Prasad 2018
Prasad 2018
Prasad 2018
PII: S0144-8617(17)31166-9
DOI: https://doi.org/10.1016/j.carbpol.2017.10.020
Reference: CARP 12869
To appear in:
Please cite this article as: Prasad, Kamalesh., Mondal, Dibyendu., Sharma,
Mukesh., Freire, Mara G., Mukesh, Chandrakant., & Bhatt, Jitkumar.,
Stimuli responsive ion gels based on polysaccharides and other polymers
prepared using ionic liquids and deep eutectic solvents.Carbohydrate Polymers
https://doi.org/10.1016/j.carbpol.2017.10.020
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Stimuli responsive ion gels based on polysaccharides and other polymers
prepared using ionic liquids and deep eutectic solvents
Kamalesh Prasad,* a,b Dibyendu Mondal,c Mukesh Sharma,d Mara G. Freire,d Chandrakant
Mukesh,e and Jitkumar Bhatt a,b
a
Natural Products and Green Chemistry Division, CSIR-Central Salt & Marine Chemicals
Research Institute, G. B Marg, Bhavnagar-364002 (Gujarat), India, Phone No : +91-278-
2567760. Fax No. +91-278-2567562. Email: kamlesh@csmcri.res.in/
drkamaleshp@gmail.com]
b
AcSIR- Central Salt & Marine Chemicals Research Institute, G. B Marg, Bhavnagar-364002
(Gujarat), India
c
Centre for Nano and Material Science, Jain University, Bangalore 562112, India
d
CICECO – Aveiro Institute of Materials, Chemistry Department, University of Aveiro, 3810-
193 Aveiro, Portugal.
e
Department of Chemistry, Indian Institute of Technology, Delhi-110016
Highlights
Stimuli responsive ion gels in ionic liquids/deep eutectic solvents are discussed
Seaweed polysaccharides, gum based polysaccharides and DNA are covered.
The pH responsive behaviour of a polymerizable IL based nanogel is also discussed.
Abstract: Ion gels and self-healing gels prepared using ionic liquids (ILs) and deep eutectic
solvents (DESs) have been largely investigated in the past years due to their remarkable
applications in different research areas. Herewith we provide an overview on the ILs and DESs
used for the preparation of ion gels, highlight the preparation and physicochemical
characteristics of stimuli responsive gel materials based on co-polymers and biopolymers, with
special emphasis on polysaccharides and discuss their applications. Overall, this review
summarizes the fundamentals and advances in ion gels with switchable properties prepared
using ILs or DESs, as well as their potential applications in electrochemistry, in sensing devices
Keywords: Ion gel; ionic liquid; deep eutectic solvent; polysaccharides; biopolymer; co-
1
Introduction
considerable attention from the scientific community due to their potential applications for drug
delivery, as biosensors, shape memory materials, coating and textiles (Stuart et al., 2010; Yang
and Urban 2013). Almost all polymeric gels, irrespective of their synthetic or bio-based origin,
show both liquid like flow and elastic behaviour. These characteristics make them good
candidates for the fabrication of functional materials. Self-repairing is one of the most
the numerous approaches to introduce the self-repairing ability in gels, one of the most popular
is based on the addition of cross-linkers (Urban, 2012). There are several reports of self-healing
polymeric gel systems fabricated mainly by cross-linking with groups containing the –NH-CO-
moiety capable of forming reversible covalent bonds (Hager et al., 2010; Kushner et al., 2009;
Phadke et al., 2012). The formation of these self-healing materials involves the sharing of
electrons among the host and the guest molecules leading to the formation of covalent bonds.
important role, for instance in the replication of DNA, in the folding of proteins into intricate
three-dimensional forms, and in the detection of molecular signals (Berg, Tymoczko & Stryer,
2002).
external stimuli, such as heating, which is a popular way to regain the structural integrity in
structurally damaged polymers (Cho et al., 2010). After heating, the healing agent moves to
the damaged part and promotes the self-healing by initiating suitable polymeric entanglements.
