Design and applications of interpenetrating polymer network hydrogels. A review

Abstract 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 first 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 influence of the second network on the stimuli responsiveness of the “smart” IPN hydrogels is discussed based on the most recent publications in the field. In the second part, an overview of the most specific 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.

[1]  T. Aminabhavi,et al.  Interpenetrating polymer network blend microspheres of chitosan and hydroxyethyl cellulose for controlled release of isoniazid. , 2010, International journal of biological macromolecules.

[2]  T. Miyata,et al.  Rapid response of a poly(acrylamide) hydrogel having a semi‐interpenetrating polymer network structure , 2006 .

[3]  T. Tan,et al.  Salt-, pH- and temperature-responsive semi-interpenetrating polymer network hydrogel based on poly(aspartic acid) and poly(acrylic acid) , 2006 .

[4]  Aiqin Wang,et al.  One-step in situ fabrication of a granular semi-IPN hydrogel based on chitosan and gelatin for fast and efficient adsorption of Cu2+ ion. , 2013, Colloids and surfaces. B, Biointerfaces.

[5]  A. Bajpai,et al.  Preparation and characterization of tetracycline‐loaded interpenetrating polymer networks of carboxymethyl cellulose and poly(acrylic acid): water sorption and drug release study , 2005 .

[6]  Kinam Park,et al.  Swelling and mechanical properties of superporous hydrogels of poly(acrylamide-co-acrylic acid)/polyethylenimine interpenetrating polymer networks , 2004 .

[7]  T. Aminabhavi,et al.  Novel chitosan-based pH-sensitive interpenetrating network microgels for the controlled release of cefadroxil ☆ , 2006 .

[8]  J. Romero‐García,et al.  Synthesis and swelling characteristics of semi-interpenetrating polymer network hydrogels composed of poly(acrylamide) and poly(γ-glutamic acid) , 2006 .

[9]  A. F. Rubira,et al.  Hydrogels based on PAAm network with PNIPAAm included: hydrophilic–hydrophobic transition measured by the partition of Orange II and Methylene Blue in water , 2003 .

[10]  Seon Jeong Kim,et al.  Bending behavior of hydrogels composed of poly(methacrylic acid) and alginate by electrical stimulus , 2004 .

[11]  M. Dinu,et al.  Preparation and characterization of IPN composite hydrogels based on polyacrylamide and chitosan and their interaction with ionic dyes , 2012 .

[12]  S. Sivanesan,et al.  Equilibrium data, isotherm parameters and process design for partial and complete isotherm of methylene blue onto activated carbon. , 2006, Journal of hazardous materials.

[13]  Xiaohong Cao,et al.  Selective adsorption of uranyl ion on ion-imprinted chitosan/PVA cross-linked hydrogel , 2010 .

[14]  Jing Jing Wang,et al.  UV-curing of simultaneous interpenetrating network silicone hydrogels with hydrophilic surface , 2012, Polymer Bulletin.

[15]  Christine E Schmidt,et al.  Photopatterned collagen-hyaluronic acid interpenetrating polymer network hydrogels. , 2009, Acta biomaterialia.

[16]  Lichen Yin,et al.  Synthesis, characterization, mechanical properties and biocompatibility of interpenetrating polymer network–super‐porous hydrogel containing sodium alginate , 2007 .

[17]  M. Bercea,et al.  Semi-interpenetrated polymer networks of hyaluronic acid modified with poly(aspartic acid) , 2013, Journal of Polymer Research.

[18]  L. Poole-Warren,et al.  Silk fibroin/poly(vinyl alcohol) photocrosslinked hydrogels for delivery of macromolecular drugs. , 2012, Acta biomaterialia.

[19]  T. Aminabhavi,et al.  Preparation and in-vitro release of chlorothiazide novel pH-sensitive chitosan-N,N′-dimethylacrylamide semi-interpenetrating network microspheres ☆ , 2008 .

[20]  Lei Chen,et al.  Porous silicone hydrogel interpenetrating polymer networks prepared using a template method for biomedical use , 2011 .

[21]  A. Bajpai Blood protein adsorption onto macroporous semi-interpenetrating polymer networks (IPNs) of poly(ethylene glycol) (PEG) and poly(2-hydroxyethyl methacrylate) (PHEMA) and assessment of in vitro blood compatibility , 2007 .

[22]  Qiang Zhao,et al.  Study of the properties of hydrolyzed polyacrylamide hydrogels with various pore structures and rapid pH-sensitivities , 2010 .

[23]  Mitsuru Higa,et al.  Charge mosaic membranes with semi-interpenetrating network structures prepared from a polymer blend of poly(vinyl alcohol) and polyelectrolytes , 2013 .

[24]  E. Guibal,et al.  Interactions of metal ions with chitosan-based sorbents: a review , 2004 .

[25]  C. Wandrey,et al.  Alginate-Poly(ethylene glycol) Hybrid Microspheres with Adjustable Physical Properties , 2010 .

[26]  Shengfang Li Removal of crystal violet from aqueous solution by sorption into semi-interpenetrated networks hydrogels constituted of poly(acrylic acid-acrylamide-methacrylate) and amylose. , 2010, Bioresource technology.

[27]  M. Akashi,et al.  Novel polyion complex with interpenetrating polymer network of poly(acrylic acid) and partially protected poly(vinylamine) using N-vinylacetamide and N-vinylformamide , 2009 .

[28]  Klaus D. Jandt,et al.  Temperature-sensitive PVA/PNIPAAm semi-IPN hydrogels with enhanced responsive properties. , 2009, Acta biomaterialia.

