Nanocomposite Materials:

Chapter
5
Biomolecular Devices
CHAPTER OUTLINE
5.1.0 Introduction 145
5.2.0 Hybrid Nanocomposites 147
5.2.1 Polymers-Based Nanocomposites 148
5.2.2 Metal, Metal OxideseCarbon Nanohybrid Materials 149
5.3.0 Conclusions 156
References 156

5.1.0 INTRODUCTION
Nanocomposites are a class of nanomaterials wherein one or more phases at
nano-sized dimension (zero dimension, one dimension, and two dimen-
sions) are embedded in a ceramic, metal, or polymer material [1,2]. These
can be made by inorganic or organic components at the molecular level to
obtain new properties [1,2]. Two materials can be used to fabricate a com-
posite nanomaterial via weak interactions such as van der Waals, hydrogen
bonding, weak electrostatic interactions, or by covalent bonds [3]. The term
nanocomposite is used when discrete structural units in the individual size
regime are utilized [1e3]. Nanoparticles, nanorods, nanofibers, and carbon
nanotubes (CNTs) are examples of the discrete inorganic units of nanocom-
posite materials. A nanocomposite can show a synergistic property that is not
present in the individual component. The property of an individual compo-
nent of nanomaterial can be tailored by adding another component or mul-
tiple components of the nanomaterials. The nanocomposites exhibit
multifunctional properties such as high surface-to-volume ratio for loading
of biomolecules such as enzymes, high mechanical strength, high electrical
conductivity, redox reactivity, and catalytic activity. The researchers have
utilized the nanocomposite materials as transducer materials for enzymes-
based bionanoelectronic devices [4,5]. In addition, nanocomposite materials

Nanomaterials for Biosensors. http://dx.doi.org/10.1016/B978-0-323-44923-6.00005-4

Copyright © 2018 Elsevier Inc. All rights reserved. 145
146 CHAPTER 5 Nanocomposite Materials: Biomolecular Devices

have been used for imaging, targeted drug delivery, batteries, gas sensing,
and artificial implants [6e9]. Because of their amenability to biological
functionalization, nanofeatures, etc., nanocomposites have been found to
have biomedical applications such as in detection of cancerous cells [10]
and pathogens [11].
Many nanocomposites such as metal oxidesemetal nanohybrid materials,
metalecarbon nanomaterials, metal oxidesepolymer, etc. can be used for
fabrication of enzymatic sensors [12]. These nanocomposite materials can
be synthesized by various chemical methods including solegel route, hydro-
thermal, self-assembly process, chemical coprecipitation, etc. [13]. Specif-
ically, nanocomposite material serves as a transducer for immobilization
of enzyme molecules on its surface via physical interactions, entrapment,
or covalent interactions between them [14]. Nanocomposite materials can
be categorized as inorganic nanostructures, organic nanostructures, and
organiceinorganic hybrid nanostructures. Inorganic materials including
CNTs, gold (Au), silver (Ag), platinum (Pt), zinc oxide (ZnO), iron oxide
(Fe3O4), cerium oxide (CeO2), tin oxide (SnO2), titanium oxide (TiO2),
zirconium oxide (ZrO2), etc. can form nanocomposites by combining two
or more elements. The organic materials such as polyaniline (PANI),
polypyrrole, poly(3,4-ethylenedioxythiophene) (PEDOT), chitosan (Ch),
and others such as the self-assembled monolayer of 8-amino polythiophene,
etc. can form nanocomposite with inorganic materials to obtain enhanced
efficacy of a sensor. Some of the advantages of the inorganiceorganic
hybrid composite include film uniformity, biocompatibility, available
amines or hydroxyl groups, or carboxyl groups, etc. that can be utilized
for immobilization of living organisms or biomolecules for biosensor
applications.
A grapheneechitosan nanocomposite electrode was reported to show
enzyme loading of 1.12
109 mol/cm2, a wider detection range
(0.08e12 mM) of glucose with a low detection limit of 0.02 mM, and
higher sensitivity (37.93 A/mM cm2) due to direct electron transfer [15].
Cadmium sulfide nanocrystalseembedded CNTs-based nanocomposite
was exploited for development of enzymatic biosensor by applying the
principle of signal-on electrochemiluminescence to detect choline and
acetylcholine with improved sensing efficacy [16]. Tyrosinase enzyme
was immobilized on the surface of iron oxide nanoparticlesechitosan
nanocomposite-based electrode for detection of phenolic compounds
wherein the larger surface area of Fe3O4 nano-sized particles and the
porous chitosan network resulted in high enzyme loading, and the
entrapped enzyme could retain its bioactivity [17].
 5.2.0 Hybrid Nanocomposites 147