In such physically induced healing processes, heating promotes the movement of polymeric
chains and diffusion. In such cases the polymeric material is usually heated above its glass
2
transition temperature (Tg) (Prager et al., 1981). The heating above Tg promotes surface
rearrangement, followed by wetting, diffusion and re-entanglement of the polymer chains (Kim
Smart polymeric materials are materials that are responsive to different stimuli, such as
pH, temperature, light, solvent, magnetic field, redox and mechanical stress. Such materials
have potential interest for various fields of applications (Klaikherd, Nagamani &
Thyamanavan, 2009; Balu et al., 2014; Zhuang et al., 2013), such as in drug delivery (Li et al.,
2014; Liu et al., 2014; Lee, Lee & Park, 2014), imaging (Sundaresan et al., 2014), catalysis
(Deng et al., 2014), coatings (Zhao et al., 2014), and sensors (Kavanagh et al., 2012; Zhang et
al., 2014) (Li et al., 2012; Yan et al., 2012). Several authors have reviewed stimuli responsive
polymeric gels functionalized with metals (Weng, 2013), carbon nanotubes, graphene and
In recent years, ionic liquids (ILs) emerged as unique platforms for materials design
(Noro, Matsushita & Lodge, 2008; Smiglak et al., 2014) and as suitable solvent media for the
dissolution of several polysaccharides, including cellulose, starch, chitin and DNA (Swatloski
et al., 2002 ; Isik et al., 2014 ; Payal et al., 2015 ; Wilpiszewska & Spychaj 2011 ; Prasad et
al., 2009; Mondal et al., 2013; Sharma et al., 2013; Mukesh et al., 2013). Among these, DNA
draws special attention due to its molecular recognition, biocompatibility, biodegradability and
mechanical flexibility features, making it suitable for the design of functional materials useful
in molecular sensing in the form of DNA nanomachines and intelligent drug delivery and
programmable chemical syntheses (Bath & Turberfield, 2007). DNA based hybrid materials
and hydrogels were proposed for applications in targeted drug delivery, tissue engineering
bioanalysis, biomedicine and as stimuli-responsive materials (Lee et al., 2012; Um et al., 2006
; Peng et al., 2013). Further, due to the responsiveness of DNA towards pH and salt addition,
it is also considered as a suitable precursor for designing bio-artificial muscles (Costa, Miguel
3
& Lindman, 2007; Besteman, Eijk & Lemay, 2007). However, from the DNA based ion gel
point of view, there is only one report on the preparation of gelatin and DNA based gel polymer
electrolytes by treating them with acetic acid and LiClO4, leading to the formation of ion gels
with high ionic conductivity (Pawlicka et al., 2009). There are also limited reports on the
preparation of ion gels by the combination of DNA and ionic liquids (ILs) or deep eutectic
solvents (DESs). However, ILs are extensively used as suitable substrates for the preparation
of other ion gels (Isik et al., 2014; Seki et al., 2005; Ueki, 2008).
described by Ueki in 2014. Multi stimuli responsive polymers with switchable wettability
functionalized with imidazolium based ILs were synthesised and proposed by Döbbelin and
polymers in ILs, polymerizable ILs (PILs) were also proposed as suitable substrates for the
preparation of functional stimuli-responsive materials and ion gels suitable for gas separations
(Cowan, Gin and Noble, 2016 ; Kausar, 2017). Well-defined triblock copolymers, namely
viscoelastic ion gel with [C2mim][NTf2]) (Figure 1) with tetrahydrofuran, displaying high ionic
reactions. Very less attention has however been given to the preparation of “smart” materials
based on renewable/natural polymers, which are of particular significance in line with the
4
An overview of the current smart ion gels materials prepared using co-polymers,
biopolymers or polysaccharides and ILs or DES, as well as their potential applications, are
described and discussed below. The following section is presented according to the response
of the ion gels to external stimuli, namely pH, heat, light and magnetism. The chemical
structure of different ILs, DESs, and polymers, copolymers, biopolymers and polysaccharides
investigated for the preparation of such materials are shown in Figures 1 and 2.
