Interpretación de Polimeros

Chemical Engineering Journal xxx (2014) xxxxxx
Contents lists available at ScienceDirect
Chemical Engineering Journal

journal homepage: www.elsevier.com/locate/cej
Review
Design and applications of interpenetrating polymer network hydrogels.

A review
Ecaterina Stela Dragan
Petru Poni Institute of Macromolecular Chemistry, Aleea Grigore Ghica Voda 41 A, 700487 Iasi, Romania
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.
Please cite this article in press as: E.S. Dragan, Design and applications of interpenetrating polymer network hydrogels. A review, Chem. Eng. J. (2014),
E.S. Dragan / Chemical Engineering Journal xxx (2014) xxxxxx
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
and activator, with or without a cross-linker (Fig. 1b). If a cross-linker

is present, fully-IPN result, while in the absence of a cross-linker, a network having linear polymers embedded within the rst network is
formed (semi-IPN) [7,8,12,13].
When a linear polymer, either synthetic or biopolymer, is entrapped in a matrix, forming thus a semi-IPN hydrogel, fully-IPN
can be prepared after that by a selective cross-linking of the linear
polymer chains [1416] (Fig. 1c).
By their structure, IPN hydrogels can be classied in: (i) IPNs, formed
by two networks ideally juxtaposed, with many entanglements and
physical interactions between them; (ii) homo-IPNs, which are a special
case of IPN, where the two polymers which form the independent networks have the same structure; (iii) semi- or pseudo-IPNs, in which
one component has a linear instead of a network structure. Mechanically
enhanced IPN hydrogels as double networks, promoted by Gong et al.,
have attracted attention by their potential for biomaterials, mainly as a
replacement of natural cartilage [1719]. The particular feature of this
new type of IPN hydrogels, characterized by high resistance to wear
and high fracture strength, consists of the preparation rst of a densely
cross-linked ionic hydrogel, the second network being a neutral loosely
cross-linked network [17,18].
This review aims to give an overview on the preparation and
applications of semi- and fully-IPN hydrogels based on the most recent publications in the eld. In the rst part, the main synthesis
strategies of IPN hydrogels, their relevant properties and biomedical applications will be presented. In the second part, an overview
on the most specic applications of the IPN hydrogels in separation
processes will be given.
2. Design, characterization, and biomedical applications of IPN

hydrogels
A wide variety of hydrophilic polymers or their precursors have
been used to synthesize hydrogels, the main classes consisting of
natural polymers and their derivatives (polysaccharides and proteins), and synthetic polymers containing hydrophilic functional
groups such as COOH, OH, CONH2, SO3H, amines and R4N+,
and ether [1]. By the combination of polymers coming from these
two classes, IPN composite hydrogels can be prepared by the three
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.
2.1. Polysaccharide based IPN hydrogels

2.1.1. Chitosan
Chitosan (CS), the linear cationic polysaccharide composed of
b-(1 ? 4)-2-amino-2-deoxy-D-glucopyranose and b-(1 ? 4)-2acetamido-2-deoxy-D-glucopyranose units, randomly distributed
along the polymer chain, has attracted numerous scientists due
to its outstanding biological properties like biodegradability,
biocompatibility, and antibacterial activity. By the high content
of amino and hydroxyl functional groups, CS has also drawn attention as a biosorbent showing high potential for the adsorption of
proteins, dyes, and metal ions [20,21].
Numerous investigations were performed to prepare IPN hydrogels composed of CS, or its derivatives, and other polysaccharides,
or their derivatives, mainly in order to design novel and more efcient drug release systems. Thus, cellulose [22] and its derivatives
[2325], or AAm-g-dextran [26] have been rst blended with CS
followed by selective cross-linking of CS with glutaraldehyde
(GA). Semi-IPN hydrogels composed of cross-linked CS and entrapped AAm-g-hydroxyethyl cellulose (AAm-g-HEC) and their enhanced loading with diclofenac sodium (DS) have been recently
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
Fig. 2. Possible combinations of hydrophilic polymers used to prepare IPN

hydrogels.
reported [23], the schematic representation of their formation

being presented in Fig. 3.
The encapsulation efciency of DS in semi-IPN increased up to
83%, and the percent of in vitro release depended on the pH, the
content of the entrapped AAm-g-HEC, the cross-linking degree
and the drug loading.
Yang et al. have recently reported preparation of novel hydrogels composed of PEG grafted on carboxymethyl chitosan and alginate (Alg), and found an improvement of the protein release at pH
7.4, suggesting this composite hydrogel to be promising for protein
drug delivery in the intestine [27]. As cross-linker for CS, GA is usually used due to the fast formation of Schiff base between the NH2
groups of CS and aldehyde groups of GA. However, GA is highly
toxic in nature and therefore, pharmaceutical scientists normally
do not recommend its use in the synthesis of IPN for the purpose
of drug delivery. Recently, a new natural cross-linking agent, genipin, has been successfully used in the preparation of CS based
hydrogels [2831].
Various IPN hydrogels composed of CS and synthetic polymers
have been recently designed and investigated for their biomedical
applications, the most relevant being presented in the next three
subsections.
2.1.1.1. IPN hydrogels based on chitosan and synthetic ionic matrices. Chitosan and its derivatives have been used as components in
the formation of IPN composite hydrogels with various ionic polymers containing carboxylic groups like poly(acrylic acid) (PAA)
[32,33], copolymers of acrylic acid [3437], poly(methacrylic acid)
(PMAA) [3840], poly(N-acryloylglycine) [41], or cationic centers
like quaternary ammonium groups [42] and amine groups [43
45]. The synthesis of semi-IPN has been carried out either by
selective cross-linking of CS in the presence of a preformed
polyelectrolyte [33,38,43] or by the synthesis of the cross-linked
polyelectrolyte in the presence of CS [32,34,35,39,40,42,44].
Full-IPNs have been also prepared by the post-cross-linking of CS
entrapped in a polyelectrolyte matrix [36].
In the case of the composite IPN of CS and polyelectrolytes containing carboxylic groups, the ionic interactions between NH
3
groups of CS and COO from the anionic polyelectrolyte, which
were identied in a certain range of pH, contributed to the increase
of the mechanical properties of the gels and to the decrease of the
swelling degree because they contribute to the relative increase of
the cross-linking density of the gel [33,38,39]. However, the ionic
cross-links make the gels to be reversible responsive to variation
of the solution pH and ionic strength [32,37,38]. The interest in
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.
The semi-IPN and IPN hydrogels were characterized by FTIR,