5.2.0 HYBRID NANOCOMPOSITES

The nanocomposite materials obtained by mixing organic and inorganic
hybrid materials have been predicted to have a large number of biomedical
applications [2]. The hybrid materials are either homogeneous systems that
can be obtained from monomers and organic and inorganic components or
heterogeneous systems (also called as nanocomposites) wherein the
dimension of at least one component should be a few angstroms to several
nanometers. In 1980, the concept of organiceinorganic hybrid nanocompo-
site [2] was exploited using the soft chemistry-based processes described as
under:
n copolymerization of metal alkoxides, functional organosilanes, and
macromonomers
n encapsulation of organic components using solegel-derived metallic
oxides
n organic functionalization of nanoclays or other compounds with
lamellar structures, etc.
Nanocomposites are made of organiceinorganic hybrids such as polymere
metal or metal oxides. PolymereCNTs [18] and biopolymeremetal or metal
oxides [19] have been found to exhibit both organic and inorganic proper-
ties. The choice of a polymer in a nanocomposite is attractive due to hydro-
philic balance, chemical stability, biocompatibility, and chemical
functionalities such as solvation, wettability, and templating effect [12]. In
many cases, the organic component provides both processability of the ma-
terial and easy shaping. However, the inorganic components offer new func-
tionalities depending on shape, size, and crystalline properties of the
inorganic phase such as metal oxides, nanoclays, nanometals, etc. In addi-
tion to this, the inorganic component can be utilized to enhance redox reac-
tivity, electrochemical and electronic properties, and refraction index.
Organic molecules including macromonomers, oligomers, etc. can be inte-
grated with metal oxides or siloxaneeoxide hybrid matrices by mixing the
metal alkoxides and organosilanes in the same solvent wherein organic mol-
ecules are trapped through hydrolysis and condensation [2]. Also, organic
molecules can be incorporated via impregnating them into the porous
network. Both approaches have been established by inorganic solegel
chemistry. Covalent or ionecovalent interactions were utilized to make
strong bonds for organiceinorganic species. Silicon-containing components
are mainly used to develop the hybrid organiceinorganic nanocomposites
wherein organo-alkoxysilane molecular precursors or oligomers, i.e.,
R0 nSi(OR)4-n with n ¼ 1, 2, 3 were used as hybrid molecular precursors
[2]. In most cases, the SieC bond remains stable for hydrolysis, and the
148 CHAPTER 5 Nanocomposite Materials: Biomolecular Devices

R0 organic group provides new properties such as hydrophobicity, flexibility,

wettability, refractive index change, molecular recognition properties, etc. in
the inorganic network. Thus, the hybrid nanocomposite materials provide a
wide range of possibilities for synthesizing tailor-made materials to obtain
chemical and physical properties. Efforts are continuing for tailoring of
new hybrid nanocomposites with exciting properties toward biosensing
applications.

5.2.1 Polymers-Based Nanocomposites

Many polymer-based hybrid nanocomposites such as PANI, polypyrrole,
PEDOT, Ch, etc. with metals, oxides, and carbon materials were used for
development of biosensor devices [12]. Conjugated polymers are known
as macromolecules with electron-delocalized unsaturated backbones inter-
connected by double bonds, triple bonds, or aromatic rings, and they
show good solubility and electronic properties. The ease of synthesis, excel-
lent mechanical and charge transfer properties, and excellent dispensability
and stability of polymer-based nanocomposites make them attractive for use
in biosensor fabrication. The small dimensions and high surface-to-volume
ratio of the nanocomposite using gold nanoparticles (Au NPs) and PANI
nanofibers were used for glucose biosensor and high sensitivity was found
to be potentially suitable for glucose sensing in vitro or in vivo [4]. The
hybrid nanocomposite containing CNTs and ordered PANI was reportedly
synthesized via in situ polymerization reaction using a template of single-
walled nanotubes and reactant of aniline [20]. This nanocomposite offered
higher electrical conductivity and Seebeck coefficient than using PANI alone
resulting in enhanced carrier mobility [20]. Due to high magnetism, biocom-
patibility, and ease of functionalization the Fe3O4epolyrroleeAu
nanocomposite-based electrode was used to detect ascorbic acid [21]. It
was demonstrated that piepi interactions between graphene and polymer
play an important role in the tuning of band gap of the nanocomposite
[21]. The nanocomposites of polymers and graphene combine the advan-
tages of graphene with that of polymers providing synergistic platforms
for various biosensor applications. A nanocomposite of graphenee
polyvinylpyrrolidoneePANI (Fig. 5.1.1) was employed for development
of paper-based cholesterol biosensor [22].
Chitosan (Ch) is a promising organic bioactive polymer material [23]. It is a
linear polysaccharide consisting of b-(1-4)-linked D-glucosamine (deacety-
lated unit) and N-acetyl-D-glucosamine (acetylated unit). It has been used
to fabricate hybrid nanocomposites with inorganic components for biosensor
and biomedical applications due to their excellent film-forming ability, high
permeability, nontoxicity, biocompatibility, low cost, and easy availability.
 5.2.0 Hybrid Nanocomposites 149

