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Review
h i g h l i g h t s
Design concepts and applications of interpenetrating polymer networks hydrogels are reviewed.
Inuence of the second network on properties of IPN hydrogels is discussed.
Deswelling and mechanical properties of PNIPPAm are improved in IPN hydrogels.
IPN hydrogels are recommended as efcient sorbents for heavy metal ions.
IPN cryogels perform better than conventional hydrogels in dye removal.
a r t i c l e
i n f o
Article history:
Received 18 November 2013
Received in revised form 16 January 2014
Accepted 20 January 2014
Available online xxxx
Keywords:
Hydrogels
Interpenetrating polymer network
Dyes
Heavy metals
Sorption
a b s t r a c t
Interpenetrating polymer networks (IPN) hydrogels have gained great attention in the last decades,
mainly due to their biomedical applications. This review aims to give an overview of the recent design
concepts of IPN hydrogels and their applications in controlled drug delivery, and separation processes.
In the rst part, the main strategies for the synthesis of semi-IPN and full-IPN hydrogels, their relevant
properties, and biomedical applications are presented based on the nature of the networks, the main categories selected being: IPN hydrogels based on polysaccharides (chitosan, alginate, starch, and other
polysaccharides), protein based IPN hydrogels, and IPN hydrogels based only on synthetic polymers.
The inuence of the second network on the stimuli responsiveness of the smart IPN hydrogels is discussed based on the most recent publications in the eld. In the second part, an overview of the most
specic applications of IPN hydrogels in separation processes is critically presented. Factors which control the separations of dyes and heavy metal ions by semi-IPN and full-IPN as novel sorbents are discussed based on the recently published articles and own results. A special concern is given to the
macroporous IPN composite cryogels, which are very attractive materials for separation processes being
endowed also with a high reusability.
2014 Elsevier B.V. All rights reserved.
Abbreviations: AAm, acrylamide; AAm-g-HEC, acrylamide grafted on hydroxyethylcellulose; AAPBA, 3-acrylamidophenylboronic acid; Alg, alginate; AMPS, 2-acrylamido2-methyl-1-propansulfonic acid; BAAm, N,N0 -methylenebisacrylamide; CMC, carboxymethyl cellulose; CS, chitosan; DS, diclofenac sodium; DMAEM, 2-dimethylaminoethyl
methacrylate; DSC, differential scanning calorimetry; Dx, dextran; DxS, dextran sulfate; ECH, epichlorohydrin; EWC, equilibrium water content; GA, glutaraldehyde; GE,
gelatine; HA, hyaluronic acid; HEMA, 2-hydroxyethyl methacrylate; IA, itaconic acid; IEP, isoelectric point; IIH, ion imprinted hydrogel; IPN, interpenetrating polymer
network; LCST, lower critical solution temperature; MB, Methylene Blue; MO, methyl orange; MV, methyl violet; NaPAA, poly(sodium acrylate); NIPAAm, Nisopropylacrylamide; NVF, N-vinylformamide; PA, anionically modied potato starch; PAA, poly(acrylic acid); PAAm, poly(acrylamide); PAN, poly(acrylonitrile); PASP,
poly(aspartic acid); PDADMAC, poly(diallyldimethylammonium chloride); PDMAEM, poly(N,N-dimethylaminoethyl methacrylate); PDMC, poly(methacryloyloxyethylammonium chloride); PEG, poly(ethylene glycol); PEG-DA, poly(ethylene glycol) diacrylate; PEI, poly(ethyleneimine); PFO, pseudo-rst-order; PMAA, poly(methacrylic acid);
PMAAm, poly(methacrylamide); PS, potato starch; PSO, pseudo-second-order; PVA, poly(vinyl alcohol); PVP, poly(vinylpirrolidone); RB, rhodamine B; SA, sodium alginate;
SEM, scanning electron microscopy; SF, silk broin; SPH, super-porous hydrogel; SReq, equilibrium swelling ratio; VPTT, volume phase transition temperature.
Tel.: +40 232 217454.