differential scanning calorimetry (DSC), scanning electron microscopy (SEM), and equilibrium swelling. FTIR spectroscopy supported the presence of CS and the hydrolysis of amide groups in
full-IPN. The freeze-dried hydrogels displayed a porous morphology generated by the sublimation of water under freeze-drying
conditions. The swelling kinetics have been followed for both
semi- and full-IPN, and found that the transport of water was the
Fickian diffusion for all the gels [15].
Other strategies for the synthesis of IPN composite hydrogels
consist of the blending CS with preformed synthetic polymers like
poly(acrylamide) (PAAm) [46], polyacrylonitrile (PAN) [63,64],
poly(ethylene glycol) (PEG) [28,65,66], poly(vinyl alcohol) (PVA)
[6773], poly(vinyl pyrrolidone) (PVP) [7476], poly(dimethylsiloxane)PEG copolymer [77] followed by the selective cross-linking of CS. pH and temperature responsive semi-IPN hydrogels
have been obtained by the cross-linking of CS in the presence of
(PAN) [63,64].
2.1.1.3. IPN cryogels based on chitosan and synthetic matrices. Cryogels are 3-D macroporous polymeric gels prepared below the freezing point of the solvent (water in the case of hydrogels) [7882].
The unique feature of cryogels consists of their interconnected
macropores (with sizes between 1 and 100 lm), which allow rapid
and non-restricted mass-transport of any solute, and even microparticles [78,79,81]. Cryogels are endowed with a capillary network through which the solvent can ow by convective mass
transport, a high mechanical strength and osmotic stability, which
make them adequate materials for various biomedical applications
and bioseparations [79,82]. IPN composite cryogels for bioengineering applications have been recently developed by Kumar and
coworkers [79]. A characteristic of cryogels is their very fast swelling at equilibrium, which was found to depend on the total monomer concentration, the cross-linking density, the synthesis
temperature, etc. As already mentioned, unlike the conventional
hydrogels, cryogels have valuable mechanical properties. Thus, Jain
and Kumar [79] determined the Youngs modulus of the PAAm/CS
cryogels to get information about the pressure which they could
bear as scaffolds for biomaterial applications, and found that, by
their hydrophilic nature, cryogels had a very high exibility.
In our own investigations, we have prepared ionic composite
cryogels consisting of two independently cross-linked and oppositely charged networks [14]. Semi-IPN cryogels were prepared
rst by cross-linking polymerization of AAm with BAAm in the
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.
presence of CS, under freezing conditions, the main parameters

varied being cross-linker ratio (X), pH of the CS solution, and CS
molar mass (CS1 and CS2 having Mv = 235 kDa, and 467 kDa,
respectively). It was found that the fraction of CS trapped in the
semi-IPN cryogels increased with the increase of X, pH of CS solution, and CS molar mass. To obtain fully-IPN cryogels, the CS chains
trapped in the semi-IPN cryogels were cross-linked with ECH under alkaline conditions, as it was already shown for the synthesis
of conventional IPN hydrogels (Fig. 4). The structure of the IPN
composite gels was conrmed by FTIR spectroscopy, the hydrolysis
degree in full-IPN being also evaluated [14]. Interior morphology of
semi-IPN and IPN cryogels examined by SEM evidenced interconnected macropores with sizes in the range 3080 lm. Some SEM
images are presented in Fig. 5 to illustrate morphological changes,
which occurred during the generation of the second network in
IPN. The code of the semi-IPN hydrogels consists of semi-IPN followed by two numbers separated by dots: the rst one denotes
the CS used as trapped polymer, the second one represents the
mole number of AAm per one mole of BAAm. The code of fullIPN consists of the term IPN followed by the same numbers like
the semi-IPN used for their preparation.
As can be seen in Fig. 5, the decrease of the cross-linker ratio
from 1/40 to 1/60, for the same molar mass of CS (CS1), conducted
to about twice larger pores (average pore size 34 lm compared
with 75 lm), and to less compact pore walls, these being more
accessible for the diffusion of low molecular weight species
(IPN1.40 compared with IPN1.60).
Super-fast swelling characterized all semi-IPN cryogels, the
equilibrium swelling state being attained in 23 s, the difference
consisting of the equilibrium swelling ratio (SReq), which increased
with the decrease of the cross-linker ratio [14]. The main differences between IPN and semi-IPN cryogels concerning the swelling
kinetics was the much higher values of the SReq (155 g/g compared
with 33 g/g) and of the time necessary to reach the equilibrium
swelling, which was about 45 s (IPN) compared with 3 s (semiIPN). The increase of the time necessary to reach the equilibrium
swelling has been explained by the presence of two networks,
which respond independently to the environmental changes. The
much higher swelling ratios of IPN cryogels were explained by
the presence of the anionic matrix, which is bearing COO groups,
known for their high hydrophilicity. Both semi-IPN and IPN were
pH responsive, the SR values of semi-IPN decreasing when pH increased from 4 to 7, because the deprotonation of the amine
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-
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-
proach for the synthesis of semi-IPN SA/PNIPAAm hydrogels with

an enhanced deswelling rate compared to pure PNIPAAm consists
of the in situ generation of magnetic iron oxides by oxidation of iron
cations coordinated to the Alg network [91]. It was demonstrated
that the in situ synthesis of the iron oxide nanoparticles prevented
their diffusion out of the semi-IPN, and that the porosity of the gels
increased because a partial hydrolysis of the Alg chains occurred.
An interesting strategy for the preparation of IPN SA/PNIPAAm
recently reported consists of the preparation rst of the ionically
cross-linked SA beads, which were than soaked in the solution of
NIPAAm, cross-liker, initator followed by cross-linking polymerization of NIPAA at a temperature above the LCST of PNIPAAm [95].
The obtained composite beads changed their transparency in response to the change of temperature but kept their original shape
and size. The dynamic temperature cycling revealed the repeatability of the thermoresponsivity, a hysteresis, characteristic to the
coil/globule transition of PNIPAAm, being observed.
Synthesis of IPN composite hydrogels based on SA and other
synthetic polymers like PAAm [98], PEG [99], PVA [100], and PVP
[101] and their swelling properties and applications for controlled
release of bioactive agents were also recently reported. In situ
formed IPN hydrogels based on a physical network of calcium
Alg interpenetrated with a chemical cross-linked network based
on dextran derivatized with HEMA were prepared and evaluated
for the protein release, mechanical characteristics and biocompatibility [102].
2.1.3. Starch and derivatives
As the second abundant polysaccharide after cellulose, starch
offers an interesting set of characteristics, including biodegradability, biocompatibility, and bioactivity. Native starch granules are
water insoluble, containing two major components: (1) amylose,