n FIGURE 5.1.1 (A) Schematic of a paper-based biosensor for cholesterol detection. The enzymatic bioreaction on the sensor interface made by the hybrid
nanocomposite of grapheneepolyvinylpyrrolidoneepolyaniline (G/PVP/PANI). The biochemical reaction is between cholesterol and cholesterol oxide (ChOx).
(B) Sensor calibration plot for the range of 50 mM to10 mM and inset showing calibration plot between 50 mM and 1 mM of cholesterol [22].

Ch has many reactive amino groups that can be used in chemical modifica-
tions to prepare a variety of useful derivatives. The chemical modification of
Ch can provide a hydrophilic environment for the biomolecules. Specif-
ically, the amino or hydroxyl groups in the hybrid nanocomposites of Ch
can be chemically modified by covalent interactions with biomolecules.
The chemical structure of Ch is shown in Fig. 5.1.2. Ch was used to fabricate
nanocomposite (Fig. 5.1.2) with iron oxide nanoparticles (CheFe3O4) for
detection of ochratoxin-A via the electrochemical technique [24]. In another
application, Khan et al. reported a Ch-based hybrid nanocomposite with zinc
oxide nanoparticles for detection of cholesterol, and this nanocomposite
showed excellent enzyme activity due to its good biocompatibility [25].

5.2.2 Metal, Metal OxideseCarbon Nanohybrid

Materials
The nanocomposite of CNTs and nanostructured metal oxides (nMOs)
shows unique properties for construction of biosensor devices [26]. CNTs
150 CHAPTER 5 Nanocomposite Materials: Biomolecular Devices

n FIGURE 5.1.2 Schematic presentation of an immunosensor fabrication using chitosan (Ch)eiron oxide (Fe3O4) hybrid nanocomposite, chemical structure of Ch,
and the biochemical reaction [24].

are promising building blocks for nanohybrid materials [26]. The CNTs and
nMO nanohybrid can provide excellent biosensing characteristics. With a
large surface area, a high aspect ratio, structural integrity, high oxidation sta-
bility, and chemical inertness, CNTs can yield suitable nanohybrid materials
to obtain nanobiointerfaces with bio-species and enhanced biosensing
efficacy. Nanohybrid materials based on CNTs including inorganic speciese
CNTs and organic specieseCNTs can be synthesized by numerous
techniques by attaching nanoparticles to CNTs (ex situ) or directly on the
surface of CNTs (in situ). The synergistic effect of CNTemetal oxide
heterostructures combines properties of both these nanocomposites, and
their superior electrochemical properties make them ideal candidates for
electrochemical biosensors. TiO2eCNTs, NiOeCNTs, Fe3O4eCNTs,
Co3O4eCNTs, ZnOeCNTs, CeO2eCNTs, ZrO2eCNTs, etc. are examples
of the nanohybrids that are being explored for biosensors development.
Carboxyl groups present on the surface of CNTs are often employed for
the attachment of amine-terminated or mercapto-terminated nMO via amide
bonds achieved by direct conjugating mercapto-terminated or amine-
terminated nanoparticles with carboxylated CNTs or after converting
 5.2.0 Hybrid Nanocomposites 151

carboxyl groups into thiol groups to anchor colloidal nanoparticles [27].