pH or proton (H+) responsive ion gels show different behaviour upon changes in the pH
of the system ((Noro, Matsushita & Lodge, 2008; Mukesh et al., 2014; Hashimoto, 2016; Xie,
2014). Towards the development of such ion gels, Xie and co-workers (2014) have reported
dye-IL based proton responsive transparent, ion-conducting, and flexible ion gels, which
exhibit reversible colour change depending on the concentration of protons or hydroxide ions.
Researchers first prepared the imidazolium based IL having methyl orange [C4mim][MO] as
counter ion (Figure 1A), followed by the addition of poly(methylmethacrylate) (PMMA) and
an another IL, namely [C4mim][N(Tf)2] (Figure 1A), in the presence of acetone. Uniformity
and absence of defects in the ion gels were confirmed by scanning electron microscopy (SEM),
FT-IR spectroscopy and thermo gravimetric (TGA) studies. Moreover, no significant shifts in
FT-IR bands after the IL incorporation were observed, indicating that the interactions between
the IL and PMMA are weak and may led to the IL leaching from the gel matrix. Recently,
Hashimoto et al., (2016) have disclosed the preparation of tetra-armed polyethylene glycol
based ion gels with high-toughness using imidazolium based aprotic ILs ([C2mim][N(Tf2)])
with buffering properties (Hashimoto, 2016). The authors showed that by controlling the pH,
the properties of the ion gel can be manipulated. An ideal and homogenous polymer network
was formed when pH was controlled by adding aprotic ILs with buffering characteristics,
5
whereas the ion gel system without buffering ILs showed discrete polymer network with
In order to fulfil the requirements of biomedical applications, efforts have been made
polysaccharide for a wide number of applications (Roy, Cambre, & Sumerlin, 2010 ; Stuart et
al., 2010). In order to prepare a suitable pH and electric responsive material for drug delivery
applications, chitosan films loaded with ILs or salts, such as choline chloride and choline
prepared, followed by studies on the drug release kinetics at different pH values (Dias, et al.,
2013). The drug release kinetics showed that the release of dexamethasone sodium phosphate
does not occur by simple diffusion or swelling; it is instead controlled by the interactions
occurring between the chitosan film, dexamethasone sodium phosphate and choline
nontoxic ion gel with hemocompatible features. The ion gel thus obtained showed a pH
responsive release of indomethacin. Moreover, the drug immobilized in the gel matrices can
be stored at room temperature for a long period (up to 6 months) without degradation (Mukesh
et al., 2016a). Self polymerization of HEMA in ChCl-Or 1:1.5 (Figure 1B) resulting in the
formation of highly stretchable ion gel with good capacitance behaviour was obtained (Mukesh
et al., 2016b). The use of DESs for the preparation of pH responsive DNA based ion gels was
also explored by Mukesh & Prasad (2015). The formation of three different morphologies of
6
DNA was observed in a DES composed of ChCl-EG 1:2, which is known to solubilize high
concentrations of DNA (Mondal et al, 2013). In this work, DNA was converted into pH
reversible ion gels, comprising aggregated DNA structures (pH 2.98), spheroid shaped DNA
chemical and structural stability of DNA in all the formats were confirmed. The micro-sized
DNA assemblies as well the micro-hydrogels are useful for applications in targeted gene or
drug delivery.
Besides the use of co-polymers for the preparation of pH responsive ion gels, recently,
pH responsive polymerized bio-ionic liquid based nanogel matrices were proposed for the
delivery of an anticancer drug (Mukesh et al., 2014). pH-responsive nanogel systems with an
and cross-linking of a polymerizable bio-based ionic liquid [Ch][acrylate] (Figure 1A). The
nanogel thus obtained showed prolonged drug delivery (10 days) for an anticancer drug (5-
fluorouracil) at pH 1.2 (stomach pH) at the physiological human body temperature (37 oC).