2030% of the starch granules, which consists of linear chains of
a-(1-4-linked-D-glucose) units, and (2) amylopectin, which consists of branched chains of a-(1-4-linked-D-glucose) units interlinked by a-(1-6-linked-D-glucose) linkages, in proportion of 70
80%. Various modications of starch were developed to improve
its hydrophilic character [103,104]. Native and modied starches
have been used as raw materials in the preparation of biodegradable hydrogels for biomedical applications [105,106]. For many
applications, multicomponent hydrogels as semi-IPN or IPN show
improved mechanical properties, faster response rate and diffusion
of solutes [107110]. The swelling/diffusion properties such as initial swelling rate, swelling rate constant, SReq, mechanism of water
diffusion of the semi-IPN hydrogels prepared by the cross-linking
copolymerization of AAm and sodium methacrylate in the
presence of starch have been investigated by Keshavara Murthy
et al. [107]. The high EWC of these composite hydrogels recommends them as novel biomaterials in biomedical/pharmaceutical
technology or as moisture maintenance materials in agriculture
elds.
Amphoteric semi-IPN composite hydrogels have been prepared
by the graft copolymerization of AA onto cationic starch in the
presence of either PDADMAC [109] or poly(methacryloyloxyethylammonium chloride) (PDMC) [110]. The existence of salt linkages
between the carboxyl groups in cationic starch-g-AA network and
quaternary ammonium groups on PDMC chains has been testied
by FT-IR spectroscopy. The swelling studies showed a high swelling
capacity in distilled water and outstanding pH-sensitivity of the
semi-IPN hydrogels. It was also found that the hydrogels containing more PDMC were not sensitive in the basic medium, which
endowed the hydrogel with potential application in agriculture.
In our own research, native potato starch (PS) or anionically
modied PS (PA) have been entrapped in a PAAm matrix, both conventional semi-IPN hydrogels [111,112] and semi-IPN cryogels
being prepared [113115]. Anionically modied PS has been prepared by the alkaline hydrolysis of the nitrile groups in PS-g-PAN
[111]. The properties of the gels have been further modulated by
controlled hydrolysis under alkaline conditions (0.5 M NaOH, 4 h
at 25 C). Formation of semi-IPN hydrogel and the main functional
groups after the controlled hydrolysis can be seen in Fig. 6.
To evaluate the sorption mechanism of water in the conventional hydrogels, the swelling data were analyzed by the empirical
equation of Frenson and Peppas [116], swelling being controlled by

a Fickian diffusion when PS was used as entrapped polymer
(n < 0.45), and by an Anomalous transport (0.45 < n < 0.89) when
PA was entrapped in PAAm matrix [111]. Multiresponsive semiIPN composite cryogels as rods have been prepared by the radical
cross-linking copolymerization of AAm with BAAm in the presence
of PS or PA, under the freezing point of the solvent (18 C) [114].
Fig. 7 shows that the gels morphology was inuenced by the composition of the gels and also by the controlled hydrolysis. The code
of the semi-IPN hydrogels consists of semi-IPN followed by two
numbers separated by dots: the rst one represents the mole number of AAm per one mole of BAAm, and the second one represents
the initial concentration of monomers. The letter H denotes the
samples after the controlled hydrolysis.
As can be seen, before hydrolysis, the PAAm/PA60.5 composite
cryogel had a sponge like structure, with interconnected pores,
macropores with sizes of about 60 lm, while the PAAm/PS60.5
composite cryogel revealed pores with sizes around 39 lm. The
pore size in PAAm/PA60.5 was less inuenced by the hydrolysis,
while the pore size increased up to 50 lm, after the hydrolysis of
PAAm/PS60.5. This shows that the presence of PA, bearing a high
number of negative charges, diminished the level of hydrolysis of
the amide groups attached to the matrix, while the presence of native PS enhanced the hydrolysis level. The pore size also increased
by the decrease of the cross-linker ratio from 1/60 to 1/80. All composite cryogels presented a super-fast swelling, the main difference consisting of the time necessary to attain the equilibrium
swelling, this being around 30 s in the case of PAAm/PS gels and
15 s in the case of PAAm/PA gels, at the same cross-linker ratio
(1/60) [114]. The anionic character of the gels having PA as entrapped polymer, and of the composite cryogels having gelatinized
PS entrapped in the PAAm matrix, only after hydrolysis, has been
demonstrated by the fast increase of SReq values at pH > 3. The
rapid response rate to the external stimuli of the smart hydrogels
is the most essential function for their applications, and therefore
various methods have been used to increase the response kinetics.
The study of the deswelling/reswelling kinetics of the composite
gels, having a low cross-linker ratio (1/80), in ethanol/pure water,
and 1 M NaCl/pure water showed a higher responsivity of the
anionic gels prepared with the initial monomer concentration, Co,
of 3% compared to the gels having Co = 5%, and this support their
potential as smart materials [114].
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]).
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.
2.1.4. Other polysaccharides