Without conjugating, nMO can be directly attached to the surface of carbox-
ylated CNTs due to the hydrophilic nature of CNTs, for example, nanostruc-
tured MnO2, MgO, and TiO2 were used to attach to the surface of CNTs
[28e30]. Capping agents were used to obtain uniform distribution and better
adhesion of nMO on CNTs due to their week interactions resulting in
nonuniform distribution of nMO. The TiO2 nanoparticles produced using
the solegel technique were capped by cetyltrimethyl ammoniumbromide
to conjugate with 2-amino-ethylphosphoric acidemodified CNTs [31]
wherein the phosphonic groups were well distributed on CNTs surface for
attachment of the TiO2 nanoparticles by producing a driving force
(Fig. 5.1.3A). Similarly, SiO2 nanoparticles [31] were anchored to
alkoxysilane-modified CNTs (Fig. 5.1.3B).
Iron oxide (Fe3O4) nanoparticles were anchored on the surface of carboxyl-
ated CNTs [32] to immobilize acetylcholinesterase via covalent interactions

n FIGURE 5.1.3 Decoration of nanostructured titanium dioxide (TiO2) (A) and silicon dioxide (SiO2) (B) at the surface carbon nanotubes (CNTs) [31].
152 CHAPTER 5 Nanocomposite Materials: Biomolecular Devices

for detection of organophosphorus insecticides (Fig. 5.1.4). This biosensor

showed a good sensitivity of 0.475 mA/mM, a low limit of detection
(0.1 nM), reusability of more than 50 times, and stability of 2 months for
the detection of pesticide [32]. Zirconia (ZrO2)-grafted CNTs-based nucleic
acid biosensing platforms were developed for detection of Mycobacterium
tuberculosis [33]. SnO2 and ZnO nanoparticles-based CNT nanocomposites
were utilized for selective detection of dopamine [34]. The excellent redox
properties of TiO2eCNT nanocomposite was used to detect leukemia cells
[35]. In addition to nMO incorporation onto CNTs, metal nanoparticles
such as platinum (Pt), gold (Au) etc. were explored to prepare nanocompo-
sites with CNTs to stabilize immobilization of biomolecules and selective
conjugations for the development of nanoelectronic biosensors. Hrapovic
et al. demonstrated the incorporation of Pt nanoparticles on the surface
CNTs for detection of biomolecules [36].
Graphene and its derivatives such as graphene oxide (GO), reduced gra-
phene oxide (rGO), and nitrogen-doped graphene were explored as
scaffolds to grow nMO as well as metal nanoparticles for biosensors

n FIGURE 5.1.4 Schematic presentation of an amperometric biosensor using iron oxide (Fe3O4)ecarbon nanotubes (CNTs) nanocomposite [32]. AChe,
acetylcholinesterase; ATCl, acetylthiocholine chloride; c-MW CNTs, multiwalled CNTs; NH2, amine.
 5.2.0 Hybrid Nanocomposites 153

development [37]. Individually, the applications of GO and rGO were

widely explored for electrochemical as well as optical biosensing due to their
inherent properties [38]. However, researchers made continuous effort for
graphene-based nanocomposite materials to improve biosensors characteris-
tics. Unlike coiled structures of CNTs, flats-like graphene structures and
sheets are more useful and convenient for nanostructured metal or metal
oxides loading as well as immobilization of biomolecules. Researches
show that the edges of graphene sheets are more reactive to organic or inor-
ganic nanostructured materials than basal plane. The nanocomposites of
graphene-based materials with nMO play an important role toward the
construction of biosensors. The single-layered GO shows excellent redox
behavior of [Fe(CN)6]3/4 mediator for detection of glucose concentration
via the cyclic voltammetry technique [39]. Zhao et al. recently deposited
nanostructured ZnO on chemically reduced graphene film to obtain direct
electron transfer between glucose oxidase (GOx) and the electrode [40].
The direct electron transfer was attributed to the nanostructured ZnO wiring
between the redox center of the enzyme and electrode [40]. In the band struc-
ture diagram before (Fig.5.1.5A) and after (Fig.5.1.5B) the contact of nano-
structured ZnO and graphene, the energy band of ZnO was found to bend
downward due to its higher work function when compared with that of
graphene, resulting in the formation of an electron antiblock layer
(Fig. 5.1.5). It appeared that the heterostructure of this nanocomposite

