pH/temperature‐responsive semi‐IPN hydrogels composed of alginate and poly(N‐isopropylacrylamide)

Amino semitelechelic poly(N‐isopropylacrylamide) (PNIPAAm) was prepared by radical polymerization with aminoethanethiol hydrochloride as a chain‐transfer agent. Semi‐interpenetrating polymer network (semi‐IPN) hydrogels, composed of alginate and amine‐terminated PNIPAAm, were prepared by crosslinking with calcium chloride. From the swelling behaviors of semi‐IPNs at various pH's and Fourier transform infrared spectra at high temperatures, the formation of a polyelectrolyte complex was confirmed from the reaction between carboxyl groups in alginate and amino groups in modified PNIPAAm. Semi‐IPN hydrogels reached an equilibrium swelling state within 24 h. The water state in hydrogels, investigated by differential scanning calorimetry, showed that sample CAN55 [alginate/PNIPAAm (w/w) = 50/50] exhibited the lowest equilibrium water content and free water content among the hydrogels tested, which was attributed to its more compact structure compared to other samples and the high content of interchain bonding within the hydrogels. Alginate/PNIPAAm semi‐IPN hydrogels exhibited a reasonable sensitivity to the temperature, pH, and ionic strength of swelling medium. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 83: 1128–1139, 2002     

Preparation and characterization of pH‐ and temperature‐responsive semi–interpenetrating polymer network hydrogels based on linear sodium alginate and crosslinked poly(N‐isopropylacrylamide)

In this study, pH‐ and temperature‐responsive hydrogels based on linear sodium alginate (SA) and crosslinked poly(N‐isopropylacrylamide) (PNIPAAm) were prepared by semi‐interpenetrating network (semi‐IPN) technique. The dually responsive hydrogels were characterized by FTIR, DSC, and SEM, and their temperature‐ and pH‐responsive behaviors were investigated by measuring equilibrium swelling ratios and pulsatile swelling experiments. The results showed that these hydrogels underwent volume phase transition at around 33°C irrespective of the pH value of the medium, but their pH sensitivity was evident only below their volume phase transition temperature. Under basic conditions, the swelling ratios of SA/PNIPAAm semi‐IPN hydrogels were greater than that of pure PNIPAAm hydrogel and increased with increasing SA content incorporated into the hydrogels, but the case was inverse under acidic conditions. The pulsatile swelling experiments indicated that the higher the SA content in SA/PNIPAAm semi‐IPN hydrogels, the faster the response rate to both pH and temperature change. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 97: 1931–1940, 2005     

Development and characterization of thermosensitive hydrogels based on poly(N‐isopropylacrylamide) and calcium alginate

This work refers to the synthesis and characterization of thermosensitive hydrogels based on interpenetrating polymer networks (IPNs) of poly(N‐isopropylacrylamide) (PNIPAAm) and calcium alginate in the form of films. The influence of the crosslinking degree of PNIPAAm and alginate content on thermal, swelling, mechanical, and morphological properties of hydrogels is investigated in detail. Characterization of pure PNIPAAm hydrogels and IPN hydrogels was performed by FTIR, DSC, DMA, and SEM. In addition, the studies of equilibrium swelling behavior as well as swelling, deswelling, and reswelling kinetics are performed. The results obtained imply the benefits of synthesizing IPNs based on PNIPAAm and calcium alginate over pure PNIPAAm hydrogels. The presence of calcium alginate contributes to the improvement of mechanical properties, the deswelling rate of hydrogels, and the network porosity, without altering the thermosensitivity of PNIPAAm significantly. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

Swelling behavior of semi‐interpenetrating polymer network hydrogels composed of poly(vinyl alcohol) and poly(acrylamide‐co‐sodium methacrylate)

Interpenetrating polymer network (IPN) hydrogels based on poly(vinyl alcohol) (PVA) and poly(acrylamide‐co‐sodium methacrylate) poly(AAm‐co‐SMA) were prepared by the semi IPN method. These IPN hydrogels were prepared by polymerizing aqueous solution of acrylamide and sodium methacrylate, using ammonium persulphate/N,N,N¹,N¹‐tetramethylethylenediamine (APS/TMEDA) initiating system and N,N¹‐methylene‐bisacrylamide (MBA) as a crosslinker in the presence of a host polymer, poly(vinyl alcohol). The influence of reaction conditions, such as the concentration of PVA, sodium methacrylate, crosslinker, initiator, and reaction temperature, on the swelling behavior of these IPNs was investigated in detail. The results showed that the IPN hydrogels exhibited different swelling behavior as the reaction conditions varied. To verify the structural difference in the IPN hydrogels, scanning electron microscopy (SEM) was used to identify the morphological changes in the IPN as the concentration of crosslinker varied. In addition to MBA, two other crosslinkers were also employed in the preparation of IPNs to illustrate the difference in their swelling phenomena. The swelling kinetics, equilibrium water content, and water transport mechanism of all the IPN hydrogels were investigated. IPN hydrogels being ionic in nature, the swelling behavior was significantly affected by environmental conditions, such as temperature, ionic strength, and pH of the swelling medium. Further, their swelling behavior was also examined in different physiological bio‐fluids. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 98: 302–314, 2005     