Many other polysaccharides or their derivatives have been used
in the preparation of semi-IPN or IPN composite hydrogels, the
most employed being: cellulose [117], carboxymethylcellulose
(CMC) [118123], hyaluronic acid (HA) [124128], kappa-karrageenan [129131], xantan [132], guar gum [133], chondroitin sulfate [124,134], etc. Semi-IPN hydrogels composed of cross-linked
PAA and entrapped CMC have been prepared by Bajpai and Mishra,
the network parameters (average molecular weight between crosslinks, crosslink density) being evaluated from the water sorption
capacity [118]. The release proles of the entrapped drug (tetracycline) were investigated as a function of the IPN composition [119].
The hydrophilic character of CMC was further increased by grafting
NaAA in the presence of the linear PVP and a cross-linker, novel
superabsorbent semi-IPN composite hydrogels being thus prepared by Wang et al. [122]. The gels structure, the network parameters and the pH responsiveness have been evaluated as a function
of the gel composition. The incorporation of PVP improved the
swelling capabilities, swelling kinetics and salt-resistant properties
of the composite hydrogel, which recommend them as potential
candidate for water-manageable materials or drug delivery
systems.
Hyaluronic acid (HA), frequently mentioned as hyaluronan owing to its existence as polyanion, is a linear polysaccharide of high
molecular weight consisting of two alternating disaccharide units
of b-1,4-D-glucuronic acid and b-1,3-N-acetyl-D-glucosamine
[125]. HA is the most commonly exploited natural polysaccharide
in scaffold assembly for tissue engineering and as component for
implant materials. HA is very hydrophilic and inuences several
cellular functions such as migration, adhesion and proliferation,
contributing to the regulation of water balance, behaving like a lubricant by protecting the articular cartilage surface, acting as a
scavenger molecule for free radicals [124]. HA-based materials offer excellent biocompatibility, biodegradability, and versatility in
producing materials for tissue engineering scaffolds. One drawback
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
temperature of 18 C) than in the case of conventional hydrogels

(gel preparation temperature of 5 and 25 C), being less inuenced
by the cross-linker ratio (Fig. 8 up, right).
The interior morphology of the semi-IPN cryogels is illustrated
by the SEM image included in Fig. 8 (down, left), interconnected
pores with sizes of about 120 lm being visible. The uniaxial compression measurements performed on equilibrium swollen PAAm/
DxS composite hydrogels showed that hydrogels highly stable
against the mechanical forces were obtained by conducting the
cross-linking copolymerization at subzero temperature (Fig. 8
down, right).
2.2. Protein based IPN hydrogels
Various proteins were used in the preparation of IPN composite
hydrogels in combination with either synthetic polymers or with
gelatin (GE), the protein derived from collagen. The main goal in
this case was to enhance the blood biocompatibility of the semiIPN hydrogels [139], and biological activity of synthetic polymers
[140,141] or, as recently reported, to increase the structural stability of the GE nanobers [142]. In the last case, polyethyleneglycol
diacrylate (PEG-DA) was used as a cross-linker because, unlike the
other cross-linkers which interact directly with gelatin, PEG-DA
undergoes free radical cross-linking polymerization with no
reaction with the functional groups of GE, creating a matrix which
enhanced the structural stability of the semi-IPN scaffold in
aqueous solutions. Macroporous IPN composite hydrogels have
been prepared by Jain et al. by cryogelation technique, when the
cross-linking polymerization of acrylonitrile in the presence of
GE and cross-linking of GE with GA simultaneously occurred [139].
Silk broin (SF), another biopolymer intensively used in the
preparation of IPN hydrogels, is a brous protein of silk ber and
consists of heavy (350 kDa) and light (25 kDa) chain polypeptides,
connected by a disulde link [143]. The regenerated ber has been
considered as candidate for biomaterials owing to its good

mechanical strength in the wet state, biocompatibility for the
growth of cells, and high resistance against enzymatic degradation.
As it was already mentioned, there are numerous studies to reduce
the limitations of hydrogels composed of PNIPAAm, such as the
lack of biocompatibility, deswelling rate, and mechanical properties. PNIPAAm hydrogels have a very slow deswelling rate due to
the formation of a skin layer, which interrupts the release of internal water molecules in the deswelling process (skin effect). Synthesis of multicomponent materials like IPNs of PNIPAAm and SF was
developed by Gil and Hudson [143] to improve the deswelling
kinetics by suppressing the skin layer formation. IPN composite
hydrogels composed of SF and other synthetic polymers
[144,145], by their good mechanical properties, are of interest in
tissue engineering and regenerative medicine.
Silk sericin is a water soluble globular protein derived from silkworm, which has been used by Wu et al. in the preparation of IPN
hydrogels with PNIPAAm [146] and PMMA [147], the last one
being a fast pH-responsive hydrogel. Other protein based IPN
hydrogels are composed of brin and PEG [148], brin and HA
[149], soy protein and PNIPAAm [150,151], collagen and HA
[152], PAAm and poly(c-glutamic acid) [153].
2.3. IPN hydrogels based only on synthetic polymers

The large variety of this category of IPN composite hydrogels is
explained by the numerous possibilities to combine synthetic polymers, which structures could be practically designed according to
the imagination of the investigator. Unlike the biopolymers, which
structures depend on many natural factors, the structure of synthetic polymers can be designed and reproduced whenever they
are requested. In a rst attempt to group these IPN hydrogels,
the following two main classes are proposed:
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).
10
IPN hydrogels based on nonionic synthetic polymers, where

