NANOTECHNOLOGY ADVANCES

ELECTROCHEMICAL IN
BIOSENSING
Presented By: Sher Afgan

University Of Lahore
 Introduction
■ Nanoparticle technology plays a key role in providing opportunities and
possibilities for the development of new generation of sensing tools. The
targeted sensing of selective biomolecules using functionalized
nanoparticles has become a major research thrust in the last decade. NP-
based sensors are expected to change the very foundations of sensing and
detecting biomolecules. NP-based sensors are expected to change the
very foundations of sensing and detecting biomolecules. In this review,
we will discuss the use ofsurface functionalized NPs for smart sensor
fabrication leading to detection of specific biomolecules and heavy metal
ions.
 Nanomaterials as sensors
■ Nanotechnology is playing an increasingly important role in the
development of biosensors. The sensitivity and performance of
biosensors is being improved by using nanomaterials for their
construction. The use of these nanomaterials has allowed the introduction
of many new signal transduction technologies in biosensors. Portable
instruments capable of analyzing multiple components are becoming
available. This work reviews the status of the various nanostructurebased
biosensors. Biosensors, developed by integrating the biological and
physicochemical/mechanical properties (of transducers), which can have
enormous implication in healthcare, food, agriculture and biodefence.
Nanomaterials as Biosensors
 The Functions of Nanoparticles

■ Many kinds of nanoparticles, including metal

nanoparticles, oxide nanoparticles, semiconductor
nanoparticles, and even composite nanoparticles, have
been widely used in electrochemical sensors and
biosensors
 Classification of Nanoparticles on the basis of their function

Basic functions of nanoparticles can be mainly classified as:

■ Immobilization of biomolecules;
■ Catalysis of electrochemical reactions;
■ Enhancement of electron transfer;
■ Labeling biomolecules and
■ Acting as reactant
 Immobilization of Biomolecules

■ Generally, the adsorption of biomolecules directly onto naked surfaces of

bulk materials may frequently result in their denaturation and loss of
bioactivity. However, the adsorption of such biomolecules onto the
surfaces of nanoparticles can retain their bioactivity because of the
biocompatibility of nanoparticles. Since most of the nanoparticles carry
charges, they can electrostatically adsorb biomolecules with different
charges. Besides the common electrostatic interaction, some
nanoparticles can also immobilize biomolecules by other interactions.
For example, it is reported that gold nanoparticles can immobilize
proteins through the covalent bonds formedbetween the gold atoms and
the amine groups and cysteine residues of proteins.
Catalysis of Electrochemical Reactions

■ Many nanoparticles, especially metal nanoparticles have excellent catalytic properties.

The introduction of nanoparticles with catalytic properties into electrochemical sensors
and biosensors can decrease overpotentials of many analytically important
electrochemical reactions, and even realize the reversibility of some redox reactions,
which are irreversible at common unmodified electrodes. For instance, a sensitive
NOmicrosensor was developedthrough the modification of a platinum microelectrode
with gold nanoparticles in which gold nanoparticles catalyze the electrochemical
oxidation of NO with an overpotentialdecrease of about 250 mV.
Catalysis of Electrochemical Reactions
■ The catalytic oxidation of NO can also be observed at dense gold nanoparticle film
modified electrodes. Based on the selective catalysis of nanoparticles, selective
electrochemical analysis could be achieved.
■ Platinum nanoparticles are another type of nanoparticle that exhibit good catalytic
properties and have been used in electrochemical analysis.
 Enhancement of Electron Transfer

■ Electrical contacting of redox-enzymes with electrodes is akey process in the

construction of third-generation enzymeelectrodes. While enzymes usually lack direct
electricalcommunication with electrodes due to the fact that the active centers of
enzymes are surrounded by considerably thick insulating protein shells, and the electron
transfer between electrodes and the active centers are blocked, the conductivity
properties of nanoparticles, mostly metal nanoparticles at nanoscale dimensions made
them suitable for enhancing the electron transfer between the active centers of enzymes
and electrodes acting as electron transfer “mediators” or “electrical wires”.
 Enhancement of Electron Transfer

■ Silver nanoparticles, as well as gold nanoparticles, have good conductivity, and they can
also be used to enhance the electron transfer between proteins and electrodes.
Assembled silver nanoparticles on to pyrolytic graphite electrodes, and then
immobilized cytochromecon these nanoparticles. It was reported that silver
nanoparticles act as the electrical bridge that “wires” the electron transfer between
cytochrome c and the electrode, and the electron transfer rate constant was about 15.8 s.
The direct electron transfer between myoglobin and the electrode has also been
elucidated by the same group with silver nanoparticles. Some nonmetal nanoparticles,
such as oxide nanoparticles and semiconductor nanoparticles, can also enhance the
electron transfer between proteins and electrodes in certainsystems. For instance,
horseradish peroxidase was mixedwith TiO2 nanoparticles and immobilized onto
pyrolyticgraphite electrodes, which resulted in direct electron transfer.
 NONENZYMATIC SENSORS

