PLASMA POLYMERIZED HYDROGEL

THIN FILMS FOR

APPLICATIONS IN SENSORS AND
ACTUATORS

Guided By: Submitted By:

Mr. Harekrushna Sutar, Priyanka Sahoo
Assistant Professor, Roll No.-34556
Dept. of Chemical Engg. Regd. No.-1501105056
 Contents:
• Introduction- What is hydrogel?
• Bulk Hydrogel
• Surface attachment techniques
• Plasma Polymerization
• Cross-Linker
• Applications in sensors and actuators
• Different types of sensitive hydrogels
• Bio-sensors Implementation
• Conclusion
• References
Introduction:
What is hydrogel?
 Hydrogels, an important class of soft materials are water
swollen polymeric networks that are capable of absorbing
large quantities of water while retaining their physical integrity.
 “Intelligent” hydrogels respond to environmental triggers such
pH, temperature and electric fields to undergo volume change
wherein the polymeric network expands upon absorption of
water or collapses by releasing the absorbed water.
 They are water soluble cross-linked polymeric structures derived
from hydrophilic monomers.
 They are prepared by the polymerization of one or more
monomers, and are cross-linked in a variety of way:
(i)Radiation Cross-linking
(ii)Covalent cross-linking through the use of chemical cross-linking
agent
(iii)Physical cross-linking through various intermolecular forces
such as hydrogen bonds and strong van der Waals interactions
between polymeric chains.
Bulk Hydrogel:
 In this type, crosslink density is an important parameter that
controls the mechanical properties and water uptake capacity,
and can be varied to obtain desired properties,
 For example, in the case of thin films of thermo responsive poly-(N-
isopropyl acrylamide), it is produced by techniques such as:
 surface grafting
 photo-polymerization
 plasma polymerization
 The phase transition behavior is significantly different relative in bulk
hydrogels, and is believed to be the result of the constraining
substrate.
 In the thin film geometry, the hydrogel is unable to expand or
contract in the lateral directions, thus confining the motion to a
single direction, normal to the substrate.
Formation techniques of hydrogel:
Surface Grafting Photo- Plasma
Polymerization Polymerization
Surface attachment techniques:
 Stable attachment of hydrogel layers onto a solid substrate is
of major importance for many applications, such as coatings
and sensing layers.
 Depending on the chemical nature of the hydrogel polymer
and the substrate material, specific surface bonding
strategies have been developed.
 There are two general methods employed for attaching
hydrogel polymers on surfaces.
 The first technique is “grafting to” technique, where a
preformed polymer chain is attached to the substrate.
 The other method is “grafting from” technique, which involves
the growing of polymer chain from substrate.
 The “grafting to“ technique can be divided into two types:
I. Chemical “Grafting to”
II. Photochemical “Grafting to”
“Grafting to” method
 In this technique, a preformed polymer chain is attached to the
substrate either by covalent bond or by physical means via
attractive interactions of adsorbed polymer with substrate.
 When this method is combined with interchain cross-linking,
thick polymer networks can be formed from many polymer
chains and simultaneously attach to the substrate.
(I) Chemical “Grafting to”
It employs a preformed polymer chain that is covalently bound to
a substrate surface by a chemical reaction between a functional
group on the polymer backbone and on the substrate.
(II) Photochemical “Grafting to”
A common photo-reactive group that has been incorporated into
polymer chains and used for surface-grafting of hydrogel layers to
solid substrates is the phenyl azide moiety. Upon irradiation with
light, this group inserts into C-H bonds at the substrate surface.
“Grafting from” method
 The general concept behind the “grafting from” technique is
based on the polymer chain growth starting from an initiator site
at the substrate surface.
 By the incorporation of monomer molecules from the
surrounding medium, polymer brush layers with typically low film
thicknesses limited by the chain length, have been prepared.
 If concurrent or subsequent cross-linking occurs during polymer
growth, polymer networks films are formed.
 Employing this technique, cross-linked poly-(N-Isopropyl
acrylamide) hydrogel layers with carboxyl groups were
prepared on amino propyl silane-modified silica particles.
Plasma Polymerisation:
 It is one of the method to prepare hydrogel thin films because
polymerization, cross-linking and thin film deposition are combined in a
single process.
 During plasma polymerization, well-adhering, cross-linked polymer films
are deposited directly on a substrate; subsequent exposure of polymer
film to water results in the formation of a hydrogel structure and
removal of uncross-linked polymeric segments.
 It is typically carried out using electrically-driven, low-pressure cold
plasma, which are characterized by low degree of ionization and low
energies than hot plasmas.
 The monomers used can be broadly grouped under following
categories:
i. Hydrocarbons containing polar groups
ii. Fluorocarbons
iii. Silicon containing monomers
iv. Metal containing monomers
Cross-linker:
 It is defined as the molecular entity at which three or more
chains can join to form a crosslink point and turn the polymer
into a network.
 It can occur by two ways:
 In-situ crosslinking
 It relies on the formation of polymer chain in the presence of
a cross-linking monomer with two or more polymerizable sites.
 Post-synthetic crosslinking
 The polymer is first formed on a substrate from a soluble
precursor polymer, followed by cross-linking in second step.
 The cross-linking process may involve exposure to chemical
agents, elevated temperature or UV-radiations
Applications in sensors and actuators:
 Hydrogels , mostly in the form of thin films, have found applications
in sensors as the active layers on a variety of transducers.
 Certain Hydrogel layers possess inherent sensitivity to analytes such
as moisture and volatile organic compounds, and thus may be
used in sensors.
 Sensing is accomplished by monitoring changes in the transducer
signal in response to analytes , which can adsorb and interact with
the hydrogel matrix through various non-covalent forces. However,
such sensors suffer from poor selectivity due to cross or multiple
reactivity.
 Hydrogels are capable of swelling when exposed to water, the
volume change in hydrogels has therefore led to application in
actuators.
 The actuation response time of hydrogel is dictated by their size
and diffusivity.
 Hydrogel films have been used to sense pH, glucose, ions and
antigens.
Different types of sensitive hydrogels