PHEMA, PEG, PAAm, PVA represent the most employed polymers in the preparation of semi-IPN or IPN composite hydrogels, mainly for biomedical applications and separation
processes [154164].
Ionic IPN hydrogels, such as: anionic [165179], cationic
[180185], and anionic/cationic [186191]. Polyampholyte IPN
hydrogels based exclusively on synthetic polymers have been
only seldom reported [192,193].
A particular type of IPN hydrogels based only on synthetic polymers, is that of homo-IPN [155,158], comprehensively discussed by
Chirila et al. taking as a model homo-IPN based on HEMA [155].
The majority of the IPN composite hydrogels based on synthetic polymers are responsive at two [169,171,172,194,195] or
three external stimuli [173,178,181]. The second network or just
the entrapped linear polymer in semi-IPN could alter the responsivity of the gels. Thus, it was observed that the responsiveness
(deswelling/reswelling kinetics) of the semi-IPN hydrogels is
much faster than that of the single-network hydrogels both in
the case of homo-semi-IPN [158] and hetero-semi-IPN
[164,172,180], excepting the poly(styrenesulfonic acid sodium
salt) entrapped into the PNIPAM matrix, which had an opposite
effect, an irreversible collapse of semi-IPN being reported, i.e.
the composite gel did not restore their volume by reswelling
after shrinking [170]. Furthermore, semi-IPN hydrogels having
temperature responsive swelling properties have been generated
by entrapping PVP in a P(HEMA/IA) matrix, the conventional
(HEMA/IA) matrix having no thermosensitivity [194].
To increase the drug loading capacity of hydrogels for hydrophobic drugs, Huang et al. have prepared a multiple-responsive
semi-IPN hydrogel based on b-cyclodextrin-ECH (b-CD-ECH) entrapped in a matrix of poly(3-acrylamidophenylboronic acid-co2-dimethylaminoethyl
methacrylate)
[P(AAPBA-co-DMAEM)]
[181]. The drug release was slower than in the conventional P(AAPBA-co-DMAEM) hydrogel due to the presence of b-CD, and was
inuenced by pH, temperature, ionic strength and the glucose concentration. The method 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, at least in one case [176].
IPN hydrogels having anionic and cationic groups attached to
different chains (networks) are stabilized not only by covalent
bonds but also by ionic bonds, which contribute to the increase
of their mechanical strength and to the pH and ionic strength
reversible responsiveness [189,191]. At a certain ratio between
the opposite charges they could form polyion complexes, which
are an interesting class of functional materials with various applications as biomaterials, drug delivery systems, dumping materials, etc. An interesting approach to design ionic IPN hydrogels
having a controlled ratio between cationic and anionic groups
was proposed by Ajiro et al. who prepared IPN of PAA and protected poly(vinylamine), the primary amine groups available in
IPN being generated by the selective hydrolyzes of N-vinylformamide (NVF) in NVF-co-N-vinylacetamide [186], the ratio between
anionic and cationic groups being controlled by the content in
PAA. IPN hydrogels endowed with enhanced mechanical properties were prepared by a sequential technique incorporating a second polymer network (PAN) inside a super-porous hydrogel
(SPH) [196]. Mechanical properties including compressive
strength and elasticity were signicantly improved up to 50-fold
times as compared with a control SPH. The incorporation of the
second polymer network did not decrease the fast swelling of
SPHs due to the initial interconnected pore structure.
3. Separations mediated by IPN hydrogels

3.1. Characterization of sorption properties
To evaluate the sorption capacity for ionic species, the behavior
of various IPN hydrogels in the presence of ionic dyes or heavy metal ions has been evaluated, usually in batch mode. From the determination of the residual concentration of the dye or metal ion as a
function of various parameters, the adsorption or binding capacity,
q, expressed by Eq. (1), and the removal efciency, R, %, expressed
by Eq. (2) can be calculated.
qe
C o C e V
;
W
mg=g
R C o C e =C o 100
1
2
where Co and Ce are the initial and nal concentrations, respectively,

V is the volume of the aqueous phase (L), and W is the amount of the
dried composite gel (g).
The main factors which inuence the sorption process are: pH,
sorbent dosage, temperature and the initial concentration of solute. The interference with other ionic species should be also considered. Sorption mechanism and its potential rate-controlling
steps, which help in the evaluation of the sorbent quality, are
examined by tting various kinetic models on the experimental
data, the most employed being: pseudo-rst-order (PFO) kinetic
model [197], pseudo-second-order (PSO) kinetic model [198], Weber and Morris kinetic model [199], and Elovichs kinetic model
[200,201]. Plotting the sorbed amount of solute on the solid surface
(mg/g) versus the equilibrium concentration of solute in solution
(mg/L), at a constant temperature, gives an experimental isotherm.
The experimental binding isotherms are described by theoretical
isotherms, such as: Langmuir [202], Freundlich [203], Sips or LangmuirFreundlich [204,205], DubininRadushkevich [201], and
Tempkin [206,207].
The thermodynamic parameters of sorption (DGo, DSo and DHo)
are examined by performing sorption experiments at various temperatures [201,205]. The relation between the Langmuir constant,
KL, or the equilibrium constant of adsorption, KC, and the free energy of adsorption (DGo) is given by Eq. (3):
DGoads RT ln K C
Eq. (4) allows evaluating the thermodynamic parameters of the

adsorption process by plotting ln KC versus 1/T, according to the
Vant Hoff equation:
ln K C
DSoads DHoads

R
RT
The feasibility of sorption is indicated by the sign of DGo, the

negative values of DGo indicating the sorption is spontaneous
and thermodynamically favorable. The sign of DHo indicates if
the process is endo- or exothermic and gives information about
the sorption mechanism.
3.2. Sorption of dyes
Water pollution with dyes is becoming a huge environmental
problem due to the large variety of dyes used in textile, paper, plastics, and cosmetic industries, which discharge a large amount of
efuents including dyes. Majority of the dyes are toxic, carcinogenic, and nonbiodegradable. Conventional methods like biological
treatment, coagulation/occulation, chemical precipitation, solvent extraction, membrane ltration, and oxidation, employed
for the dye removal from industrial waste waters, are not always
11
effective. Adsorption is considered an effective and economical

method to remove dyes even at high concentrations, having some
advantages such as exibility in the selection of the adequate sorbent and operation, and the production of efuents suitable to be
reused [20,21,208,209]. Therefore, the interest focused on nding
novel sorbents with high adsorption capacities, fast adsorption/
desorption rate, and easy separation and regeneration strongly increased last decade [210,211]. In this context, multicomponent
hydrogels as semi-IPN or IPN incorporating either synthetic polymers [175,212216] or polymers coming from bioresources
[15,111,112,217222] are gaining more and more interest for
application in the preparation of hydrogel-based sorbents.
Semi-IPN and IPN based on PVA and poly(AA-co-HEMA) with
various compositions were prepared by Mandal et al. and their
sorption capacity for rhodamine B (RB) and methyl violet (MV)
from dilute aqueous solution have been investigated [214]. It
was found that the sorption capacity of both dyes at pH 7 increased
with the increase of the copolymer content in the gel, and the sorption of MV was always higher than that of RB because, beside the
cationic groups, RB contains a carboxylic group, which at pH 7 is
also ionized and repels the similar groups of hydrogel. The dye
adsorption of both dyes was lower on IPN than on semi-IPN, situation attributed to the tighter network structure of the IPN. Such
hydrogels could be effective in the removal of traces of dyes from
water. The inuence of the dye concentration in the feed solution
on the binding mechanism of cationic dyes (MV and basic fuchsin)
on the semi-IPN composed of CMC and P(AAm-co-HEMA) (PAMHEMA) as a matrix has been deeply investigated by Bhattacharyya
and Ray [222]. All the hydrogels showed chemical sorption at
low concentration of the dye, and physical sorption at high concentrations. Solpan et al. prepared SA/PAAm semi-IPN conventional
hydrogels containing 3 wt.% SA entrapped in PAAm matrix, and followed their usability in the removal of some textile dyes [220]. For
all cationic dyes, S type adsorption isotherms were found, the
adsorption capacities at pH 7 and 25 C being in the order:
MV > methylene blue (MB) > Safranine-O > Magenta.
Considerable interest has been lately focused on the macroporous hydrogels, characterized by a faster response rate at small
changes of the external stimuli than the conventional hydrogels.
Ionic multicomponent cryogels, having enhanced mechanical and
chemical resistance, have been tested as novel sorbents in the separation processes of small ionic species and in bioseparations
[14,82,223,224]. Table 1 summarizes some of the recently reported
results on the sorption of dyes, either on conventional IPN hydrogels or on IPN cryogels.
In our research, the sorption of two ionic dyes, the anionic dye
Direct Blue 1 (DB1) and the cationic dye MB on the semi- and full-
IPN hydrogels based on PAAm and CS was investigated on both