[29]  Aiqin Wang,et al.  Preparation and characterization of a novel pH-sensitive chitosan-g-poly (acrylic acid)/attapulgite/sodium alginate composite hydrogel bead for controlled release of diclofenac sodium , 2009 .

[30]  M. Dinu,et al.  Preparation and characterization of novel composites based on chitosan and clinoptilolite with enhanced adsorption properties for Cu2+. , 2010, Bioresource technology.

[31]  Li Wang,et al.  Synthesis and characterization of pH‐ and temperature‐sensitive silk sericin/poly(N‐isopropylacrylamide) interpenetrating polymer networks , 2006 .

[32]  G. Bowlin,et al.  Semi-interpenetrating network (sIPN) gelatin nanofiber scaffolds for oral mucosal drug delivery. , 2013, Acta biomaterialia.

[33]  Wenhui Wu,et al.  Synthesis and properties of thermo-responsive guar gum/poly(N-isopropylacrylamide) interpenetrating polymer network hydrogels , 2008 .

[34]  Zhiliang Wang,et al.  Studies on chitosan and poly(acrylic acid) interpolymer complex. I. Preparation, structure, pH‐sensitivity, and salt sensitivity of complex‐forming poly(acrylic acid): Chitosan semi‐interpenetrating polymer network , 1997 .

[35]  Mingzhu Liu,et al.  Synthesis and properties of thermo- and pH-sensitive poly(diallyldimethylammonium chloride)/poly(N,N-diethylacrylamide) semi-IPN hydrogel , 2010 .

[36]  Florica Doroftei,et al.  Macroporous composite IPN hydrogels based on poly(acrylamide) and chitosan with tuned swelling and sorption of cationic dyes , 2012 .

[37]  Ping Zhu,et al.  Preparation and characterization of IPN hydrogels composed of chitosan and gelatin cross-linked by genipin. , 2014, Carbohydrate polymers.

[38]  Biman B Mandal,et al.  Silk fibroin/polyacrylamide semi-interpenetrating network hydrogels for controlled drug release. , 2009, Biomaterials.

[39]  S. Ali,et al.  Synthesis of copolymeric acrylamide/potassium acrylate hydrogels blended with poly(vinyl alcohol): Effect of crosslinking and the amount of poly(vinyl alcohol) on swelling behavior , 2005 .

[40]  Su Ryon Shin,et al.  Swelling characterizations of chitosan and polyacrylonitrile semi‐interpenetrating polymer network hydrogels , 2003 .

[41]  Pierre-Emile Duhamel,et al.  Progress in the development of interpenetrating polymer network hydrogels. , 2008, Polymers for advanced technologies.

[42]  A. Tsatsakis,et al.  Macroporous polymeric hydrogels formed from acrylate modified polyvinyl alcohol macromers , 2011 .

[43]  L. Mattoso,et al.  Synthesis and characterization of a starch‐modified hydrogel as potential carrier for drug delivery system , 2008 .

[44]  N. Manolova,et al.  pH-Sensitive Hydrogels Composed of Chitosan and Polyacrylamide – Preparation and Properties , 2004 .

[45]  T. Tan,et al.  Synthesis and properties of thermo- and pH-sensitive poly(N-isopropylacrylamide)/polyaspartic acid IPN hydrogels , 2012 .

[46]  M. Kurisawa,et al.  Formation and stability of interpenetrating polymer network hydrogels consisting of fibrin and hyaluronic acid for tissue engineering. , 2013, Acta biomaterialia.

[47]  S. Kundakcı Investigation of Swelling/Sorption Characteristics of Highly Swollen AAm/AMPS Hydrogels and Semi IPNs with PEG as Biopotential Sorbent , 2011 .

[48]  S. Sajeesh,et al.  Interpolymer complex microparticles based on polymethacrylic acid‐chitosan for oral insulin delivery , 2006 .

[49]  E. K. Park,et al.  Preparation of alginate/poly(N‐isopropylacrylamide) semi‐interpenetrating and fully interpenetrating polymer network hydrogels with γ‐ray irradiation and their swelling behaviors , 2006 .

[50]  D. Apopei,et al.  Synthesis and swelling behavior of pH-sensitive semi-interpenetrating polymer network composite hydrogels based on native and modified potatoes starch as potential sorbent for cationic dyes , 2011 .

[51]  Yingde Cui,et al.  Preparation and properties of temperature‐sensitive soy protein/poly(N‐isopropylacrylamide) interpenetrating polymer network hydrogels , 2011 .

[52]  S. I. Kim,et al.  Electrical/pH responsive properties of poly(2‐acrylamido‐2‐methylpropane sulfonic acid)/hyaluronic acid hydrogels , 2004 .

[53]  P. Badot,et al.  Application of chitosan, a natural aminopolysaccharide, for dye removal from aqueous solutions by adsorption processes using batch studies: A review of recent literature , 2008 .

[54]  E. Solak Preparation and Characterization of IPN Microspheres for Controlled Delivery of Naproxen , 2011 .

[55]  Xiangke Wang,et al.  Sorption of Heavy Metal Ions from Aqueous Solutions: A Review , 2011 .

[56]  Jide Wang,et al.  Structure and characterization of amphoteric semi-IPN hydrogel based on cationic starch , 2009 .

[57]  Seon Jeong Kim,et al.  Synthesis and characteristics of Semi-interpenetrating polymer network hydrogels based on chitosan and poly(hydroxy ethyl methacrylate) , 2005 .