E-mail address: sdragan@icmpp.ro
http://dx.doi.org/10.1016/j.cej.2014.01.065
1385-8947/ 2014 Elsevier B.V. All rights reserved.
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http://dx.doi.org/10.1016/j.cej.2014.01.065
Contents
1.
2.
Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 00
Design, characterization, and biomedical applications of IPN hydrogels . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 00
2.1.
Polysaccharide based IPN hydrogels . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 00
2.1.1.
Chitosan . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 00
2.1.2.
Alginate . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 00
2.1.3.
Starch and derivatives . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 00
2.1.4.
Other polysaccharides . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 00
2.2.
Protein based IPN hydrogels . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 00
2.3.
IPN hydrogels based only on synthetic polymers . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 00
3.
Separations mediated by IPN hydrogels . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 00
3.1.
Characterization of sorption properties . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 00
3.2.
Sorption of dyes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 00
3.3.
Sorption of heavy metal ions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 00
3.3.1.
IPN hydrogels based on biopolymers . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 00
3.3.2.
IPN hydrogels based on synthetic polymers . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 00
3.3.3.
Ion imprinted IPN hydrogels . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 00
3.4.
Desorption and reusability . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 00
4.
Summary of the benefits of semi-IPN compared to single-network hydrogels, and of the influence of the second network on the properties of IPN
hydrogels. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 00
5.
Conclusions and perspectives . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 00
Acknowledgement . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 00
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 00
1. Introduction
Hydrogels are three-dimensional, hydrophilic, polymeric networks capable to retain large amounts of water, or biological uids,
characterized by a soft and rubbery consistence, being thus similar
with living tissues [1,2]. Hydrogels may be chemically stable or
reversible (physical gels) stabilized by molecular entanglements,
and/or secondary forces including ionic, H-bonding or hydrophobic
interactions, these hydrogels being nonhomogeneous [1,2]. Examples of reversible hydrogels are ionotropic hydrogels formed by
the interaction between a polyelectrolyte and an oppositely
charged multivalent ion, and the polyelectrolyte complexes (complex coacervates) formed by the interaction between two oppositely charged polyelectrolytes. Physical gels can be disintegrated
by changes in the environment conditions such as ionic strength,
pH, and temperature. Physical hydrogels have numerous biomedical applications in drug delivery, wound dressing, tissue engineering and so on. Covalently cross-linked networks form permanent or
chemical gels [1]. Smart hydrogels are able to signicantly
change their volume/shape in response to small alterations of certain parameters of the environment. Responsive hydrogels have
numerous applications, the most of them being focused on biological and therapeutic demands [35], and sensing applications [6].
However, single-network hydrogels have weak mechanical properties and slow response at swelling. To enhance the mechanical
strength and swelling/deswelling response, multicomponent networks as interpenetrating polymer networks (IPNs) have been
designed.
IPNs are alloys of cross-linked polymers, at least one of them being
synthesized and/or cross-linked within the immediate presence of the
other, without any covalent bonds between them, which cannot be separated unless chemical bonds are broken [79]. The combination of the
polymers must effectively produce an advanced multicomponent polymeric system, with a new prole [10]. According to the chemistry of
preparation, IPN hydrogels can be classied in: (i) simultaneous IPN,
when the precursors of both networks are mixed and the two networks
are synthesized at the same time by independent, noninterfering routs
such as chain and stepwise polymerization [7,9,11] (Fig. 1a), and (ii)
sequential IPN, typically performed by swelling of a single-network
hydrogel into a solution containing the mixture of monomer, initiator
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Fig. 1. Schematic representation of the IPN formation: (a) simultaneous strategy; (b) sequential strategy; (c) selective cross-linking of a linear polymer entrapped in semiIPN.
routes presented in Fig. 1. The most often encountered combinations of polymers used to prepare IPN composite hydrogels are
summarized in Fig. 2.
In the next subsections, each group of IPN hydrogels will be presented based on the literature information and our own investigations in the eld.