conventional hydrogels [15] and cryogels [14]. It was found that
semi-IPN hydrogels preferentially sorbed DB1, owing to the positively charged groups from CS, while the full-IPN sorbed a much
higher amount of MB than semi-IPN, the time required to achieve
the equilibrium sorption of the dye being about 40 min, for both
types of gels. The strong interaction of IPN with cationic dye has
been attributed to the presence of anionic charges, COO. The controlling mechanism of adsorption was investigated by tting three
kinetic models on the experimental data: the PFO kinetic model
[197], the PSO kinetic model [198], and the intra-particle diffusion
model by Weber and Morris [199]. It was found that the theoretical
qe,calc values estimated by PFO kinetic model were very close to the
experimental values, for both semi-IPN and full-IPN, and this supported physisorption as the main controlling mechanism of sorption. Information about the boundary layer diffusion effect were
obtained from the Weber and Morris plots, the highest value of
the diffusion rate constant, Ci, being found for the highest amount
of the dye adsorbed [15]. Fully-IPN PAAm/CS cryogels with a MB
sorption capacity, estimated by tting Sips model, of
755.5 mg MB/g gel have been also prepared [14]. The fully-IPN
cryogels showed excellent properties in separation of MB from
its mixture with methyl orange (MO).
Semi-IPN composite cryogels having PA as entrapped polymer
in a matrix of PAAm, endowed with enhanced sorption of MB from
aqueous solutions, have been recently reported [112,115]. The
sorption capacity has further increased by a controlled hydrolysis
of PAAm matrix, owing to the increase of the density of active
COO groups. The shape of the sorption isotherm changed from
an isotherm of L type, before hydrolysis, to an H type isotherm,
after hydrolysis, which supports a very high afnity of the hydrolyzed composite gel for the cationic dye. The sorption kinetic has
been better described by the PFO kinetic model and this showed
the overall adsorption process appearing to be controlled by physisorption owing to the electrostatic attraction between cationic dye
and COO groups of cryogel.
3.3. Sorption of heavy metal ions
Among the water pollutants, heavy metal ions are considered
the most dangerous due to their non-biodegradability, high toxicity and carcinogenic effects. Various methods have been developed
for removal of heavy metals, based on physical, chemical, electrical, thermal and biological principles. As for the removal of dyes,
adsorption is preferred owing to its wide range of applicability, feasibility and exibility. In this context, a large variety of sorbents
based on the renewable resources have been lately reported in
Table 1
Maximum equilibrium sorption capacity of IPN hydrogels for ionic dyes.
Sorbent
Dye
Sorbent dosage, g/L
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]
12
literature [226230]. The specic applications of IPN hydrogels for

the removal of heavy metal ions are presented in the next
subsections.
3.3.1. IPN hydrogels based on biopolymers
IPN hydrogels based on biopolymers have lately found their deserved place [231239]. Chitosan [235,239], alginate [234,236],
starch [238], cellulose derivatives [232], and other polysaccharides
[233] constitute partners in the preparation of semi- or full-IPN
hydrogels with promising sorption properties for heavy metal ions,
some results being summarized in Table 2.
Chauhan and Mahajan have followed the sorption of metal
ions (Fe2+, Cu2+ and Cr6+) from aqueous solution on semi-IPN
composite hydrogels prepared by the incorporation of cellulose
derivatives in a matrix of poly(methacrylamide) (PMAAm) and
observed that the sorption capacity and the sorption mechanism
of the metal ions were strongly inuenced by the functional
groups of the gel [232]. As can be seen in Table 2, the sorption
capacity of Fe2+ and Cu2+ dramatically increased after the transformation of the amide groups of the matrix into COO groups,
by partial hydrolysis. Before the hydrolysis, the metal ion uptake
was more a sorption process, while after hydrolysis, chelation
and ion exchange are the main driving forces for the metal uptake. On the other side, no sorption of Cr6+ ions was found after
the partial hydrolysis, this being explained by the large size of the
ion in hydrated state. Wang et al. have recently reported preparation of semi-IPN hydrogels composed of CS-g-PAA as a matrix
and GE as entrapped protein with very high sorption capacities
for Pb2+ [235] and Cu2+ [237], the equilibrium of sorption being
attained in about 15 min. The equilibrium adsorption isotherm
was tted by the non-linear form of the Langmuir isotherm,
and the sorption kinetic was well described by the PSO kinetic
model indicating the chemisorption by chelation of metal ions
as the mechanism of sorption. The presence of GE chains enhanced the mechanical strength of semi-IPN composite hydrogels
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 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+
Sorbent dosage, g/L
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]).
theoretical sorption capacity of 40.72 mg Cu2+/g, 19.72 mg Cd2+/g,