[58]  G. Güçlü,et al.  Study on a novel polyampholyte nanocomposite superabsorbent hydrogels: Synthesis, characterization and investigation of removal of indigo carmine from aqueous solution , 2011 .

[59]  T. Aminabhavi,et al.  Semi-interpenetrating polymer network microspheres of gelatin and sodium carboxymethyl cellulose for controlled release of ketorolac tromethamine , 2006 .

[60]  Anil Kumar Bajpai,et al.  Responsive polymers in controlled drug delivery , 2008 .

[61]  J. Ong,et al.  The effect of cross-linking of chitosan microspheres with genipin on protein release , 2007 .

[62]  T. Kurokawa,et al.  Super tough double network hydrogels and their application as biomaterials , 2012 .

[63]  T. Tan,et al.  Swelling kinetics of poly(aspartic acid)/poly(acrylic acid) semi-interpenetrating polymer network hydrogels in urea solutions , 2010 .

[64]  D. Tuncaboylu,et al.  Tough interpenetrating Pluronic F127/polyacrylic acid hydrogels , 2013 .

[65]  Yu Fang,et al.  Preparation and properties of chitosan-poly(N-isopropylacrylamide) full-IPN hydrogels , 2001 .

[66]  A. M. Dave,et al.  Novel route to synthesis of allyl starch and biodegradable hydrogel by copolymerizing allyl-modified starch with methacrylic acid and acrylamide , 2003 .

[67]  Loo-Teck Ng,et al.  IPNs based on chitosan with NVP and NVP/HEMA synthesised through photoinitiator-free photopolymerisation technique for biomedical applications , 2005 .

[68]  J. Cauich‐Rodríguez,et al.  Interpenetrated Chitosan-Poly(Acrylic Acid-Co-Acrylamide) Hydrogels. Synthesis, Characterization and Sustained Protein Release Studies , 2011 .

[69]  Li Fei-fei Application of Chitosan , 2010 .

[70]  Yong‐Ill Lee,et al.  Development of semi-interpenetrating carbohydrate polymeric hydrogels embedded silver nanoparticles and its facile studies on E. coli , 2010 .

[71]  N. Peppas,et al.  Morphology of poly(methacrylic acid)/poly(N-isopropyl acrylamide) interpenetrating polymeric networks , 2002, Journal of biomaterials science. Polymer edition.

[72]  M. Pulat,et al.  Fluconazole release through semi-interpenetrating polymer network hydrogels based on chitosan, acrylic acid, and citraconic acid , 2009 .

[73]  J. Stejskal,et al.  Phase transition in swollen gels. 6. Effect of aging on the extent of hydrolysis of aqueous polyacrylamide solutions and on the collapse of gels , 1984 .

[74]  Jens Lienig,et al.  Review on Hydrogel-based pH Sensors and Microsensors , 2008, Sensors.

[75]  T. Guo,et al.  Hemoglobin recognition by imprinting in semi-interpenetrating polymer network hydrogel based on polyacrylamide and chitosan. , 2005, Biomacromolecules.

[76]  Wanzhi. Wei,et al.  Direct electrochemistry and electrocatalysis of hemoglobin entrapped in semi-interpenetrating polymer network hydrogel based on polyacrylamide and chitosan. , 2007, Bioelectrochemistry.

[77]  Danying Zuo,et al.  Removal of anionic dyes from aqueous solutions by adsorption of chitosan-based semi-IPN hydrogel composites , 2012 .

[78]  P. Colombo,et al.  Preparation and characterization of chitosan based micro networks: Transposition to a prilling process , 2004 .

[79]  Aiqin Wang,et al.  Efficient Adsorption and Recovery of Pb(II) from Aqueous Solution by a Granular pH-Sensitive Chitosan-based Semi-IPN Hydrogel , 2012 .

[80]  L. Lebrun,et al.  Removal of heavy metal ions from aqueous solutions by filtration with a novel complexing membrane containing poly(ethyleneimine) in a poly(vinyl alcohol) matrix , 2008 .

[81]  Aiqin Wang,et al.  Preparation and swelling properties of semi‐IPN hydrogels based on chitosan‐g‐poly(acrylic acid) and phosphorylated polyvinyl alcohol , 2009 .

[82]  Megat Ahmad Kamal Megat Hanafiah,et al.  Adsorption of dyes and heavy metal ions by chitosan composites: A review , 2011 .

[83]  E. Kokufuta,et al.  Polyampholyte gels of a cross-linked polyanion or polycation network into which an oppositely charged polyion was immobilized , 2013, Colloid and Polymer Science.

[84]  W. Weber,et al.  Kinetics of Adsorption on Carbon from Solution , 1963 .

[85]  Seon Jeong Kim,et al.  Synthesis and characteristics of interpenetrating polymer network hydrogels composed of alginate and poly(diallydimethylammonium chloride) , 2004 .

[86]  M. Dinu,et al.  Porous Semi-Interpenetrating Hydrogel Networks Based on Dextran and Polyacrylamide With Superfast Responsiveness , 2011 .

[87]  Dong-sheng Wang,et al.  A fast pH-responsive IPN hydrogel: Synthesis and controlled drug delivery , 2010 .

[88]  Aiqin Wang,et al.  Synthesis and swelling properties of pH-sensitive semi-IPN superabsorbent hydrogels based on sodium alginate-g-poly(sodium acrylate) and polyvinylpyrrolidone , 2010 .

[89]  Dursun Saraydın,et al.  Synthesis, Characterization and Evaluation of IPN Hydrogels for Antibiotic Release , 2004, Drug delivery.