 pH-sensitive hydrogel:
 pH –sensitive hydrogels respond to changes in pH due to
ionization of acidic or basic side groups.
 By monitoring the volume change of hydrogels in response to
pH, it is possible to sense pH.
 Glucose-sensitive hydrogel:
 It has been developed by incorporating glucose oxidase, or
lectins such as phenylboronic acid moiety in the hydrogel
matrix.
 Glucose-oxidase converts glucose to gluconic acid, thereby
causing decrease in the pH of hydrogel environment and
volume change.
 Ion-sensitive hydrogel:
 In ion-sensitive hydrogel, divalent cations such as Ca2+ form
ionic crosslinks with alginate hydrogels.
 Hence, it causes shrinkage or swelling in response to
environment changes in the ion concentration.
 Antigen responsive hydrogels:
 It appear to consist of reversible crosslinks formed between an
antigen and the corresponding antibody immobilized in the
hydrogel network.
 When exposed to free antigen, the hydrogel swell because
the free antigen displaces the immobilized antigen bound to
the antibody in the network which results in bond breakage.
Bio-sensor implementation:
 Representative examples of biosensor schemes relying on
molecular imprinted hydrogels, responsive gels modified with
enzymes, and biosensors taking advantage of nucleic acids
and immunoassays are introduced and their performance
characteristics are discussed as follows.
 Basically four types are being described:
 Molecular-imprinted Hydrogel-based Biosensors
 Enzyme based Biosensors
 Nucleic-acid based Biosensors
 Immunoassay-based Biosensors
Molecular imprinted Hydrogel-based Biosensors:
 In Biosensors, hydrogel-based molecular imprinted matrices with
responsive properties were shown to amplify the detected optical
changes through additional binding-induced collapse or swelling.
 A molecular imprinted hydrogel with an acryloamide-
acrylamidophenyl boronic acid co-polymer was developed for
detection of β-nicotinamide adenine dinucleotide (NAD+),β-
nicotinamide adenine dinucleotide phosphate (NADP+) and their
reduced form.
 The binding of target molecules triggers its swelling.
 Besides monolithic molecular imprinted hydrogel films, microgels
were used for a construction of a binding matrix which offers
faster diffusion of analytes to the polymer.
 Poly(N-(N-propyl)acrylamide) microgel particles with a diameter
of 300 nm were imprinted by theophylline and attached to a gold
surface.
Enzyme-based Biosensors:
 Employing of enzyme recognition elements offers a possibility for
detection of numerous analytes important for medical diagnostics.
 The interaction of an enzyme with respective target analyte
typically triggers a catalytic reaction, which changes the
characteristics of the local environment in the hydrogel (e.g., pH).
 When the enzyme is immobilized in a hydrogel responsive to these
changes, these variations can be translated to swelling or collapse
of the gel and subsequently converted to an optical output of the
sensor.
 A sucrose biosensor was developed based on an agarose guar
gum-based binding matrix with incorporated acid invertase and
glucose oxidase.
 In another work, silver nanoparticles were coated with a responsive
hydrogel (composed of acrylamide, bisacrylamide and
polyvinylpyrrolidone) in order to function in a glucose biosensor.
Nucleic acid-based Biosensors:
 Hydrogel matrices carrying oligonucleotide probes were
implemented for the detection of nucleic acids by using SPR and
