al., 2007). r2017.
Reproduced with permission from the Elsevier Science Ltd.

synthesis of palladium, zinc oxide, and magnetite NPs (Bhattacharya and Gupta, 2005;
El-Rafie et al., 2013) (Fig. 15.13).
The synthesis of gold NPs is reported using the fungus Trichothecium species via
both intracellular and extracellular methods. The results showed quick formation of
gold NPs of different shapes, such as spherical, rod-like, and triangular (Ahmad et al.,
2005). It was also observed that the proteins and enzymes, which were released under
 Ionic liquid based colloidal nanoparticles: applications in organic synthesis 295

Figure 15.13 TEM micrograph of Ag NPs prepared by using polysaccharides extracted from
different marine macro algae, that is, (A) Ulva fasciata, (B) Pterocladia capillacae, (C) Jania rubins,
and (D) Colpmenia sinusa (El-Rafie et al., 2013). r2013. Reproduced with permission from the Elsevier
Science Ltd.

stationary condition during the reaction, did not release under the shaking condition
and result in the formation of desired extracellular or intracellular gold NPs.
Moreover, the gold NPs did not show toxicity to the cells, and the growth of cells
continued even after the biosynthesis of gold NPs.

15.6 Conclusion
ILs are versatile solvents, having many desirable characteristics such as high thermal sta-
bility, nonvolatile nature, and their ability to dissolve a variety of compounds.
Moreover, after use, they can be easily recovered, recycled, and reused. Many of the
physical and chemical properties of ILs can be tailored to meet task-specific require-
ments, this is easily done by choice of appropriate cation and anion. A combination of
diverse range of organic cations and organic and inorganic anions has been explored as
ILs. In addition to being used as solvent, they are often used as catalysts. IL-mediated
synthesis of NPs has become a well-established field, where ILs are not only used as
solvents, but also as stabilizing or capping agents, thereby eliminating the need for any
296 Metal Nanoparticles for Drug Delivery and Diagnostic Applications

other external stabilizing or capping agent. The ability of ILs to be “custom-made” is

particularly useful for NP synthesis, where the nature of ILs is known to be directly
linked to the size and shape of obtained NPs, thereby providing an easy means of con-
trolling size and shape of NPs.

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