[90]  Henry T. Peng,et al.  Hydrogel-elastomer composite biomaterials: 3. Effects of gelatin molecular weight and type on the preparation and physical properties of interpenetrating polymer networks , 2008, Journal of materials science. Materials in medicine.

[91]  K. Yam,et al.  Preparation of single or double-network chitosan/poly(vinyl alcohol) gel films through selectively cross-linking method , 2009 .

[92]  A. Hardikar,et al.  pH-sensitive freeze-dried chitosan-polyvinyl pyrrolidone hydrogels as controlled release system for antibiotic delivery. , 2000, Journal of controlled release : official journal of the Controlled Release Society.

[93]  I. D. Mall,et al.  Adsorptive removal of phenol by bagasse fly ash and activated carbon: Equilibrium, kinetics and thermodynamics , 2006 .

[94]  A. Hill,et al.  Sequential homo-interpenetrating polymer networks of poly(2-hydroxyethyl methacrylate): Synthesis, characterization, and calcium uptake , 2012 .

[95]  Zheng Wang,et al.  pH-sensitive interpenetrating network hydrogels based on chitosan derivatives and alginate for oral drug delivery. , 2013, Carbohydrate polymers.

[96]  M. Dinu,et al.  Comparative rheological study of ionic semi-IPN composite hydrogels based on polyacrylamide and dextran sulphate and of polyacrylamide hydrogels , 2012, Colloid and Polymer Science.

[97]  C. Mijangos,et al.  Poly(vinyl alcohol)–poly(acrylic acid) interpenetrating networks. Study on phase separation and molecular motions , 2005 .

[98]  A. Pourjavadi,et al.  Semi‐IPN carrageenan‐based nanocomposite hydrogels: Synthesis and swelling behavior , 2010 .

[99]  I. Langmuir THE ADSORPTION OF GASES ON PLANE SURFACES OF GLASS, MICA AND PLATINUM. , 1918 .

[100]  J. Mano,et al.  Drug release of pH/temperature-responsive calcium alginate/poly(N-isopropylacrylamide) semi-IPN beads. , 2006, Macromolecular bioscience.

[101]  Q. Tang,et al.  Synthesis of polyacrylate/polyethylene glycol interpenetrating network hydrogel and its sorption of heavy-metal ions , 2009, Science and technology of advanced materials.

[102]  Usman Sorathia,et al.  Interpenetrating Polymer Networks: An Overview , 1990 .

[103]  J. Romero‐García,et al.  Synthesis and swelling properties of pH- and temperature-sensitive interpenetrating polymer networks composed of polyacrylamide and poly(γ-glutamic acid) , 2011 .

[104]  Riccardo A.A. Muzzarelli,et al.  Genipin-crosslinked chitosan hydrogels as biomedical and pharmaceutical aids , 2009 .

[105]  Aiqin Wang,et al.  pH-responsive carboxymethylcellulose-g-poly(sodium acrylate)/polyvinylpyrrolidone semi-IPN hydrogels with enhanced responsive and swelling properties , 2011 .

[106]  E. Drăgan,et al.  Enhanced sorption of methylene blue from aqueous solutions by semi-IPN composite cryogels with anionically modified potato starch entrapped in PAAm matrix , 2013 .

[107]  J. Sreeramulu,et al.  Semi-IPNs of starch and poly(acrylamide-co-sodium methacrylate): Preparation, swelling and diffusion characteristics evaluation , 2006 .

[108]  G. Chauhan,et al.  Study on the synthesis, characterization, and sorption of some metal ions on gelatin- and acrylamide-based hydrogels , 2003 .

[109]  Boonsri Kusuktham Preparation of interpenetrating polymer network gel beads for dye absorption , 2006 .

[110]  B. Ji,et al.  Mechanical properties of semi-interpenetrating polymer network hydrogels based on poly(2-hydroxyethyl methacrylate) copolymer and chitosan , 2008 .

[111]  B. Sreedhar,et al.  Hydrogel–silver nanoparticle composites: A new generation of antimicrobials† , 2010 .

[112]  In Young Kim,et al.  Swelling characterization of the semiinterpenetrating polymer network hydrogels composed of chitosan and poly(diallyldimethylammonium chloride) , 2004 .

[113]  Sang Jun Park,et al.  Synthesis and characteristics of the interpenetrating polymer network hydrogel composed of chitosan and polyallylamine , 2002 .

[114]  Yingde Cui,et al.  Thermosensitive soy protein/poly(n-isopropylacrylamide) interpenetrating polymer network hydrogels for drug controlled release , 2011 .

[115]  Investigation of thermo-responsive optical properties of a composite hydrogel , 2010 .

[116]  Mingzhu Liu,et al.  Preparation, properties, and drug release of thermo- and pH-sensitive poly((2-dimethylamino)ethyl methacrylate)/poly(N,N-diethylacrylamide) semi-IPN hydrogels , 2011 .

[117]  Xiaoyun Liu,et al.  Study of pH/temperature dual stimuli‐responsive nanogels with interpenetrating polymer network structure , 2012 .

[118]  Q. Nguyen,et al.  Fabrication of ion-exchange ultrafiltration membranes for water treatment: I. Semi-interpenetrating polymer networks of polysulfone and poly(acrylic acid) , 2006 .

[119]  N. Muangsin,et al.  Chitosan/Polyethylene Glycol Beads Crosslinked with Tripolyphosphate and Glutaraldehyde for Gastrointestinal Drug Delivery , 2010, AAPS PharmSciTech.

[120]  C. Vasile,et al.  Kinetics of Swelling and Drug Release from PNIPAAm/Alginate Stimuli Responsive Hydrogels , 2009 .