Synthesis and properties of the semi‐interpenetrating polymer network–like,thermosensitive poly(N‐isopropylacrylamide) hydrogel

A new strategy was used to prepare a semi‐interpenetrating polymer network (semi‐IPN)–like poly(N‐isopropylacrylamide) (PNIPAAm) polymeric hydrogel, consisting of either low (2300) or high (33,000) molecular weight linear PNIPAAm chains and the crosslinked PNIPAAm network. The properties of the resulting PNIPAAm hydrogels were characterized by DSC and SEM as well as their swelling ratios at various temperatures, the deswelling in hot water (48°C), and the oscillating shrinking–swelling properties within small temperature cycles. It was found that the deswelling rate of these semi‐IPN–like PNIPAAm hydrogels was improved if the molecular weight and/or composition of the linear PNIPAAm chains within the semi‐IPN–like PNIPAAm hydrogels were increased. This improved deswelling rate was attributed to the fast response nature of the linear PNIPAAm chains and the increased pore number in the matrix network, which provided numerous water channels for the water to diffuse out during the deswelling process at a temperature above the lower critical solution temperature. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 89: 1935–1941, 2003     

Thermal characteristics of interpenetrating polymer networks composed of poly(vinyl alcohol) and poly(N‐isopropylacrylamide)

Interpenetrating polymer networks (IPNs) composed of poly(vinyl alcohol) (PVA) and poly(N‐isopropylacrylamide) (PNIPAAm) were prepared by the sequential‐IPN method. The thermal characterization of the IPNs was investigated using differential scanning calorimetry (DSC), thermogravimetric analysis (TGA), and dielectric analysis (DEA). Depression of the melting temperature (T_m) of the PVA segment in IPNs was observed with increasing PNIPAAm content using DSC. DEA was employed to ascertain the glass‐transition temperature (T_g) of IPNs. From the result of DEA, IPNs exhibited two T_g values, indicating the presence of phase separation in the IPNs. The thermal decomposition of IPNs was investigated using TGA and appeared at near 200°C. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 90: 881–885, 2003     

Novel PDMS‐based membranes: Sodium chloride and glucose permeability

Permeation of sodium chloride and glucose through polydimethylsiloxane‐poly(N‐isopropylacrylamide) (PDMS‐PNIPAAm) interpenetrating polymer networks (IPNs) of two different microstructures was investigated. We have successfully developed small‐molecule permeable IPNs, by modifying PDMS film structure. A group of PDMS films was prepared using conventional solvent casting (SC) method and another group produced by introducing oil, followed by SC and leaching the oil out (SCOL method). Scanning electron microscopy (SEM) and attenuated total reflection fourier transformer infrared (ATR‐FTIR) spectroscopy results confirmed the presence of PNIPAAm in the SC and SCOL IPNs. Results obtained from spectra of differential scanning calorimetry (DSC) showed that these IPNs had a phase transition temperature at about 32°C. Permeation measurements showed that the presence of PNIPAAm as the second phase in the IPN, improved the permeability of PDMS film. According to the results, maximum permeation coefficient was related to SCOL IPN containing 15.8% ± 0.3%PNIPAAm, at 23°C (5.98 × 10^?7 ± 7.93 × 10^?9 cm²/s for sodium chloride and 3.6 × 10^?7 ± 7 × 10^?9 cm²/s for glucose). These results suggested that these PDMS‐PNIPAAm IPNs with sodium chloride and glucose permeability may be further developed as ophthalmic biomaterials or corneal replacements. © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

Swelling and diffusion characteristics of novel semi‐interpenetrating network hydrogels composed of poly[(acrylamide)‐ co‐(sodium acrylate)] and poly[(vinylsulfonic acid), sodium salt]