Protein +
synthetic
polymer
Chitosan + other
polysaccharides
Design of IPN
hydrogels
Polysaccharide
based IPN hydrogels
Chitosan +
synthetic polymers
Alginate +
synthetic polymers
Only
synthetic
polymers
Other
polysaccharides +
synthetic polymers
Starch +
synthetic polymers
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Fig. 3. Schematic representation of the synthesis of CS/AAm-g-HEC semi-IPN hydrogel (reproduced with permission from Ref. [23]).
the preparation of IPN composite hydrogels based on CS and polyanions containing carboxylic groups has been motivated by the
nding of more efcient systems for the sustained release of proteins [34,36,40] and drugs [35].
Guo and coworkers have reported an interesting approach to
obtain thermo- and pH-responsive semi-IPN polyampholyte
hydrogels based on carboxymethyl chitosan and poly(dimethylaminoethyl methacrylate) (PDMAEM) [44]. The semi-IPN hydrogel
shrunk most at the isoelectric point (IEP) and swelled when pH
deviated from the IEP. In the presence of PDMAEM, which present
a lower critical solution temperature (LCST), the swelling ratio of
the composite gel dramatically decreased between 30 and 50 C,
at pH 6.8. The key advantage of this composite hydrogel is that
the release rate of coenzyme A could be modulated as a function
of temperature, being higher at 50 C than at 37 and 25 C, at pH
6.8, making the semi-IPN hydrogel of great promise in pH/temperature responsive drug delivery systems.
2.1.1.2. IPN hydrogels based on chitosan and synthetic nonionic
matrices. Numerous IPN composite hydrogels have been prepared
by cross-linking polymerization of nonionic monomers in the presence of CS, the most employed monomers being acrylamide (AAm)
[4652], N-isopropylacrylamide (NIPAAm) [53,54], N,N-dimethylacrylamide [55], and 2-hydroxyethyl methacrylate (HEMA) [5659].
Currently, the modulation of the mechanical properties and the
water content of hydrogels by the preparation of the above
mentioned IPN gels are expected, one main purpose being their
use in biomedical applications such as controlled release systems
and as scaffolds in tissue engineering. Kim et al. described an interesting approach for the preparation of semi-IPN composed of CS
and poloxamer [60]. Their strategy consisting of photo-crosslinking the poloxamer macromer in the presence of CS coupled
with freeze-drying to obtain sponge type hydrogels. These IPN
composite hydrogels demonstrated rapid water adsorption, high
mechanical strength, and interconnected pores, which recommend
them for wound dressing application.
In our own research, we have prepared rst semi-IPN hydrogel
composed of CS as entrapped polymer in a matrix of PAAm, as conventional composite hydrogels [15]. Formation of full-IPN hydrogels was performed by a selective cross-linking of CS with
epichlorohydrin (ECH) (Fig. 1c), in alkaline medium, when a simultaneous generation of anionic sites on the PAAm matrix, by the
partial hydrolysis of amide groups [61,62], occurred. The formation
of IPN is schematically presented in Fig. 4.
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APS
TEMED
ECH/2 M NaOH
o
24 h/22 C
PAAm network
PAAm network
CS chains
CS network
Fig. 4. Schematic representation of the formation of IPN hydrogels composed of CS and PAAm.
groups in CS occurred, while the IPN cryogels, having two independent networks responsive at pH, behaved completely different.
Thus, the swelling feature at pH < 3 has been dominated by the cationic network based on CS, the carboxylic groups being less hydrophilic at this pH. At pH > 4, the gel dramatically swelled due to the
electrostatic repulsion between COO groups.