[121]  Mingzhu Liu,et al.  A novel triple-responsive poly(3-acrylamidephenylboronic acid-co-2-(dimethylamino) ethyl methacrylate)/(β-cyclodextrin-epichlorohydrin)hydrogels: Synthesis and controlled drug delivery , 2011 .

[122]  Wenbo Li,et al.  A novel multi-responsive polyampholyte composite hydrogel with excellent mechanical strength and rapid shrinking rate. , 2010, Journal of colloid and interface science.

[123]  Mingzhu Liu,et al.  Synthesis and swelling properties of pH-sensitive hydrogels based on chitosan and poly(methacrylic acid) semi-interpenetrating polymer network , 2005 .

[124]  D. Kohane,et al.  HYDROGELS IN DRUG DELIVERY: PROGRESS AND CHALLENGES , 2008 .

[125]  Baolin Guo,et al.  Preparation and release profiles of pH/temperature-responsive carboxymethyl chitosan/P(2-(dimethylamino) ethyl methacrylate) semi-IPN amphoteric hydrogel , 2007 .

[126]  L. Lebrun,et al.  Characterisation of metal-complexing membranes prepared by the semi-interpenetrating polymer networks technique. Application to the removal of heavy metal ions from aqueous solutions , 2012 .

[127]  Mingzhu Liu,et al.  Synthesis and characterization of thermo- and pH-sensitive kappa-carrageenan-g-poly(methacrylic acid)/poly(N,N-diethylacrylamide) semi-IPN hydrogel , 2009 .

[128]  O. Fichet,et al.  Fibrin-polyethylene oxide interpenetrating polymer networks: new self-supported biomaterials combining the properties of both protein gel and synthetic polymer. , 2011, Acta biomaterialia.

[129]  Seon Jeong Kim,et al.  Electromechanical properties of hydrogels based on chitosan and poly(hydroxyethyl methacrylate) in NaCl solution , 2004 .

[130]  M. Dinu,et al.  Sorption Isotherms of Heavy Metal Ions onto Semi-Interpenetrating Polymer Network Cryogels Based on Polyacrylamide and Anionically Modified Potato Starch , 2012 .

[131]  Allan S Hoffman,et al.  Hydrogels for biomedical applications. , 2002, Advanced drug delivery reviews.

[132]  Ö. Üzüm,et al.  Water and dye sorption studies of novel semi IPNs: Acrylamide/4‐styrenesulfonic acid sodium salt/peg hydrogels , 2013 .

[133]  S. I. Kim,et al.  Characterization of the water state of hyaluronic acid and poly(vinyl alcohol) interpenetrating polymer networks , 2004 .

[134]  G. Bayramoglu,et al.  Adsorption kinetics and thermodynamic parameters of cationic dyes from aqueous solutions by using a new strong cation-exchange resin. , 2009 .

[135]  Y. Ho Review of second-order models for adsorption systems. , 2006, Journal of hazardous materials.

[136]  Wim E Hennink,et al.  In situ forming IPN hydrogels of calcium alginate and dextran-HEMA for biomedical applications. , 2011, Acta biomaterialia.

[137]  Hyun-chul Lee,et al.  Preparation of semi-interpenetrating polymer networks composed of chitosan and poloxamer. , 2006, International journal of biological macromolecules.

[138]  Q. Tang,et al.  A multifunctional hydrogel with high conductivity, pH-responsive, thermo-responsive and release properties from polyacrylate/polyaniline hybrid , 2008 .

[139]  Yongkang Gao,et al.  Preparation of fast pH-responsive ferric carboxymethylcellulose/poly(vinyl alcohol) double-network microparticles , 2009 .

[140]  S. Ray,et al.  Synthesis of full and semi Interpenetrating hydrogel from polyvinyl alcohol and poly (acrylic acid-co-hydroxyethylmethacrylate) copolymer: Study of swelling behavior, network parameters, and dye uptake properties , 2012 .

[141]  U. Wichai,et al.  Semi-interpenetrating polymer network hydrogels between polydimethylsiloxane/polyethylene glycol and chitosan , 2010 .

[142]  Murat Torun,et al.  The usability of (sodium alginate/acrylamide) semi‐interpenetrating polymer networks on removal of some textile dyes , 2008 .

[143]  E. A. Sosnov,et al.  New silicone hydrogels based on interpenetrating polymer networks comprising polysiloxane and poly(vinyl alcohol) networks , 2009 .

[144]  K. Br,et al.  Current status of DNA vaccines in veterinary medicine. , 2000 .

[145]  Xiamei Zhong,et al.  Fabrication of interpenetrating polymer network to enhance the biological activity of synthetic hydrogels , 2013 .

[146]  G. Chauhan,et al.  Use of novel hydrogels based on modified cellulosics and methacrylamide for separation of metal ions from water systems , 2002 .

[147]  Aiqin Wang,et al.  One-step fabrication in aqueous solution of a granular alginate-based hydrogel for fast and efficient removal of heavy metal ions , 2013, Journal of Polymer Research.

[148]  Lichen Yin,et al.  Superporous hydrogels containing poly(acrylic acid-co-acrylamide)/O-carboxymethyl chitosan interpenetrating polymer networks. , 2007, Biomaterials.

[149]  J. Desbrières,et al.  Hydrogels based on carboxymethylcellulose and poly (vinyl alcohol) for controlled loading and release of chloramphenicol , 2007 .

[150]  Ashveen Nand,et al.  Temperature and pH sensitive hydrogels composed of chitosan and poly(ethylene glycol) , 2008 .

