Rapid temperature/pH response of porous alginate-g-poly(N-isopropylacrylamide) hydrogels

To improve the swelling and deswelling rate, comb-type macroporous hydrogels were prepared. The temperature-sensitive poly(N-isopropylacrylamide) (PNIPAAm) was grafted on the surface or bulk of the pH-responsive alginate. The larger surface area in pores and free chain mobility by comb-type graft copolymer reached its equilibrium swollen state within a minute. The swelling ratio of porous hydrogel in equilibrium state was over fifteen times greater than that of nonporous hydrogels. The increase of surface area by pores caused water molecules to transfer easily in and out of the matrix, resulting in a rapid deswelling. The degree of change in swelling ratio during deswelling might be affected by the phase transition behavior of PNIPAAm attached on only the surface of the pore rather than PNIPAAm grafted into mainchain of alginate. Surface-grafted alginate/PNIPAAm gels had a suitable mechanical strength without collapsing during the repeatable shrinkage and expansion due to swelling and deswelling, whereas bulk-grafted gels easily collapsed.     

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     

Synthesis and Characterization of Temperature-Sensitive Poly(N-isopropylacryamide) Hydrogel with Comonomer and Semi-IPN material

A series of temperature and pH sensitive hydrogels were synthesized using N-isopropylacrylamide (NIPAAm) as main monomer, sodium alginate (SA) as semi-IPN material, ethyl acrylate (EA) and acrylic acid (AA) as comonomer, and N-maleyl chitosan (N-MACH) as cross-linker. The temperature and pH sensitive behavior, swelling/deswelling kinetics of the hydrogels were investigated. And the mechanism of the phase transition was summed up. Sodium alginate/Poly(N-isopropylacryamide) semi-interpenetrating polymer network (SA/PNIPAAm semi-IPN) hydrogels exhibited a lower critical solution temperature (LCST) at about 32 °C with no significant deviation from the conventional PNIPAAm hydrogels. Poly(N-isopropylacryamide-co-ethyl acrylate) (P(NIPAAm-co-EA)) hydrogels exhibited LCST at 29–31°C, increasing the amount of EA in the hydrogel gradually decreased the LCST. Poly(N-isopropylacryamide-co-acrylic acid) [P(NIPAAm-co-AA)] hydrogels exhibited LCST at 34–39°C, with decreasing NIPAAm/AA from 96/4 to 92/8 and 90/10, the LCST increased from 34°C to 37°C and 39°C. In the swelling/deswelling kinetics, all the dried hydrogels exhibited fast swelling/deswelling behavior, which might be attributed to macroporous structures of the hydrogels.     

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     

Synthesis and characterization of pH‐ and temperature‐sensitive silk sericin/poly(N‐isopropylacrylamide) interpenetrating polymer networks

Interpenetrating polymer networks (IPNs) composed of silk sericin (SS) and poly(N‐isopropylacrylamide) (PNIPAAm) were prepared simultaneously. The properties of the resultant IPN hydrogels were characterized by differential scanning calorimetry and SEM as well as their swelling behavior at various temperatures and pH values. The single glass transition temperature (T_g) presented in the IPN thermograms indicated that SS and PNIPAAm form a miscible pair. The swollen morphology of the IPNs observed by SEM demonstrated that water channels (pores present in SEM micrographs) were distributed homogeneously through out the network membranes. The swelling ratio of the IPNs depended significantly on the composition, temperature and pH of the buffer solutions. The dynamic transport of water into the IPN membrane was analyzed based on the Fickian equation. Copyright © 2006 Society of Chemical Industry     

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     

Dual‐responsive semi‐interpenetrating network beads based on calcium alginate/poly(N‐isopropylacrylamide)/poly(sodium acrylate) for sustained drug release