■ The pursuit of electrochemical systems for bimolecular detection has received

significant attention over the last two decades. Electroanalysis toward small molecules
is also of importance in a variety of areas. Enzymatic sensors possess high selectivity
but suffer from limitations such as instability, complicated modification procedures, and
critical microenvironmental factors. Such limitations stimulate the development of
nonenzymatic electrochemical sensors with simple modification procedures and good
stability. Enzyme-free electrochemical sensors have been widely used for determining
the presence of hydrogen peroxide, glucose, and dopamine. The perspectives and
current challenges of enzyme-free electrochemical sensors were discussed by Chen et al
Miao et al. recently reviewed electrocatalysis and electroanalysis of nickel, itsoxides,
hydroxides, and oxyhydroxides toward small molecules. Following are some examples
of nonenzymatic sensors for the detection of small molecules.
 ELECTROCHEMICAL ENZYME-
BASED BIOSENSORS
■ Electrochemical enzyme-based biosensors, a subclass of chemical sensors, combine the
high specificity of the enzyme with the sensitivity of electrochemical transducers.
Enzyme electrodes are electrochemical probes with a thin layer of immobilized enzyme
on the surface of the working electrode. The enzyme is the most critical component of
the enzyme electrode since it provides the selectivity for the sensor and catalyzes the
formation of the electroactive product for detection. In the past two years, there were
some review articles that focused on the development of various materials, techniques,
and applications of electrochemical enzyme-based biosensors.
 Immobilization Strategies
■ The immobilization of enzymes is one of the key steps in developing high-performance
biosensors, since it will affect the loading as well as the bioactivity of the enzymes. To
date, different methods have been studied to achieve efficient enzyme immobilization,
such as covalently binding enzymes onto the substrate surface or incorporating enzymes
into different matrixes. The development of the synthesis of nanomaterials provides
enormous opportunities for tailoring their properties, thus enhancing their functions and
application in immobilization of enzymes. A great number of nanostructured materials
with different sizes, shapes, and compositions have been synthesized and utilized as
novel electrode materials for immobilization of desired enzymes. Due to the
homogeneous spherical shape, high conductivity, and large surface area for
biomolecularconjugation, graphite NPs, consisting of several stacked graphene sheets,
were reported to construct an enzymebiosensor to detect glucose in real
samples.Aftermodification, GOx was linked with graphite NPs through an amide bond.
 CONCLUSIONS
■ Inherent sensitivity, simplicity, speed, and cost benefits continue to be strong driving forces for
the development of electrochemical sensors and biosensors. In this Review, we have summarized
remarkable advances in the development of novel ultrasensitive electrochemical assays based on
nanomaterials and nanostructures. There have been thousands of sensor papers published during
the past two years, where electrochemical sensors represent the most rapidly growing class.
Compared to other methods, such as spectroscopy and chromatography, the electrochemical
measurements are much cheaper and simpler and easier to miniaturize, which makes them more
suitable forPOC detection, particularly for delivering benefits for resourcelimited areas in both
developed and developing countries.Besides that, a wide variety of strategies are used to improve
the efficacy of sensing. Signal amplification for detection to utilize NPs as carriers or tracers,
catalysts, and electronic conductors and produce a synergic effect among catalytic activity,
conductivity, and biocompatibility has been achieved. New developments in nanotechnology and
material science as well as in custom engineering of biorecognitioncomponents have advanced
the progress of useful and reliable electrochemical sensors and biosensors.
 CONCLUSIONS
■ The materials and biomaterials with rich nanostructures not only improve the electronic
properties and increase the effective electrode surface for transferring electrochemical
signal but also produce detectable signals for indirect detection of targets. Thus, the
resulting methods possess high sensitivity and good specificity. The synergy of
multifunctional materials, recognition elements, and electrochemical methods is
improving the selectivity, stability, and reproducibility, thus promoting the development
of sensors for assays and bioassays.Significant advances have been made in several
areas related to the design and application of electrochemical sensors and biosensors.
However, there is still much effort needed to implement these ultrasensitive sensors and
biosensors for realworld applications. The integration of electrochemical sensors into
(paper-based) microfluidic formats with the incorporation of unique materials for
detection needs to be extensively explored in the future. The development of these
systems would also lead to significant advantages compared to the current analytic
systems, in terms of simplicity, speediness, cost, and automation. We envision that a
sensing device that can simultaneously monitor the levels of cell, DNA, RNA, protein,
and small molecule-related markers in a single miniaturized and user-friendly format
will offer the promise of practical applications.
 Thanks

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