[151]  Geoffrey R. Mitchell,et al.  Multi-responsive hydrogels based on N-isopropylacrylamide and sodium alginate , 2011 .

[152]  J. Sreeramulu,et al.  Swelling behavior of semi‐interpenetrating polymer network hydrogels composed of poly(vinyl alcohol) and poly(acrylamide‐co‐sodium methacrylate) , 2005 .

[153]  M. Ilavský,et al.  Phase transition in swollen gels , 1982 .

[154]  Charles W. Peak,et al.  A review on tough and sticky hydrogels , 2013, Colloid and Polymer Science.

[155]  M. Dinu,et al.  Sorption of Methylene Blue onto Ionic Composite Hydrogels Based on Polyacrylamide and Dextran Sulfate: Kinetics, Isotherms, and Thermodynamics , 2012 .

[156]  W. Jo,et al.  Synthesis and physical properties of pH-sensitive semi-IPN hydrogels based on poly(dimethylaminoethyl methacrylate-co-PEG dimethacrylate) and poly(acrylic acid) , 2006 .

[157]  M. Dinu,et al.  Adsorption characteristics of UO(2)(2+) and Th(4+) ions from simulated radioactive solutions onto chitosan/clinoptilolite sorbents. , 2011, Journal of hazardous materials.

[158]  Feipeng Wu,et al.  pH switching on-off semi-IPN hydrogel based on cross-linked poly (acrylamide -co -acrylic acid) and linear polyallyamine , 2005 .

[159]  S. Ray,et al.  Kinetic and equilibrium modeling for adsorption of textile dyes in aqueous solutions by carboxymethyl cellulose/poly(acrylamide-co-hydroxyethyl methacrylate) semi-interpenetrating network hydrogel , 2013 .

[160]  J. Filipović,et al.  Antimicrobial P(HEMA/IA)/PVP semi-interpenetrating network hydrogels , 2013, Polymer Bulletin.

[161]  M. Karlsson,et al.  Pore structure in supermacroporous polyacrylamide based cryogels. , 2005, Soft matter.

[162]  Lichen Yin,et al.  Polymer–protein interaction, water retention, and biocompatibility of a stimuli‐sensitive superporous hydrogel containing interpenetrating polymer networks , 2008 .

[163]  Anuj Tripathi,et al.  Multi-featured macroporous agarose-alginate cryogel: synthesis and characterization for bioengineering applications. , 2011, Macromolecular bioscience.

[164]  S. Ray,et al.  Synthesis, characterization, swelling and drug release behavior of semi-interpenetrating network hydrogels of sodium alginate and polyacrylamide. , 2014, Carbohydrate polymers.

[165]  Qingchun Zhao,et al.  Polyacrylonitrile/Silica Nanospheres with Three- Dimensional Interpenetrating Network Structure and Their Application for Removal of Pb(II) from Water , 2012 .

[166]  A. Gonzalez-Alvarez,et al.  Swelling characterization and drug delivery kinetics of polyacrylamide-co-itaconic acid/chitosan hydrogels , 2009 .

[167]  T. Kurokawa,et al.  Double‐Network Hydrogels with Extremely High Mechanical Strength , 2003 .

[168]  M. Dinu,et al.  Evaluation of Cu2+, Co2+ and Ni2+ ions removal from aqueous solution using a novel chitosan/clinoptilolite composite: Kinetics and isotherms , 2010 .

[169]  Jinghong Ma,et al.  Preparation and characterization of pH‐ and temperature‐responsive semi–interpenetrating polymer network hydrogels based on linear sodium alginate and crosslinked poly(N‐isopropylacrylamide) , 2005 .

[170]  Seon Jeong Kim,et al.  Synthesis and characteristics of interpenetrating polymer network hydrogel composed of chitosan and poly(acrylic acid) , 1999 .

[171]  A. Takahara,et al.  Simultaneous and sequential micro-porous semi-interpenetrating polymer network hydrogel films for drug delivery and wound dressing applications , 2009 .

[172]  M. Rosa,et al.  Semi-interpenetrated Hydrogels Composed of PVA and Hyaluronan or Chondroitin Sulphate: Chemico-Physical and Biological Characterization , 2012 .

[173]  J. Desbrières,et al.  Thermodynamic investigation of thermoresponsive xanthan-poly (N-isopropylacrylamide) hydrogels , 2011 .

[174]  T. Aminabhavi,et al.  Temperature sensitive semi‐IPN microspheres from sodium alginate and N‐isopropylacrylamide for controlled release of 5‐fluorouracil , 2008 .

[175]  T. Aminabhavi,et al.  Synthesis and characterization of semi-interpenetrating polymer network microspheres of acrylamide grafted dextran and chitosan for controlled release of acyclovir , 2007 .

[176]  K. Y. Foo,et al.  Insights into the modeling of adsorption isotherm systems , 2010 .

[177]  André Margaillan,et al.  Recent advances on ion-imprinted polymers , 2013 .

[178]  G. Limousin,et al.  Sorption isotherms: A review on physical bases, modeling and measurement , 2007 .

[179]  J. San Román,et al.  Starch-based biodegradable hydrogels with potential biomedical applications as drug delivery systems. , 2002, Biomaterials.

[180]  H. Freundlich Über die Adsorption in Lösungen , 1907 .

[181]  S. Vicini,et al.  Stimuli responsive gels based on interpenetrating network of chitosan and poly(vinylpyrrolidone) , 2005 .