fluorescence spectroscopy.
 For instance, a water-soluble polythiophene polymer composed
of poly(3-[(S)-5-amino-5-carboxyl-3-oxapentyl]-2,5-thiophenylene
hydrochloride) (POWT) with zwitterionic peptide-like side chains
was used for detection of single stranded DNA.
 The zwitterionic side-chains carry serine carboxylic groups and an
amino group, which are responsible for pH-dependent
conformational transitions in the gel.
 Refractive index changes associated with these conformational
changes were translated to a sensor signal by SPR. In addition, the
POWT exhibits fluorescence characteristics sensitive to
electrostatic interaction of polymer chains.
 Another type of nucleic acid biosensor, based on an aptamer-
crosslinked polyacrylamide hydrogel, was developed for
detection of small molecules such as adenosine and cocaine.
Immunoassay-based Biosensors:
 Immunoassays represent an established method for detection of
chemical and biological analytes owing to commercial availability of
antibodies against a wide range of analytes, their versatility and high
affinity.
 In biosensors with hydrogel binding matrix, antibodies are immobilized in
a hydrogel film, which exhibits a huge binding capacity and highly
open network structure through which molecular analytes can rapidly
diffuse.
 These materials offer the advantage of an increased binding capacity
and decreased steric hindrance with respect to more traditional
monolayer architectures.
 A biosensor based on surface plasmon resonance imaging (SPRi)
employed a hydrogel matrix composed of poly(ethylene glycol)
methacrylate and 2-hydroxyethyl methacrylate with a lateral gradient.
 In another immunosensor, detection of free prostate specific antigen (f-
PSA) was carried out by using a highly swollen, 1 μm thick hydrogel
binding matrix of photo-crosslinked carboxymethyl dextran.
Conclusion:
 A new class of monomers has been used to prepare plasma polymerized hydrogel
films.
 Molecular structure of the films has been characterized by EDS and XPS
spectroscopies.
 Variable duty cycle pulsed plasma polymerization has been shown to be an
effective route to control moisture uptake and thermo responsive behavior of the
films.
 Hydrogel materials possess many properties that endow them with attractive
features for a wide range of applications. Specifically, the thin-film format of
hydrogels attached to solid surfaces is of great technological interest, as it
represents a “smart” coating that can be micro structured and integrated into micro
fabrication processes.
 In important areas such as medical diagnostics and environmental monitoring,
hydrogel materials allowed impressive advances in biosensor performance and
helped to push these technologies towards applications.
 We expect that future biosensor technologies will increasingly take advantage of
“smart” hydrogels with responsive properties, which will increase their sensitivity
and allow implementation of new simplified detection schemes.
References:

 https://smartech.gatech.edu/handle/1853/19827
 https://patents.google.com/patent/US20070010596
 http://ma.ecsdl.org/content/MA2005-01/45/1738.abstract
 http://www.mdpi.com/2077-0375/2/1/40/htm
 Plasma polymerized hydrogel thin films for applications in sensors and actuators
by Prabhakar A. Timirisa
https://www.researchgate.net/publication/27535222_Plasma_polymerized_hydrog
el_thin_films_for_applications_in_sensors_and_actuators