Remarkably, no substantial drug delivery was observed at pH values of 5 and 7.4. The
prolonged drug release profile makes the reported nanogel system a potential candidate as drug
nanocarrier vehicles for the in vivo delivery of stomach specific therapeutic agents.
Ion gels in which their properties can be tuned by temperature as external stimuli are known as
thermo-responsive ion gels. Such ion gels have several potential applications, such as in
reversible water uptake, actuators, optical sensors, and in flexible optical devices (Noro et al.,
2013; Noro, Matsushita & Lodge 2008; Vidyasagar, Handore & Sureshan, 2011; Benito-Lopez
7
Temperature responsive viscoelastic properties of supramacromolecular ion gels were prepared
in an IL, [C2mim][N(Tf2)] (Figure 1A), via H-bonding between the end blocks of a triblock
(P2VP-PEA-P2VP) (Figure 2), and a homopolymer (Noro, Matsushita & Lodge, 2008). The
prepared ion gel showed reversible gel like properties up to 141.5 °C; above this temperature
it behaves like a viscous liquid. The authors have also showed that the relaxation time of the
system increases by ~11 times on cooling from the gel point (141.5 °C) down to 30 °C. The IL
was found to maintain good solvent conditions over a wide range of temperatures. Ru et al.
(2013) have explored IL-modified alkoxysilane based thermally reversible, flexible, and
ionic liquid ([NH2-C4im]Br) (Figure 1 A) was used for the study. The thermal reversibility of
the ion gels was tested by a heating-cooling process, whereas the material showed fluid nature
at 60 °C, and upon cooling down to room temperature the ion gel property was restored and
the process was shown to be repeatable for several times. Such thermo-responsive luminescent
materials have potential application towards the development of flexible optical devices.
Thermo-reversible supramolecular polymer ion gels were also prepared by Noro et al., (2013).
The reported ion gels were prepared by mixing a poly (4-vinylpyridine)-b-poly(ethyl acrylate)-
chloride in presence of the IL [C2mim][N(Tf2)] (Figure 1A). The authors have showed that the
metal-ligand coordination between zinc and pyridine group in the presence of IL was the
driving force towards the formation of gel as confirmed by FT-IR spectroscopy. Heating-
actuation behaviour in comparison to its hydrogel counterpart. This ion gel was prepared by
8
encapsulating [C2mim][EtSO4] into a cross-linked poly(N-isopropylacrylamide) matrix. The
authors showed that the ion gel has temperature responsive reversible swelling and shrinking
behaviours, whereas the corresponding hydrogel did not show any of such behaviours.
Apart from the use of polymers and copolymers of synthetic origin for designing
thermo-reversible ion gels, ion gels based on biopolymers were also reported. Guar gum (GG)
a branched α-D-galactopyranose unit at C-6 (Figure 2). [C4mim]Cl (Figure 1A) was used for
treatment to obtain hard gel materials. The obtained hard material was compressed (ca. 10
MPa) to get stable thin films. These films showed a fracture stress of 17 MPa with a fracture
strain of 18.2 % under tensile mode and became hard on heating, meaning that they could be
arranged to a target shape at higher temperatures (Figure 4). This high temperature shapeability
at room temperature (Prasad, Kaneko & Kadokawa, 2009a; Mine et al., 2010). The same ionic
liquid, i.e. [C4mim]Cl, was used to prepare functional ion gels of xanthan gum (Izawa and
Kadokawa, 2010). The ion gels thus obtained showed good mechanical properties and thermally
induced shape-memory effect. The specific association of the IL in the gels and interaction of the
imidazolium cation with xanthan gum chains were suggested as the main reasons behind the
production of such unique functional gels. Another IL, namely [C4mim]CH3COO (Figure 1), was
used as solvent media to produce acetylated and carbanilated agarose, which was found to be
thermoreversible. Furthermore, the researchers were able to prepare self-healing ion gels of
9
Guar gum (GG) ion gels and their nanocomposite gels incorporating multiwalled carbon