9.31 mg Ni2+/g, and 7.48 mg Zn2+/g.
3.3.2. IPN hydrogels based on synthetic polymers
IPN hydrogels based only on the synthetic polymers have been
also evaluated as sorbents for heavy metal ions [11,240243]. In a
semi-IPN hydrogel composed of PEG entrapped in a polyacrylate
(PAC) matrix, the sorption capacity of metal ions, reported by Tong
et al., has been a function of the ratio between PAC and PEG being
maximum at a ratio of 6, because PAC, by the presence of COO
groups, is more effective in coordination of heavy metal ions than
PEG [241]. The maximum sorption capacity found, in optimum
conditions, for Ni2+, Cr3+, and Cd2+ has been: 102.34 mg/g,
49.38 mg/g, and 33.41 mg/g, respectively.
Stimuli-responsive semi-IPN hydrogels composed of PNIPAAm
as matrix and NaPAA as entrapped homopolymer and their sorption properties for Cu2+ have been reported by Yamashita et al.
[242]. The IPN hydrogels exhibited volume-phase transition behavior in the adsorption conditions, i.e. the IPN hydrogel adsorbed sufciently Cu2+ ions below the volume phase transition temperature
(VPTT) but not above the VPTT. Above the VPTT, when the gels collapsed, only water has been released and not metal ions, making
these gels very convenient sorbents for applications in an intelligent recovery system of metal ions.
Wang et al. prepared IPN hydrogels with enhanced adsorption
properties for heavy metal ions either simultaneous, by free radical/cationic photopolymerization of 2-acrylamido-2-methyl-1propansulfonic acid (AMPS) and triethylene glycol divynil ether
(DVE-3) [11], or by the sequential strategy with poly(PEGDA),
and PMAA as the two independent networks [240]. Adsorption
properties of the IPN hydrogels for the removal of Cu(II), Cd(II),
and Pb(II), compared with single networks, have been examined
in batch mode, under non-competitive conditions. The adsorption
capacity of simultaneous IPN hydrogels increased with the increase
of AMPS content in the IPN hydrogel, for all metal ions, the optimum pH being 5 [11]. The adsorption capacity of the sequential
IPN hydrogels increased with the increase of PMAA content in
the IPN hydrogel up to about 35%, the optimum pH being 5
[240]. A synergistic complexation of metal ions with the two polymer chains in sequential IPN was assumed to explain the increase
of the experimental sorption capacity compared with the theoretical sorption capacity calculated taking into account the contribution of each individual network. As Table 2 shows, the sorption
capacity of IPN hydrogels was higher for Pb(II) than for Cu(II)
and Cd(II), due to the smaller atomic radius of Pb(II). The adsorption capacity of the IPN gels increased almost linearly with the increase of the initial concentration of metal ion, the experimental
isotherms being better described by the Freundlich isotherm, suggesting the adsorption was heterogeneous, in multi-layer pattern
[11]. Examination of the sorption mechanism revealed a diffusion
controlled transport mechanism of metal ion sorption on that
IPN hydrogel. In general, the equilibrium of metal ion sorption
has been established within 1015 min, i.e. very fast compared
with the single network hydrogels [11,240,241].
Metal complexing membranes have been prepared by semi-IPN
technique and their sorption properties for Pb2+ [244246], Hg2+,
Cd2+, and Cu2+ [244,245] have been investigated. Thus, Bessbousse
et al. have fabricated composite membranes based on a large variety of complexing polymers, such as poly(ethyleneimine) (PEI),
poly(allylamine), CS, PVPy, poly(vinylimidazole), PVP, entrapped
within a matrix of PVA [244,245]. For the retention of individual
ions, the order of selectivity was: Hg2+ > Cu2+ > Pb2+ > Cd2+. The
highest sorption capacities have been found for Hg2+, on the majority of the composite membranes, an interpretation of the results in
the frame of Hard and Soft Acids and Bases theory being attempted
by the authors [245]. The afnity sequence in binary mixtures has
13
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
14
metal ions from the sequential poly(PEGDA)/PMAA IPN hydrogels,

using dilute HCl as desorption agent, showed that the desorption
ratio was higher than 96%. The reuse of the gels in the second cycle
of sorption showed a sorption capacity of around 93% from the initial capacity for all metal ions, and this support the suitability of
the gels for repeated applications [240]. The adsorption capacity
of semi-IPN hydrogel composed of CS-g-PAA as a matrix and GE
as entrapped polymer for Pb2+ [235] and Cu2+ [237] slightly decreased with increasing the number of consecutive adsorbtion/
desorption cycles, the regeneration and metal ion recovery capabilities being improved by the presence of GE. The thermoresponsive
semi-IPN hydrogels composed of PNIPAAm as matrix and NaPAA as
entrapped homopolymer have been easily recycled using 0.01 N
HCl as desorption agent, in swollen state of the gel (20 C), and
regenerated by alkali treatment (0.1 N NaOH) [242].
In conclusion, the IPN hydrogels are endowed with a high level
of reusability [111,219,222,240,242], which is of great practical
signicance, this being further increased by the synthesis of hydrogels at subzero temperatures [14,115].
4. Summary of the benets of semi-IPN compared to singlenetwork hydrogels, and of the inuence of the second network
on the properties of IPN hydrogels
IPNs, as a particular class of polymer blends, have been developed with the aim to improve at least one property of the constituent networks. The main advantages of IPNs are that
relatively dense hydrogel matrices can be produced, which feature stiffer and tougher mechanical properties, more widely controllable physical properties, and (frequently) more efcient drug
loading compared to single-network hydrogels [4,7,13]. The loading capacity of the CS/PNIPAAm IPN with DS signicantly increased compared to pure PNIPAAm hydrogel, the sharp
thermosensitivity of the PNIPAAm phase being preserved [53].
The diffusion of drugs out of hydrogel matrices has been improved by applying the IPN strategy of synthesis [13]. However,
semi-IPNs can more effectively preserve rapid kinetic response
rates to pH or temperature, the benets of IPNs in controlled
drug delivery (modifying pore size, slowing drug release) being
maintained [13].
The inuence of the second network on the properties of IPN
hydrogels should be correlated with the conditions in which the
generation of the second network occurred. Thus, the SReq and
the time necessary to reach the equilibrium swelling have been
higher in the case of PAAm/CS IPN cryogel compared to the
semi-IPN cryogel, the second network being generated by the CS
cross-linking in alkaline medium, when partial hydrolysis of PAAm
occurred [14]. The increase of the time necessary to reach the
equilibrium swelling has been attributed to the presence of two
oppositely charged networks, and the much higher SReq of IPN
cryogels were explained by the generation of the anionic matrix,
bearing COO groups, during the formation of the second
network.
There are numerous studies focused on the decrease of the
limitations of hydrogels composed of PNIPAAm, such as the lack
of biocompatibility, deswelling rate, and mechanical properties.
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
applications in the design of drug release systems. Both semiIPN [8894,143] and full-IPN [95,96] have been investigated.
Thus, the drug release from semi-IPN hydrogel beads composed
of linear PNIPAAm entrapped in Ca-Alg matrix was higher at
37 C than at 25 C and showed that the Ca-Alg/PNIPAAm beads
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].
5. Conclusions and perspectives