[182]  Sang Hoon Lee,et al.  Electrical response characterization of chitosan/polyacrylonitrile hydrogel in NaCl solutions , 2003 .

[183]  Huining Xiao,et al.  Structure and properties of cellulose/poly(N-isopropylacrylamide) hydrogels prepared by SIPN strategy. , 2013, Carbohydrate polymers.

[184]  P. R. van Weeren,et al.  Hyaluronic acid and dextran-based semi-IPN hydrogels as biomaterials for bioprinting. , 2011, Biomacromolecules.

[185]  Mingzhu Liu,et al.  Synthesis and characterization of κ‐carrageenan/poly(N,N‐diethylacrylamide) semi‐interpenetrating polymer network hydrogels with rapid response to temperature , 2008 .

[186]  T. Nishimura,et al.  Preparation of IPN‐type stimuli‐Responsive heavy‐Metal‐Ion adsorbent gel , 2003 .

[187]  C. Gérente,et al.  Application of Chitosan for the Removal of Metals From Wastewaters by Adsorption—Mechanisms and Models Review , 2007 .

[188]  Zhenbin Chen,et al.  MMTCA recognition by molecular imprinting in interpenetrating polymer network hydrogels based on poly(acrylic acid) and poly(vinyl alcohol). , 2008, Macromolecular bioscience.

[189]  E. Gil,et al.  Effect of silk fibroin interpenetrating networks on swelling/deswelling kinetics and rheological properties of poly(N-isopropylacrylamide) hydrogels. , 2007, Biomacromolecules.

[190]  Jing Jing Wang,et al.  Enhanced adsorption of heavy metal ions onto simultaneous interpenetrating polymer network hydrogels synthesized by UV irradiation , 2013, Polymer Bulletin.

[191]  A. Concheiro,et al.  Temperature-sensitive chitosan-poly(N-isopropylacrylamide) interpenetrated networks with enhanced loading capacity and controlled release properties. , 2005, Journal of controlled release : official journal of the Controlled Release Society.

[192]  Ö. Üzüm,et al.  Equilibrium swelling studies and dye sorption characterization of AAm/SA hydrogels cross‐linked by PEGDMA and semi‐IPNs with PEG , 2012 .

[193]  Seon Jeong Kim,et al.  Synthesis and characteristics of a semi‐interpenetrating polymer network based on chitosan/polyaniline under different pH conditions , 2005 .

[194]  A. R. Khokhlov,et al.  Collapse of thermosensitive polyelectrolyte semi-interpenetrating networks , 2012 .

[195]  Jaehwan Kim,et al.  Cellulose–chitosan interpenetrating polymer network for electro‐active paper actuator , 2009 .

[196]  N. Sahiner,et al.  Novel hydrogel particles and their IPN films as drug delivery systems with antibacterial properties. , 2012, Colloids and surfaces. B, Biointerfaces.

[197]  Kinam Park,et al.  Superporous IPN hydrogels having enhanced mechanical properties , 2003, AAPS PharmSciTech.

[198]  Yi Gao,et al.  Synthesis and characteristics of an amphoteric semi‐IPN hydrogel composed of acrylic acid and poly(diallydimethylammonium chloride) , 2007 .

[199]  A. F. Rubira,et al.  Water affinity and permeability in membranes of alginate-Ca2+ containing poly(n-isopropylacrylamide) , 2002 .

[200]  Ö. Üzüm,et al.  Swelling characterization of novel ternary semi‐IPNs: acrylamide/1‐vinylimidazole/PEG hydrogels , 2007 .

[201]  I. El-Sherbiny,et al.  Preparation, characterization, swelling and in vitro drug release behaviour of poly[N-acryloylglycine-chitosan] interpolymeric pH and thermally-responsive hydrogels , 2005 .

[202]  S. I. Kim,et al.  Properties of the Interpenetrating Polymer Network Hydrogels Composed of Poly(vinyl alcohol) and Poly(diallyldimethylammonium chloride) , 2002 .

[203]  G. Chauhan,et al.  Synthesis and characterization of novel guar gum hydrogels and their use as Cu2+ sorbents. , 2009, Bioresource technology.

[204]  B. Mattiasson,et al.  Evaluation of selective composite cryogel for bromate removal from drinking water. , 2010, Journal of separation science.

[205]  Genqi Liu,et al.  Electroresponsive behavior of 2‐hydroxypropyltrimethyl ammonium chloride chitosan/poly(vinyl alcohol) interpenetrating polymer network hydrogel , 2012 .

[206]  T. Aminabhavi,et al.  Novel interpenetrating polymer network microspheres of chitosan and methylcellulose for controlled release of theophylline , 2007 .

[207]  N. Peppas,et al.  Influence of copolymer composition on non‐fickian water transport through glassy copolymers , 1983 .

[208]  M. Low Kinetics of Chemisorption of Gases on Solids. , 1960 .

[209]  Mingzhu Liu,et al.  Swelling mechanism of porous P(VP‐co‐MAA)/PNIPAM semi‐IPN hydrogels with various pore sizes prepared by a freeze treatment , 2009 .

[210]  Jing Wang,et al.  Thermoresponsive Ion-Imprinted Hydrogels with Interpenetrating Network Structure for Removal of Heavy Metal Ions , 2013 .

[211]  Jingjing Wang,et al.  Enhanced adsorption properties of interpenetrating polymer network hydrogels for heavy metal ion removal , 2011 .

[212]  J. Filipović,et al.  Preparation and characterization of pH-sensitive hydrogels based on chitosan, itaconic acid and methacrylic acid , 2011 .