A series of novel semi‐interpenetrating polymer networks (IPNs) composed of poly[(acrylamide)‐co‐(sodium acrylate)] with varying amounts (5, 10, and 15 wt%) of poly[(vinylsulfonic acid), sodium salt] was synthesized. The semi‐IPN hydrogels were characterized by infrared spectroscopy. The swelling behavior of these IPNs was studied in distilled water/physiological solutions/buffer solutions/salt solutions. As the amount of poly[(vinylsulfonic acid), sodium salt] increased in the network, the swelling capacity of the semi‐IPNs increased considerably. The swelling and diffusion characteristics such as water penetration velocity (v), diffusion exponent (n), and diffusion coefficient (D) were calculated in distilled water, as well as in other physiological solutions. The highest swelling capacity was noted in urea and glucose solutions. The semi‐IPN hydrogels followed non‐Fickian diffusion behavior in water and physiological fluids, whereas Fickian behavior was observed in buffer solutions. The stimuli‐responsive characteristics towards physiological fluids, salt concentration, and temperature of these semi‐IPN hydrogels were also investigated. The swelling behavior of the semi‐IPNs decreased markedly with an increase of the concentration of the salt solutions. Copyright © 2006 Society of Chemical Industry     

Thermal characterizations of semi‐interpenetrating polymer networks composed of poly(ethylene oxide) and poly(N‐isopropylacrylamide)

Poly(N‐isopropylacrylamide) (PNIPAAm)/poly(ethylene oxide) (PEO) semi‐interpenetrating polymer networks (semi‐IPNs) synthesized by radical polymerization of N‐isopropylacrylamide (NIPAAm) in the presence of PEO. The thermal characterizations of the semi‐IPNs were investigated by differential scanning calorimetry (DSC), thermogravimetric analysis (TGA), and dielectric analysis (DEA). The melting temperature (T_m) of semi‐IPNs appeared at around 60°C using DSC. DEA was employed to ascertain the glass transition temperature (T_g) and determine the activation energy (E_a) of semi‐IPNs. From the results of DEA, semi‐IPNs exhibited one T_g indicating the presence of phase separation in the semi‐IPN, and T_gs of semi‐IPNs were observed with increasing PNIPAAm content. The thermal decomposition of semi‐IPNa was investigated using TGA and appeared at around 370°C. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 90: 3922–3927, 2003     

Thermo‐ and pH‐responsive behaviors of graft copolymer and blend based on chitosan and N‐isopropylacrylamide

Thermo‐ and pH‐sensitive polymers were prepared by graft polymerization or blending of chitosan and poly(N‐isopropylacrylamide) (PNIPAAm). The graft copolymer and blend were characterized by Fourier transform‐infrared, thermogravimetric analysis, X‐ray diffraction measurements, and solubility test. The maximum grafting (%) of chitosan‐g‐(N‐isopropylacrylamide) (NIPAAm) was obtained at the 0.5 M NIPAAm monomer concentration, 2 × 10⁻³ M of ceric ammonium nitrate initiator and 2 h of reaction time at 25°C. The percentage of grafting (%) and the efficiency of grafting (%) gradually increased with the concentration of NIPAAm up to 0.5 M, and then decreased at above 0.5 M NIPAAm concentration due to the increase in the homopolymerization of NIPAAm. Both crosslinked chitosan‐g‐NIPAAm and chitosan/PNIPAAm blend reached an equilibrium state within 30 min. The equilibrium water content of all IPN samples dropped sharply at pH > 6 and temperature > 30°C. In the buffer solutions of various pH and temperature, the chitosan/PNIPAAm blend IPN has a somewhat higher swelling than that of the chitosan‐g‐NIPAAm IPN. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 78: 1381–1391, 2000     

Preparation,characterization, and drug‐release properties of pH/temperature‐responsive poly(N‐isopropylacrylamide)/chitosan semi‐IPN hydrogel particles

Novel poly(N‐isopropylacrylamide) (PNIPAAm)/chitosan (CS) semi‐interpenetrating polymer network hydrogel particles were prepared by inverse suspension polymerization. The prepared particles were sensitive to both temperature and pH, and they had good reversibility in solution at different temperatures and pH values. The swelling ratios of PNIPAAm/CS hydrogel particles decreased slightly with the addition of CS, which did not shift the lower critical solution temperature. The drug‐release behavior of the particles was investigated using cyclic adenosine 3′,5′‐monophosphate (cAMP) as a model drug. The release of cAMP from the hydrogel particles was affected by temperature, pH, and the CS content in the particles. These results showed that semi‐IPN hydrogel particles appeared to be of great promise in pH‐ and temperature‐sensitive oral drug release. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Synthesis and characteristics of the interpenetrating polymer network hydrogel composed of chitosan and polyallylamine