2.1.2. Alginate
Sodium alginate (SA) is a linear polysaccharide, derived from
sea algae composed of 1-4-linked b-D-mannuronic acid (M) and
a-L-guluronic acid (G), arranged in a blockwise fashion as homopolymer blocks (MM, GG) or alternating blocks of M and G with
different M/G ratios [83]. It can be easily cross-linked by divalent
ions (for example Ca2+), which bind the guluronic residues with
the transformation in hydrogel. Due to this characteristic, SA has
been widely used in conditioning of fabrics, foods, and various drug
delivery systems. For the preparation of IPN composite hydrogels,
SA was combined with various synthetic polymers [84]. Temperature and pH responsive IPN hydrogels, composed of SA and
poly(diallyldimethylammonium chloride) (PDADMAC), have been
prepared by Kim et al. by a sequential strategy [10]. The pHresponsiveness of the IPN hydrogels in the pH range 26 showed
that the swelling ratios increased with increasing pH value, having
a maximum at pH 4, but decreased in the range 46. When the carboxylic acid groups are below pKa values, they are in the form of
COOH. As the pH of the solution increased, the COOH were ionized to COO, and the resulting electrostatic repulsion causes the
hydrogels to swell. On the other hand, in this range of pH, the
COO in Alg and the ammonium sites in PDADMAC coexisted,
and formed polyelectrolyte complexes resulting in a decrease of
the swelling ratio of the IPN hydrogels.
Various IPN composite hydrogels, composed of SA and synthetic
polymers containing carboxylic groups, with novel properties like
super-porous [16], electrical sensitivity [85], drug controlled release [86], multi-responsive [87,88] have been designed. Superporous IPN composite hydrogels were prepared by Yin et al. [16]
through sequential cross-linking, by fast cross-linking polymerization of AAm and sodium acrylate in the presence of SA as entrapped polymer and sodium bicarbonate as blowing agent. CaCl2
was applied to cross-link the SA chains in semi-IPN gels. Owing
to their high porosity, the IPN hydrogels thus prepared had a fast
swelling and a high swelling ratio, this being affected by the exter-
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Semi-IPN1.40
Semi-IPN1.60
IPN1.40
IPN1.60
Fig. 5. SEM images of semi-IPN composite cryogels composed of CS entrapped in PAAm matrix with two cross-linker ratios (up), and of the full-IPN resulted by the selective
cross-linking of CS with ECH (down).
nal pH and ionic strength. The IPN hydrogels had a high mechanical strength and a good biocompatibility.
Alg based IPN have gained widespread interest for industrial
applications as actuators or muscles close materials. To realize
such materials, polymer gels with fast electric response and a high
mechanical strength were required. IPN composite hydrogels
based on PMAA and SA, showed a signicant and quick bending
when subjected to an electric eld, in HCl solution, and therefore
the authors assumed that this hydrogel could be useful for articial
organ components, such as muscle-like contractile structure, sensors, and electric current modulated drug delivery systems [85].
It is known that PNIPAAm, one of the most widely studied thermo-responsive polymers, has a slow response rate at the temperature changes. Synthesis of multi-responsive IPN composite
hydrogels, based on SA and PNIPAAm, constitutes one of the strategies adopted by numerous groups to increase the porosity of the
gels and thus to achieve gels with a faster response rate as required
for drug release systems. Both semi-IPN [8894] and full-IPN
[95,96] have been investigated. The pH/temperature sensitive release of indomethacin from semi-IPN hydrogel beads composed of
Ca-alginate and previously synthesized PNIPAAm has been reported by Shi et al. [97]. A drastic change in the drug release was
achieved by alternating the pH of the buffer solution between 2
and 7. The drug release was higher at 37 C than at 25 C and
showed that the Ca-alginate/PNIPAAm beads had potential as effective pH/temperature responsive delivery system of bioactive
agents. The pulsatile swelling/deswelling behavior of semi-IPN
hydrogels composed of cross-linked PNIPAAm and linear SA revealed that the process was repeatable, by alternating both temperature and pH, their mechanical strength making them suitable for
stimuli-responsive drug release systems [93]. An interesting ap-
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APS
TEMED
0.5 M NaOH
4 h, 25 oC
Fig. 6. Schematic representation of the PAAm/PA semi-IPN hydrogel formation and of the controlled hydrolysis (with permission from Ref. [115]).