[213]  Jinwon Park,et al.  Preparation of interpenetrating polymer network composed of poly(ethylene glycol) and poly(acrylamide) hydrogels as a support of enzyme immobilization , 2008 .

[214]  B. Matsuhiro,et al.  Preparation and characterization of hydrogels based on homopolymeric fractions of sodium alginate and PNIPAAm. , 2013, Carbohydrate polymers.

[215]  G. Demirel,et al.  Semi-interpenetrating polymer networks (IPNs) for entrapment of glucose isomerase , 2006 .

[216]  Bo Mattiasson,et al.  Polymeric cryogels as promising materials of biotechnological interest. , 2003, Trends in biotechnology.

[217]  V. Choudhary,et al.  Radiation synthesis of interpenetrating polymer networks based on N-vinyl pyrrolidone – acrylic acid copolymer and gelatin. I. Swelling, morphology, and thermal characterization for biomedical applications , 2007 .

[218]  A. F. Rubira,et al.  Hydrogels based on chemically modified poly(vinyl alcohol) (PVA-GMA) and PVA-GMA/chondroitin sulfate: Preparation and characterization , 2012 .

[219]  Xiaoyuan Yu,et al.  Chemical modification of chitosan by tetraethylenepentamine and adsorption study for anionic dye removal. , 2011, Carbohydrate research.

[220]  Era Jain,et al.  Macroporous interpenetrating cryogel network of poly(acrylonitrile) and gelatin for biomedical applications , 2009, Journal of materials science. Materials in medicine.

[221]  Aiqin Wang,et al.  Synthesis, characterization, and swelling behaviors of chitosan‐g‐poly(acrylic acid)/poly(vinyl alcohol) semi‐IPN superabsorbent hydrogels , 2011 .

[222]  Dong Wang,et al.  Synthesis and characterization of novel aromatic azo bond-containing pH-sensitive and hydrolytically cleavable IPN hydrogels. , 2006, Biomaterials.

[223]  S. Gunasekaran,et al.  Synthesis and characterization of pH‐ and salt‐responsive hydrogels based on etherificated sodium alginate , 2010 .

[224]  H. Bhojya Naik,et al.  Synthesis and characterization of chitosan-based pH-sensitive semi-interpenetrating network microspheres for controlled release of diclofenac sodium. , 2009, Carbohydrate research.

[225]  S. Ashwal,et al.  Evaluation of Coma , 2009 .

[226]  C. Mijangos,et al.  In situ Synthesis of Magnetic Iron Oxide Nanoparticles in Thermally Responsive Alginate-Poly(N-isopropylacrylamide) Semi-Interpenetrating Polymer Networks. , 2009, Macromolecular rapid communications.

[227]  D. Apopei,et al.  Multiresponsive macroporous semi-IPN composite hydrogels based on native or anionically modified potato starch. , 2013, Carbohydrate polymers.

[228]  B. Sivasankar,et al.  Synthesis and characterization of semi-interpenetrating polymer networks using biocompatible polyurethane and acrylamide monomer , 2009 .

[229]  Ashok Kumar,et al.  Designing Supermacroporous Cryogels Based on Polyacrylonitrile and a Polyacrylamide–Chitosan Semi-interpenetrating Network , 2009, Journal of biomaterials science. Polymer edition.

[230]  Xinghai Yu,et al.  Preparation and properties of a degradable interpenetrating polymer networks based on starch with water retention, amelioration of soil, and slow release of nitrogen and phosphorus fertilizer , 2013 .

[231]  S. Gunasekaran,et al.  Selected properties of pH‐sensitive, biodegradable chitosan–poly(vinyl alcohol) hydrogel , 2004 .

[232]  S. Ray,et al.  Synthesis of interpenetrating network hydrogel from poly(acrylic acid-co-hydroxyethyl methacrylate) and sodium alginate: modeling and kinetics study for removal of synthetic dyes from water. , 2013, Carbohydrate polymers.

[233]  K. Varaprasad,et al.  Poly(acrylamide-chitosan) Hydrogels: Interaction with Surfactants , 2010 .

[234]  A. Bajpai,et al.  Ionizable interpenetrating polymer networks of carboxymethyl cellulose and polyacrylic acid: Evaluation of water uptake , 2004 .

[235]  Hongwei Ma,et al.  Preparation and characterization of pH- and temperature-responsive nanocomposite double network hydrogels. , 2013, Materials science & engineering. C, Materials for biological applications.

[236]  Jide Wang,et al.  The Swelling Behaviors and Network Parameters of Cationic Starch-g-Acrylic Acid/Poly(dimethyldiallylammonium chloride) Semi-Interpenetrating Polymer Networks Hydrogels , 2008 .

[237]  Ji‐Heung Kim,et al.  Dye adsorption characteristics of alginate/polyaspartate hydrogels , 2008 .

[238]  F. Soleimani,et al.  Synthesis of pH-Sensitive Hydrogel Based on Starch-Polyacrylate Superabsorbent , 2012 .

[239]  M. Dinu,et al.  Composite IPN ionic hydrogels based on polyacrylamide and dextran sulfate , 2011 .

[240]  D. Şolpan,et al.  Investigation of complex formation between (sodium alginate/acrylamide) semi-interpenetrating polymer networks and lead, cadmium, nickel ions , 2005 .

[241]  Chengjun Zhou,et al.  A novel polyacrylamide nanocomposite hydrogel reinforced with natural chitosan nanofibers. , 2011, Colloids and surfaces. B, Biointerfaces.

[242]  N. Peppas,et al.  Hydrogels in Pharmaceutical Formulations , 1999 .