nanotubes (MWCNT) with self and solvent responsive healing abilities were explored by our
group (Sharma et al., 2013a; Sharma et al., 2013b). In this work, ion gels in [C4mim]Cl were
process. The gels were bisected and kept one upon another or aligned horizontally with each
other in close vicinity at room temperature (30 oC). It was observed that the ion gel with 10%
w/v of GG was self-healed after 6 h of standing (Figure 5A). Further, a composite gel was
prepared in presence of 0.2% MWCNT with respect to [C4mim]Cl, and the self-healing of the
gel was observed after 5 h of standing at room temperature. The unified gel structure was
bisected and kept one upon another. The gel pieces self-healed and the process was repeated
for 3 consecutive cycles. No more cycles were achieved, may be due to the loss of the IL
mobility. [C4mim]Cl was used with a dual functionality since it behaves as a solvent and as a
junction promoter that ties guar gum chains leading to the formation of network structures
similar to physical gels. These cross-linking structures are not regular but rather form extended
junction zones due to cooperative effects. The three dimensional network upon application of
mechanical strain (higher shear rate) was disturbed, but upon release of the force, reconstitution
of the three dimensional structure took place responsible for the self-healing of the gels. The
area of the hysteresis loop formed for the GG-[C4mim]Cl gel was 2.33 x 105 Pa/s, which is
lower than that of GG-[C4mim]Cl/MWCNT (7.9 x 105 Pa/s), explaining the quicker response
of the later to mechanical strain towards self-healing. The area of the hysteresis loop after three
consecutive cycles was almost the same, indicating the ability of the materials to self-heal after
The prepared GG ion gels in [C4mim]Cl were bisected and aligned horizontally with
each other in close vicinity at room temperature, followed by placing the gel pieces in polar
aprotic solvents, namely acetone, DMSO, DMF and acetonitrile. The ion gel with 10% w/v of
10
GG healed after 1.5 h of exposure to acetone, DMSO and DMF (Figure 5B); however, no
healing was observed in acetonitrile. It should be noted that the ion gels of other
polysaccharides, such as agarose, -carrageenan and xanthan gum did not show healing
behaviour in the these polar aprotic solvents. It was proposed that the branched galactopyranose
unit of GG may play an important role in the healing process. All the other polysaccharides
mentioned above are straight chain polysaccharides, with the exception of xanthan gum which
consist of bulky side chain. The bulky side chain possibly did not favour the physical cross-
linking required for gelation (xanthan gum side chain: C24H36O18; GG side chain: C6H12O6).
On the other hand, the nanocomposite ion gel prepared with MWCNT healed upon 1 h of
Shear responsive ion gels based on Tamarind gum and IL were reported by us (Sharma et al.,
2014). Tamarind gum (TG) is a natural polysaccharide, extracted from the endosperm of the
seeds of Tamarindus indica Linn (Glicksman, 1986) (Figure 2). Chemically TG is composed
xylose, and galactose units are present in the ratio of 2.8: 2.25: 1.0 as the monomer units
(Gidley et al., 1991). TG is widely used as a thickening, stabilizing, emulsifying and gelling
agent in the food and pharmaceutical industries (Zhang et al., 2006). Stable TG ion gel was
In order to investigate the recovery of storage modulus (G´) of the ion gels upon
relaxation, the gels were fractured employing high strain followed by relaxation. The ion gel
prepared in [C4mim]Cl was initially subjected to 1% strain at 1 Hz frequency for 300 s and G´
and G´´ were monitored during the process and by fracturing the gels employing a high strain
11
at 1 Hz for 100 s. The storage modulus for TG-[C4mim]Cl gel recovered the original value
upon relaxation. The cycle could be repeated for 10 consecutive times. On the other hand, the
hydrogel did not show structure recovery upon relaxation indicating absence of thixotropic
nature.