Interpenetrating polymer network hydrogels, as a particular
category of composite materials, received a great attention last
decade owing to their improved responsiveness and mechanical
properties, which differentiate them on the single network hydrogels. Even if the fabrication of IPN hydrogels by the simultaneous
strategy has the advantage to be time- and cost-saving, it was
found that the sequential technique allows a better control of the
properties of the gels compared to the simultaneous strategy.
The limitations of hydrogels composed of PNIPAAm, such as the
lack of biocompatibility, slow deswelling rate, and poor mechanical
properties have been reduced either by incorporating PNIPAAm
linear chains in a matrix of Alg or by entrapping polysaccharides
(CS, Alg) or proteins in a network of PNIPAAm. The pulsatile
deswelling/reswelling behavior and the loading/release of drugs
have been mainly improved by the preparation of semi-IPN
hydrogels.
It was demonstrated that IPN hydrogels are endowed with very
fast kinetics for sorption of ionic species like dyes and heavy metal
ions compared with the single network hydrogels. Mechanical
properties, swelling kinetics, and reusability of IPN hydrogels in
their applications as sorbents have been further improved by conducting the synthesis of the gels under the freezing temperature of
the solvent. Ionic IPN cryogels based on synthetic polymers and
biopolymers, like CS and starch, are endowed with very fast swelling rate, a high sorption capacity for ionic species like dyes and
heavy metal ions, fast kinetics of sorption, and a high level of reusability, features which recommend them as promising sorbents in
the future. Even if it is still a challenging task, the synthesis of ion
imprinted IPN hydrogels constitutes a promising direction in
increasing the selectivity of this novel type of sorbents, which is
expected to receive much attention in the future.
[13]
[14]
[15]
[16]
[17]
[18]
[19]
[20]
[21]
[22]
[23]
[24]
[25]
[26]
[27]
Acknowledgement
[28]
This work was supported by CNCSIS-UEFISCSU by the project

PN-II-ID-PCE-2011-3-0300.
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Interpretación de Polimeros

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Chemical Engineering Journal xxx (2014) xxxxxx

Contents lists available at ScienceDirect

Chemical Engineering Journal

Design and applications of interpenetrating polymer network hydrogels.

E.S. Dragan / Chemical Engineering Journal xxx (2014) xxxxxx

and activator, with or without a cross-linker (Fig. 1b). If a cross-linker

2. Design, characterization, and biomedical applications of IPN

E.S. Dragan / Chemical Engineering Journal xxx (2014) xxxxxx

2.1. Polysaccharide based IPN hydrogels

Fig. 2. Possible combinations of hydrophilic polymers used to prepare IPN

reported [23], the schematic representation of their formation

E.S. Dragan / Chemical Engineering Journal xxx (2014) xxxxxx

The semi-IPN and IPN hydrogels were characterized by FTIR,

E.S. Dragan / Chemical Engineering Journal xxx (2014) xxxxxx

presence of CS, under freezing conditions, the main parameters

E.S. Dragan / Chemical Engineering Journal xxx (2014) xxxxxx

proach for the synthesis of semi-IPN SA/PNIPAAm hydrogels with

E.S. Dragan / Chemical Engineering Journal xxx (2014) xxxxxx

water insoluble, containing two major components: (1) amylose,

equation of Frenson and Peppas [116], swelling being controlled by

E.S. Dragan / Chemical Engineering Journal xxx (2014) xxxxxx

2.1.4. Other polysaccharides

E.S. Dragan / Chemical Engineering Journal xxx (2014) xxxxxx

temperature of 18 C) than in the case of conventional hydrogels

considered as candidate for biomaterials owing to its good

2.3. IPN hydrogels based only on synthetic polymers

E.S. Dragan / Chemical Engineering Journal xxx (2014) xxxxxx

IPN hydrogels based on nonionic synthetic polymers, where

3. Separations mediated by IPN hydrogels

where Co and Ce are the initial and nal concentrations, respectively,

Eq. (4) allows evaluating the thermodynamic parameters of the

The feasibility of sorption is indicated by the sign of DGo, the

E.S. Dragan / Chemical Engineering Journal xxx (2014) xxxxxx

effective. Adsorption is considered an effective and economical

IPN hydrogels based on PAAm and CS was investigated on both

Sorbent dosage, g/L

E.S. Dragan / Chemical Engineering Journal xxx (2014) xxxxxx

literature [226230]. The specic applications of IPN hydrogels for

Sorbent dosage, g/L

E.S. Dragan / Chemical Engineering Journal xxx (2014) xxxxxx

theoretical sorption capacity of 40.72 mg Cu2+/g, 19.72 mg Cd2+/g,

E.S. Dragan / Chemical Engineering Journal xxx (2014) xxxxxx

metal ions from the sequential poly(PEGDA)/PMAA IPN hydrogels,

E.S. Dragan / Chemical Engineering Journal xxx (2014) xxxxxx

5. Conclusions and perspectives

This work was supported by CNCSIS-UEFISCSU by the project

containing pH-sensitive and hydrolytically cleavable IPN hydrogels,

E.S. Dragan / Chemical Engineering Journal xxx (2014) xxxxxx

[67] N.V. Gupta, H.G. Shivakumar, Interpenetrating network superporous

E.S. Dragan / Chemical Engineering Journal xxx (2014) xxxxxx

[120] G. Buhus, M. Popa, C. Peptu, J. Desbrieres, Hydrogels based on

E.S. Dragan / Chemical Engineering Journal xxx (2014) xxxxxx

E.S. Dragan / Chemical Engineering Journal xxx (2014) xxxxxx

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