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PAAm/PS60.5
PAAm/PA60.5
PAAm/PA80.5
PAAm/PS60.5H
PAAm/PA60.5H
PAAm/PA80.5H
Fig. 7. SEM images of semi-IPN composite cryogels composed of PS (left) and PA (middle and right) entrapped in PAAm matrix, before (up), and after (down) the controlled
hydrolysis.
of unmodied HA is the low stability of the resulting construct because of its high water solubility, and therefore some strategies
have been developed to get stable constructs like semi-IPN hydrogels composed of HA and synthetic polymers [124] or HEMA derivatized dextran [128]. Semi-IPN with rapid response rate at
temperature composed of kappa-carrageenan and a matrix of
poly(N,N-diethylacrylamide) were recently reported [129,130].
Our own investigation on the synthesis and characterization of
semi-IPN composite hydrogels composed of PAAm as a matrix and
either dextran (Dx) [135,136] or dextran sulfate (DxS) [137,138]
were focused on: (1) the preparation of macroporous semi-IPN
composite hydrogels with super-fast responsiveness, and (2) the
characterization of the novel composites by porosity, morphology,
swelling behavior, and rheology as a function of the synthesis
parameters such as cross-linking, monomer concentration, and
synthesis temperature. The characteristics of semi-IPNs composite
hydrogels were compared with those of the cross-linked PAAm
without polysaccharide. The gel preparation temperature and the
presence of Dx or DxS were found to be the key factors determining the porous structure of the networks. Thus, the interior network structures of the semi-IPNs prepared at 18 C (cryogels)
exhibited a heterogeneous morphology consisting of pores with
sizes around 100 lm, while those formed at +5 C or +25 C
showed pores with sizes around 3 lm. The swelling ratios of the
composite hydrogels were higher than those found for the PAAm
gels, irrespective of the gel preparation temperature. Moreover,
by conducting the cross-linking polymerization reaction at
18 C, semi-IPNs with super-fast responsive rate have been obtained [135,136]. It was found that the stability of DxS into the
composite hydrogels increased with the decrease of the synthesis
temperature and with the increase of the cross-linker ratio, the
lowest percentage of DxS being released from the composite
hydrogels obtained at 18 C and having a cross-linker ratio of
1/40 (Fig. 8, up, left). The dry state porosity of the composite gels
was much higher in the case of cryogels (gel preparation
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Fig. 8. Percentage removal of DxS from semi-IPN PAAm/DxS composite hydrogels after 48 h immersion in water (pH = 5.5) at 25 C, as a function of the gel preparation
temperature (up, left); dry state porosity of semi-IPN PAAm/DxS composite hydrogels as a function of the gel preparation temperature, at two cross-linking ratios (up, right);
SEM image of semi-IPN PAAm/DxS composite cryogel at a cross-linking ratio of 1/40, Mag 100 (down, left); comparative behavior under uniaxial compression of semi-IPN
PAAm/DxS hydrogels prepared at 20 C (A) and 18 C (B) (down, right).
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10
qe
C o C e V
;
W
mg=g
R C o C e =C o 100
1
2
DGoads RT ln K C
ln K C
DSoads DHoads
R
RT
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11
Table 1
Maximum equilibrium sorption capacity of IPN hydrogels for ionic dyes.