(A) (B)
E0

ZnO CRG Pt
~5.3eV 4.42eV 5.65eV
Ec
~0.88eV
Er
3.37eV
Ev

(C) (D)
E0

ZnO Pt
~5.3eV 5.65eV ~0.35eV
Ec
Er

Ev

n FIGURE 5.1.5 Band structure of nanocomposite electrodes. The band structure before (A) and after (B) physical contact of zinc oxide (ZnO) to the graphene
film on the platinum (Pt) electrode. The band structure before (C) and after (D) physical contact of ZnO to the Pt electrode [40].
154 CHAPTER 5 Nanocomposite Materials: Biomolecular Devices

perhaps favored direct detection of the electrochemical signal of the GOx

enzyme. On the other hand, the band structure of ZnO before
(Fig. 5.1.5C) and after (Fig. 5.1.5D) contact of the Pt electrode with the
graphene film is shown in Fig. 5.1.5. The energy band of ZnOePt bends
upward due to smaller work function of ZnO as compared with that of Pt

n FIGURE 5.1.6 (A) Photograph of nanocomposites-based microfluidic immunosensors. (B) Functionalization of antibody of epidermal growth factor receptor 3
or anti-ErbB2 molecules on the surface of graphene foam and titanium dioxide nanofibers and graphene (GFnTiO2) composite electrodes using N-ethyl-N-(3-
dimethylaminopropyl) carbodiimide-N-hydroxysuccinimide (EDCNHS) chemistry followed by treating oxygen plasma [44]. CE, Counter electrode; RE, reference
electrode; WE, working electrode.
 5.2.0 Hybrid Nanocomposites 155

resulting in the formation of a w0.35-eV Schottky barrier [40]. This

Schottky barrier can block the electron transfer from ZnO to the Pt electrode.
The excellent catalytic properties of functional SnO2egraphene and electro-
spun NiOegraphene nanocomposites were fabricated as biosensing
platforms for detection of biomolecules [41,42]. A magnetically controlled
functionalized Fe3O4egrapheneegold nanocomposite-based electrochemi-
luminescence biosensor was developed for detection of HeLa cells that
offered a high sensitivity, and good stability and reproducibility [43]. The
titanium dioxide nanofibers were assembled on the scaffolds of hierarchical
porous graphene foam to make a nanocomposite (Fig. 5.1.6) for the devel-
opment of a microfluidic immunobiochip to detect a femtomolar (1.0 fM)
concentration of breast cancer biomarker [44]. Graphene was used as
scaffolds by growing metal nanoparticles to improve the catalytic perfor-
mance of the biosensor devices. It was demonstrated that direct immobiliza-
tion of biomolecules on the graphene surface was not stable and could be
easily washed away. For example, the rGO sheet was anchored by antiimmu-
noglobulin G (anti-IgG) Au NPs and used to develop a field-effect
transistorebased biosensing device (Fig. 5.1.7) [45].

(A) Anti-IgG IgG

Au NP
Source Drain
+ –

Au TRGO sheet
SiO2
Si

Gate +
(B)
TRGO Au NP-anti IgG
sheet conjugates
Au

SiO2
Si

Blocking
buffer

FET and direct current

measurements IgG

n FIGURE 5.1.7 (A) Schematic presentation of an reduced graphene oxide (rGO)-based field-effect transistor (FET) wherein anti-IgG is decorated to surface rGO
sheets via gold nanoparticles (Au NPs). (B) Stepwise illustration of the rGO-based FET biosensor. In this process, first the rGO sheets were dispersed on the
electrode surface and decorated with antibody-conjugated Au NPs via noncovalent interactions [45]. Anti-IgG, antibody of immunoglobulin G; Si, silicon; SiO2,
silicon dioxide; TRGO, thermally reduced graphene oxide.
156 CHAPTER 5 Nanocomposite Materials: Biomolecular Devices

5.3.0 CONCLUSIONS
In summary, the hybrid nanocomposite materials are not only new exciting
materials for academic research but also for their enhanced features that
allow many industrial applications. In this chapter, we have discussed the
hybrid nanocompositesebased biomolecular devices and prospects in
health care diagnostics. The preparation of most nanocomposite materials
is based on the copolymerization of functional organosilanes, monomers,
and metal alkoxides and encapsulation of organic components with
inorganic metallic oxides and nanometals, polymerization of monomers
with carbon materials. With exciting synergistic properties, the nanohybrid
composites have promising applications in the area of biomolecular devices,
and they offer high sensitivity, better stability, low limit-of-detection, and
reproducibility to detect various bio-species compared with single
componentebased biomolecular devices. Although these smart hybrid
nanocomposites can be used for development of different biomedical de-
vices, there is a lack of understanding of the structural complexity and
the prevalent interactions. There is a potential demand for the availability
of simple, easy, and low-cost single-component biomolecular devices. In
the next chapter (Chapter 6: Plasmonic Nanostructures: Fiber-Optic Biosen-
sors), we discuss the use of plasmonic nanostructures for optical biosensors
and fiber optic-based optical biosensors.

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