Magnetically responsive ion gels have potential applications due to their inherent magnetic
behaviour (Q. Yuan, 2008). In general, magnetic ion gel materials are prepared by the
(Ziółkowski et al., 2012; Xie et al., 2010). Ziółkowski and co-workers (2012) reported the
isopropylacrylamide and a phosphonium-based IL. The authors showed that after modification
of magnetic nanoparticles with silane, the ion gel became homogenous and also prevents the
leaching of nanoparticles from the gel matrix. Furthermore, the IL imparted optimal
mechanical strength and healing properties to the gel. Such magnetic ion gels with improved
mechanical stability and flexibility respond differently to external permanent magnets and
The same research group have also studied the suitability of an iron-containing
acetone (Xie et al., 2010). The authors have studied the structural changes of the IL by UV-Vis
spectroscopy upon incorporation into the polymer matrix and showed that the coordination
around the Fe (III) ion slightly changed upon incorporation; nevertheless, the magnetic
properties were similar to the pure IL. Such magnetic ion gels are exciting prototypes for
12
In addition to the stimuli responsive ion gels discussed above, other functional ion gels based
amongst the most studied polysaccharides and ILs respectively, to prepare ion gels. It was
shown that high concentrations of the polysaccharide (15% w/w) in the IL can lead to the
formation of a transparent ion gel upon standing (Kadokawa, Murakami and Kaneko, 2008;
The ion gels prepared using guar gum and [C4mim]Cl or any polysaccharide based ion
gels prepared using ILs have an inherent problem - the leaching of the IL from the polymer
matrices. Zhang et al., (2017) have recently overcame this situation by preparing a self-standing
stable guar gum film using [C4mim]Cl and an imidazolium based polymerisable ionic liquid
GG and the PIL provided an excellent dimensional stability to the ion gels with no expulsion
of the IL, even after long term standing. Such ions gels could also display high thermal stability
and electric conductivity. PILs were also used to prepare chitin/cellulose thin films by
monomers. The free radical polymerization of the later resulted in the formation of thermally
In this review, stimuli responsive ion gels prepared using polymers, co-polymers, biopolymers
and polysaccharides in ILs or DESs are overviewed and discussed, particularly ion gels
responsive to external stimuli, such as pH, temperature, stress, magnetism and solvents, and
self-healing gels. In most of the reported studies, ILs have been used as gelling media to provide
high ionic conductivity and high temperature stability and flexibility. On the other hand, in
spite of having promising features, less attention has been given to DESs for designing such
functional ion gels. DESs are considered as more benign alternatives over ILs due to the
13
possibility of their formation using bio-based starting materials. Due to the remarkable
properties of ILs or DESs to prepare stimuli responsive ion gels, other and wider stimuli
investigated in the near future. The unique characteristics of the reported stimuli-responsive
ions gels based on ILs or DESs make of them remarkable materials for applications in
electrochemistry, in sensing devices and as drug delivery vehicles, for which deeper
investigations on their potential applications and their scale-up still stand out as issues to
accomplish.
Acknowledgements
KP thanks council of scientific and industrial research (CSIR), New Delhi for the CSIR-Young
scientist Awardee project (CSIR-YSP/2011-12) and overall financial support for the research
work. MG Freire acknowledges the funds received from the European Research Council under
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Figure 1: Chemical structure, abbreviation and references reporting on ionic liquids (A) and
deep eutectic solvents (B) used to prepare ion gels.
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Figure 2: Chemical structure of monomer units of polysaccharides and other polymers used
for the preparation of stimuli responsive ion gels (a) cellulose (b) chitin (c) chitosan (d) xanthan
gum (e) agarose (f) guar gum (g) tamarind gum (h) poly(N-isopropylacrylamide) (i)
bisacrylamide.
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Figure 5: Self and solvent responsive healing ability for guar gum ion gel [Reproduced with
Figure 6: Preparation of cellulose ion gel in [C4mim]Cl (Reproduced with permission from
authors)
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