Sorbent
Dye
pH
T, C
qmax, mg/g
Reference
Anionic dyes
Semi-IPN CS/(AAm-PEG macromer)
Semi-IPN (NaAA-co-HEMA/MBA)/SA
Semi-IPN (AA-co-HEMA/MBA)/SA
Semi-IPN CS/(AAm-PEG macromer)
Methyl orange
Congo Red
Congo Red
Acid Red 18
0.6
1
1
0.6
7
7
25
25
25
25
185.24
172
149.68
342.54
[221]
[219]
[219]
[221]
Cationic dyes
Cryogel IPN PAAm/CS
Cryogel semi-IPN PAAm/PA
Semi-IPN Alg/PASP
Semi-IPN Alg/PASP
Semi-IPN (AA-co-HEMA/MBA)/SA
Semi-IPN PAMHEMA/CMC
Semi-IPN PAMHEMA/CMC
Cryogel semi-IPN PAAm/DxS
Semi-IPN AA/AM/n-BA/amylose
Methylene Blue
Methylene Blue
Methylene Blue
Malachite Green
Methyl violet
Methyl violet, 500 mg/L in feed dye
Basic fuchsin, 500 mg/L in feed dye
Methylene Blue
Crystal Violet
1
1
2
2
1
1
1
0.67
0.2
6.5
6.5
7
7
7
5.5
7.4
25
25
25
25
25
25
25
25
25
750
667.7
600700
300350
126.18
613.8
920
18.76
35.09
[14]
[115]
[217]
[217]
[219]
[222]
[222]
[224]
[225]
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and contributed to the increase of the maximum sorption of metal ions (261.08 mg Cu2+/g gel, and up to 736.95 mg Pb2+/g gel),
and to the increase of the sorbent reusability. Semi-IPN composite hydrogels composed on SA-g-PAA as a matrix and PVP and GE
as entrapped chains and their sorption capacity for Ni2+, Cu2+,
Zn2+, and Cd2+ have been reported by Wang et al., the maximum
equilibrium adsorption capacity, in non-competitive conditions,
being the highest for Cu2+ (3.22 mmol/g), and the lowest for
Cd2+ (2.91 mmol/) [236] (Table 2). The authors have tted the
experimental isotherms of sorption with three isotherm models
(Langmuir, Freundlich and Dubinin-Radushkevich), and found
the Langmuir isotherm suitable to describe the adsorption process, supporting the formation of a monolayer of metal ions in
the composite hydrogel. As shown in Fig. 9, the electrostatic
interaction and ion exchange between the COO groups from
SA and the grafted PAA, on the one side, and the cationic metal
ions, on the other side, facilitated the penetration of heavy metal
ions into the composite hydrogel, in the rst step, the chelation
of heavy metal ions with the functional groups of the composite
gel (NH2, COOH, C@O), and a chemical adsorption process occurred in the second step [236].
The adsorption mechanism has been supported also by the
sorption kinetics, which have been perfect tted by the PSO kinetic
model.
Our own research was focused on the investigation of the
equilibrium sorption capacity for Cu2+, Cd2+, Ni2+, and Zn2+ of the
semi-IPN cryogels based on PAAm as a matrix and PA as entrapped
polymer [238]. The experimental data obtained in batch mode
have been analyzed by four isotherm models: Langmuir, Freundlich,
Sips and Temkin. A comparison of the linear and non-linear regression tting of these isotherms has been performed because, sometimes, the linearization of a model function has a negative effect on
the ability of a model to t the experimental data [201,207,222].
Based on the non-linear regression method it was found that
the Sips isotherm tted the best the experimental data with a
Table 2
Maximum equilibrium sorption capacity of IPN hydrogels for heavy metal ions.
Sorbent
Metal ion
a
Semi-IPN PMAAm/CP
Hydrolyzed semi-IPN PMAAm/CPb
Semi-IPN PMAAm/HPCc
Hydrolyzed semi-IPN PMAAm/HPCb
Semi-IPN SA-g-PAA/PVP/GE
Semi-IPN SA-g-PAA/PVP/GE
Semi-IPN SA-g-PAA/PVP/GE
Semi-IPN SA-g-PAA/PVP/GE
Semi-IPN CS-g-PAA/GE
Sequential IPN poly(PEGDA)/PMAA
Sequential IPN poly(PEGDA)/PMAA
Semi-IPN poly(PEGDA)/PMAA
a
b
c
2+
Fe
Fe2+
Cu2+
Cu2+
Ni2+
Cu2+
Zn2+
Cd2+
Cu2+
Pb2+
Cu2+
Cd2+
pH
T, C
qmax, mmol/g
Reference
10
10
20
20
2
2
2
2
2
1
1
1
5
5
5
5
5.75
5
5
5
25
25
25
25
30
30
30
30
30
25
25
25
0.178
0.358
0.2
2
3.158
3.221
3.035
2.913
4.81
0.55
0.36
0.33
[232]
[232]
[232]
[232]
[236]
[236]
[236]
[236]
[237]
[240]
[240]
[240]
CP cellulose phosphate.