A temperature‐ and pH‐dependent hydrogel was studied with interpenetrating polymer network (IPN) hydrogels constructed with water‐insoluble chitosan and polyallylamine. Various IPNs were prepared from different weight ratios of chitosan–polyallylamine. Crosslinked‐IPN hydrogels exhibited relatively high equilibrium water content (EWC) in the range 80–83%. The EWC of IPN hydrogels depended on pH and the amount of complex, which is the content of chitosan and polyallylamine. The differential scanning calorimeter (DSC) thermogram of fully swollen IPN hydrogels appeared between 3 to 4 °C. The IPNs exhibited two glass‐transition temperatures (T_gs), indicating the presence of phase separation in the IPNs as exhibited by dielectric analysis (DEA). © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 86: 498–503, 2002     

Ionizable interpenetrating polymer networks of carboxymethyl cellulose and polyacrylic acid: Evaluation of water uptake

A semi interpenetrating polymer network (IPN) of carboxymethyl cellulose (CMC) and crosslinked polyacrylic acid (PAA) has been prepared and its water‐sorption capacity has been evaluated as a function of chemical architecture of the IPN, pH, and temperature of the swelling medium. The water uptake potential of the IPNs has also been investigated in inorganic salt containing aqueous solutions and simulated biological fluids. The IPN was characterized by IR spectral analysis, and the network parameters such as average molecular weight between crosslinks (M_c), crosslink density (q), and number of elastically effective chains (V_e) have been evaluated by water‐sorption measurements. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 93: 2054–2065, 2004     

Drug releasing characteristics of thermo- and pH-sensitive interpenetrating polymer networks based on poly (N-isopropylacrylamide)

Interpenetrating polymer networks (IPNs) of poly(N-isopropylacrylamide)/polyurethane (PNIPAAm/PU) and poly(N-isopropylacrylamide)/poly(acrylic acid) (PNIPAAm/PAA) were synthesized to investigate the swelling and drug releasing behavior. The presence of urethane network in PNIPAAm/PU IPNs improved the mechanical strength, but reduced the swelling and drug releasing rates because of its hydrophobic characteristics. The swelling transition temperatures of PNIPAAm gels were little affected by the incorporation of PU networks in IPN structures. The drug releasing process was analyzed with a simple exponential expression of time dependent fractional drug release. The swelling and drug releasing behavior of PNIPAAm/PAa IPNs was significantly affected by the variation of PAA compositions. The drug release process changed from anomalous to dual type via zero-order mode with increasing PAA concentration due to the competitive swelling rates between PNIPAAm and PAA during release process. The releasing rate decreased in the buffer solution of pH 7.4, but increased in that of pH 5.0 with increasing PAA concentration at both 28 and 37°C because the swelling power of PAA in pH 5.0 was much less than that in pH 7.4. © 1997 John Wiley & Sons, Inc. J Appl Polym Sci 64: 2647–2655, 1997     

Preparation and Swelling Properties of Temperature‐Sensitive Semi‐Interpenetrating Polymer Networks Composed of Poly[(N‐tert‐butylacrylamide)‐co‐acrylamide] and Hydroxypropyl Cellulose

Summary: Temperature‐responsive hydrogels based on linear HPC and crosslinked P(NTBA‐co‐AAm) were prepared by the semi‐IPN technique. The structure of these semi‐IPN hydrogels was investigated by FT‐IR spectroscopy. An increase in normalized band ratios (A₂₉₈₀/A₁₆₆₅) was observed with increasing HPC content in the initial mixture. The swelling kinetics and water transport mechanism of these semi‐IPN hydrogels were examined and their temperature responsive behaviors were also investigated by measuring equilibrium swelling ratios and pulsatile swelling experiments. The results showed that these semi‐IPN hydrogels underwent a volume phase transition between 18 and 22 °C irrespective of the amounts of MBAAm and HPC. However, below the volume phase transition temperature, their equilibrium swelling ratios were affected by the amount of MBAAm and HPC. The pulsatile swelling experiments indicated that the lower the MBAAm and the higher HPC contents in semi‐IPN hydrogels the faster the response rate temperature change.

Equilibrium swelling ratios of the semi‐IPN P(NTBA‐co‐AAm)/HPC hydrogels in water shown as a function of temperature.     