Partial saponication by immersion in 0.5 M NaOH for 48 h at 25 C.
HPC hydroxypropyl cellulose.
Fig. 9. The main mechanism for the adsorption of metal ions onto the hydrogel (reproduced with permission from Ref. [236]).
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been: Cu2+ > Hg2+ > Cd2+ > Pb2+, and in the quaternary mixtures,
the selectivity has been similar with that found for individual ions.
The better retention of Hg2+ by the PVA/PEI membrane was attributed to the high afnity of Hg2+ for this membrane.
3.3.3. Ion imprinted IPN hydrogels
Selectivity in the heavy metal ions removal is still a challenging
concern, a real progress in the led being performed by the ion-imprinted polymers, a concept similar with molecularly imprinted
polymers, recently reviewed by Branger et al. [247]. The imprinting
process renders the resulting polymer able to recognize and selectively bind the template in the environment. Ion imprinted IPN
hydrogels were also synthesized and evaluated for their capacity
to selectively adsorb heavy metal ions [248250]. The number of
publications in this eld is still low, but it is expected to increase
in the near future. Thus, Junyan et al. synthesized Cd(II) imprinted
IPN containing epoxy resin, triethylenetetramine and cadmium
methacrylate acrylamide-BAAm by in situ sequential polymerization, which was successfully applied to the analysis of two natural
water samples [248]. Liu et al. synthesized an IPN ion-imprinting
hydrogel (IIH) via cross-linking of blended CS/PVA with ethylene
glycol diglycidyl ether using uranyl ion as template [249]. The
sorption experiments were performed in batch mode, the optimum
pH was 5.06.0, and the adsorption process was well described by
both Langmuir and Freundlich isotherms. Equilibrium of sorption
was achieved within 2 h and the maximum adsorption capacity
was 156 mg/g. The most signicant results, which support the
advantage of the IIH compared to the non-imprinted hydrogel,
consist of the selective adsorption of uranyl ion in a mixture with
other heavy metal ions, the distribution ratio of IIH for uranyl ion
being 6-fold greater than that of non-imprinted hydrogel, but
was almost the same for the other heavy metal ions. A novel thermoresponsive Cu(II) ion-imprinted IPN [Cu(II)-IIH] has been recently reported by Wang and Liu [250]. The Cu(II)-IIH has been
prepared by free radical/cationic polymerization (simultaneous
strategy) of NIPAAm and triethylene glycol divinyl ether using
Cu(II) ion as template. The memory was xed by shrinking of the
gel above the VPTT, and was deleted by swelling below VPTT.
The Cu(II)-IIH showed a stronger afnity for Cu(II) ions than for
other competitor metal ions compared with the non-imprinted
IPN hydrogel.
3.4. Desorption and reusability
Preservation of the sorption capacity during the consecutive
sorption/desorption cycles is an important characteristic of all
the sorbents used in the removal of contaminants from the wastewaters. The majority of semi-IPN and IPN hydrogels used as sorbents for both dyes and heavy metal ions showed a high level of
reusability, some examples being presented in this subsection.
For example, desorption of MB from the full-IPN PAAm/CS cryogel
has been performed with 0.1 M HCl, the sorbent being regenerated
with 0.1 M NaOH. After four sorption/desorption cycles, the sorption capacity for MB remained almost unchanged [14] and this
support the high reusability of these IPN cryogels. After the controlled hydrolysis, the semi-IPN cryogels composed of PAAm and
PA, described in Section 3.2, showed almost the same sorption
capacity for MB after six consecutive sorption/desorption cycles
(around 150 mg MB/g, at an initial concentration of the dye of
157.4 mg/g, the sorbent dosage being 1 g/L) [115]. Semi-IPN hydrogel composed of CMC entrapped in a matrix of AAm and HEMA
(PAMHEMA) has been successfully reused for the sorption of basic
fuchsin and MV (Table 1), their sorption capacity being almost unchanged after ve repeated adsorption/desorption cycles [222].
Desorption of heavy metals was usually performed with dilute
solutions of HCl or HNO3 [235237,240,242]. Thus, desorption of
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have potential as effective pH/temperature responsive drug delivery system [97]. An interesting approach for the synthesis of SA/
PNIPAAm semi-IPN hydrogels, with an enhanced deswelling rate
compared to pure PNIPAAm, consists of the in situ generation
and preservation of magnetic iron oxides [91].
It was also found that the deswelling/reswelling kinetics of
the semi-IPN hydrogels based on synthetic polymers was much
faster than that of the single-network hydrogels, both for
homo-semi-IPN [158] and hetero-semi-IPN [164,172,180]. Miyata
et al. investigated the response to the solvent quality (acetone/
water mixtures) of the PAAm single network and PAAm homosemi-IPN hydrogel [158]. The fast responsiveness at shrinkage
of the PAAm homo-semi-IPN hydrogel compared to PAAm single
network has been attributed to the inherent mobility of the linear polymer chains of PAAm entangled in the cross-linked PAAm,
which respond much faster at the environment than the PAAm
network. Furthermore, the collapse of the linear PAAm chains
could accelerate the shrinkage of the network because they were
entangled in the cross-linked chains of the semi-IPN structure
[158]. Generation of temperature responsive swelling properties
in semi-IPN hydrogels by entrapping PVP in a P(HEMA/IA) matrix
has been recently reported, the single network hydrogel having
no thermosensitivity [194].
The strategy used for the synthesis of IPN could have also an
inuence on the swelling kinetics and drug release, a higher thermosensitivity being observed for sequential than for simultaneous
semi-IPN, because the sequential strategy allows a better control of
the morphology and mechanical properties of the IPN composite
hydrogels [176]. IPN hydrogels endowed with enhanced mechanical properties have been prepared by a sequential technique incorporating a second polymer network inside a super-porous hydrogel
[196]. Mechanical properties (compressive strength and elasticity)
were signicantly improved (up to 50-fold times) as compared to a
control single-network hydrogel.
The sorption capacity for cationic dyes (RB and MV) onto semiIPN and IPN hydrogels based on PVA and poly(AA-co-HEMA)
prepared by Mandal et al. was lower on IPN than on semi-IPN,
situation attributed to the tighter network structure of the IPN
[214]. Semi-IPN hydrogels composed of GE entrapped in CS-g-PAA
matrix showed very high sorption capacities for metal ions, and
very fast sorption kinetics (sorption equilibrium has been attained
in about 15 min) [235,237]. The presence of GE chains enhanced
the mechanical strength of semi-IPN hydrogels and contributed
to the increase of the maximum sorption capacity of metal ions.
An intelligent recovery system of metal ions consisting of
PNIPAAm as matrix and NaPAA as entrapped homopolymer has
been reported by Yamashita et al. [242]. The IPN hydrogel
adsorbed Cu(II) ions below the VPTT and released water above
the VPTT but not metal ions.
Wang et al. reported IPN hydrogels with enhanced adsorption
properties for heavy metal ions either simultaneous, by free radical/cationic photopolymerization of AMPS and DVE-3 [11], or by
the sequential strategy with poly(PEGDA), and PMAA as the two
independent networks [240]. Adsorption capacity of the IPN
hydrogels for Cu(II), Cd(II), and Pb(II) has been compared with that
of single networks. The adsorption capacity of simultaneous IPN
hydrogels increased with the increase of AMPS content in the IPN
hydrogel, for all metal ions [11]. The adsorption capacity of the
sequential IPN hydrogels increased with the increase of PMAA content in the IPN hydrogel, a synergistic complexation of metal ions
with the two polymer chains being assumed to explain the increase of the experimental sorption capacity compared with the
theoretical sorption capacity [240]. The sorption equilibrium has
been attained very fast compared to the single network hydrogels
[11,240,241].
Please cite this article in press as: E.S. Dragan, Design and applications of interpenetrating polymer network hydrogels. A review, Chem. Eng. J. (2014),
http://dx.doi.org/10.1016/j.cej.2014.01.065
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