Polymer–protein interaction,water retention,and biocompatibility of a stimuli‐sensitive superporous hydrogel containing interpenetrating polymer networks

The swelling of a superporous hydrogel containing poly(acrylic acid‐co‐acrylamide)/O‐carboxymethyl chitosan interpenetrating polymer networks (SPH‐IPN) was sensitive toward the pH, ionic strength, and temperature stimuli. With insulin as a model drug, polymer–protein interaction was detected, and it was physical rather than covalent. Freezing water was the majority of the imbibed water in the swollen SPH‐IPNs, and the water‐retention ability of the polymer against compression and time of exposure at 37°C was improved as the amount of the O‐carboxymethyl chitosan network increased. A 3‐(4,5‐dimethylthiazol‐2‐yl)‐2,5‐diphenyl tetrazolium bromide (MTT) assay on AD293 and RBL‐2H3 cells and an in situ lactate dehydrogenase assay and morphological study on rat intestine confirmed that the SPH‐IPNs had satisfactory biocompatibility. These pronounced properties suggested that the SPH‐IPNs could be developed as an attractive peroral delivery vehicle for peptide and protein drugs. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

A fast pH-responsive IPN hydrogel: Synthesis and controlled drug delivery

A series of fast pH-responsive silk sericin (SS)/poly(methacrylic acid) (PMAA) IPN hydrogels were prepared by the simultaneous-IPN method. The structure of the resultant IPN hydrogels was characterized by fourier transform infrared spectroscopy (FTIR) and scanning electron microscopy (SEM). The swelling experimental of the IPNs revealed that the hydrogels displayed definite pH sensitivity under physiological conditions, as well as sharp changes in the mesh size of their network as a function of the composition and pH of the swelling media. Bovine serum albumin (BSA) was chosen as a model protein to evaluate the permeation profile through the IPNs in both the simulated gastric and intestinal pH conditions. In all cases, it was found that the release rate of BSA was lower in acidic media (pH 2.6) and higher in basic media (pH 7.4).     

Studies on preparation and swelling properties of the N-isopropylacrylamide/chitosan semi-IPN and IPN hydrogels

Semi-interpenetrating network (semi-IPN) polymer gels and interpenetrating network (IPN) polymer gels with thermosensitivity were prepared by introducing a biodegradable polymer, chitosan, into the N-isopropyacrylamide (PNIPAAm) gel system. The swelling behavior, temperature sensitivity, pH sensitivity, gel strength, and drug-release behavior of PNIPAAm/chitosan semi-IPN and IPN hydrogels were investigated. The results indicated that the NIPAAm/chitosan semi-IPN and IPN hydrogels exhibited pH and temperature-sensitivity behavior and could slow drug release and diffusion from the gels. From the stress–strain curves of the hydrogels, the compression moduli of IPN gels containing crosslinked chitosan were higher than those of semi-IPN gels. This is because IPN gels have a more compact structure. The morphology of PNIPAAm/chitosan hydrogels was also investigated. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 82: 2487–2496, 2001     

New Interpenetrating Polymer Networks of N-isopropylacrylamide/ N-acryloxysuccinimide: Synthesis and Characterization

Interpenetrating polymer networks (IPNs) based on poly (N-isopropylacrylamide), PNIPAAm, and poly (N-acryloxysuccinimide), PNAS, were prepared by a sequential method; the PNIPAAm which was polymerized and crosslinked by gamma irradiation, was swelled in a solution of PNAS/polylysine, which function as crosslinking agent for this monomer and as anchoring element of vesicles. The thermosensitivity properties (limit swelling time, lower critical solution temperature (LCST) and water retention), chemical composition (FTIR and elemental analysis), thermal properties (DSC and TGA) and morphology (SEM) were studied to characterize the IPNs.     

pH‐ and temperature‐responsive IPN hydrogels based on soy protein and poly(N‐isopropylacrylamide‐co‐sodium acrylate)

pH‐ and temperature‐responsive interpenetrating polymer network (IPN) hydrogels based on soy protein and poly(N‐isopropylacrylamide‐co‐sodium acrylate) were successfully prepared. The structure and properties of the hydrogels were characterized by Fourier transform infrared spectroscopy, scanning electron microscopy, differential scanning calorimetry, and thermogravimetric analyzer. The equilibrium and dynamic swelling/deswelling behaviors and the drug release properties of the hydrogels responding to pH and/or temperature were also studied in detail. The hydrogels have the porous honeycomb structures, good miscibility and thermal stability, and good pH‐ and temperature‐responsivity. The volume phase transition temperature of the hydrogels is ca. 40°C. Changing the soy protein or crosslinker content could be used to control the swelling behavior and water retention, and the hydrogels have the fastest deswelling rate in pH 1.2 buffer solutions at 45°C. Bovine serum albumin release from the hydrogels has the good pH and temperature dependence. The results show that the proposed IPN hydrogels may have potential applications in the field of biomedical materials such as in drug delivery systems. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 39781.