To improve the mechanical strength of natural hydrogels and to obtain a sustained drug‐delivery device, temperature‐/pH‐sensitive hydrogel beads composed of calcium alginate (Ca‐alginate) and poly(N‐isopropylacrylamide) (PNIPAAm) were prepared in the presence of poly(sodium acrylate) (PAANa) with ultrahigh molecular weight (M_η ≥ 1.0 × 10⁷) as a strengthening agent. The influence of PAANa content on the properties, including the beads stability, swelling, and drug‐release behaviors, of the hydrogels was evaluated. Scanning electron microscopy and oscillation experiments were used to analyze the structure and mechanical stability of the hydrogel beads, respectively. The results show that stability of the obtained Ca‐alginate/PNIPAAm hydrogel beads strengthened by PAANa the alginate/poly(N‐isopropyl acrylamide) hydrogel bead (SANBs) was significantly improved compared to that of the beads without PAANa (NANBs) at pH 7.4. The swelling behavior and drug‐release capability of the SANBs were markedly dependent on the PAANa content and on the environmental temperature and pH. The bead sample with a higher percentage of PAANa exhibited a lower swelling rate and slower drug release. The drug release profiles from SANBs were further studied in simulated intestinal fluid, and the results demonstrated here suggest that SANBs could serve as a potential candidate for controlled drug delivery in vivo. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Preparation of alginate/poly(N‐isopropylacrylamide) semi‐interpenetrating and fully interpenetrating polymer network hydrogels with γ‐ray irradiation and their swelling behaviors

Semi‐interpenetrating polymer network (semi‐IPN) and fully interpenetrating polymer network (full‐IPN) hydrogels composed of alginate and poly(N‐isopropylacrylamide) were prepared with γ‐ray irradiation. The semi‐IPN hydrogels were prepared through the irradiation of a mixed solution composed of alginate and N‐isopropylacrylamide (NIPAAm) monomer to simultaneously achieve the polymerization and self‐crosslinking of NIPAAm. The full‐IPN hydrogels were formed through the immersion of the semi‐IPN film in a calcium‐ion solution. The results for the swelling and deswelling behaviors showed that the swelling ratio of semi‐IPN hydrogels was higher than that of full‐IPN hydrogels. A semi‐IPN hydrogel containing more alginate exhibited relatively rapid swelling and deswelling rates, whereas a full‐IPN hydrogel showed an adverse tendency. All the hydrogels with NIPAAm exhibited a change in the swelling ratio around 30–40°C, and full‐IPN hydrogels showed more sensitive and reversible behavior than semi‐IPN hydrogels under a stepwise stimulus. In addition, the swelling ratio of the hydrogels continuously increased with the pH values, and the swelling processes were proven to be repeatable with pH changes. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 100: 4439–4446, 2006     

Preparation and microstructural analysis of poly(ethylene oxide) comb‐type grafted poly(N‐isopropyl acrylamide) hydrogels crosslinked by poly(ϵ‐caprolactone)

Poly(N‐isopropyl acrylamide) (PNIPAAm)‐graft‐poly(ethylene oxide) (PEO) hydrogels crosslinked by poly(?‐caprolactone) diacrylate were prepared, and their microstructures were investigated. The swelling/deswelling kinetics and compression strength were measured. The relationship between the structure and properties of hydrogel are discussed. It was found that the PEO comb‐type grafted structure reduced the thermosensitivity and increased the compression strength. The addition of poly(?‐caprolactone) (PCL) accelerated the deswelling rate of the hydrogels. Meanwhile, the entanglement of PCL chains restrained the further swelling of the network of gels. The PCL crosslinking agent and PEO comb‐type grafted structure made the behavior of the hydrogels deviate from the rubber elasticity equations. © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

Semi‐interpenetrating networks based on poly(N‐isopropyl acrylamide) and poly(N‐vinylpyrrolidone)

Three series of novel semi‐interpenetrating polymer networks, based on crosslinked poly(N‐isopropylacrylamide), PNIPA, and different amounts of the linear poly(N‐vinylpyrrolidone), PVP, were synthesized to improve the mechanical properties and thermal response of PNIPA gels. The effect of the incorporation of the linear PVP into the temperature responsive networks on the temperature‐induced transition, swelling/deswelling behavior, and mechanical properties was studied. Polymer networks with four different crosslinking densities were prepared with varying molar ratios (25/1 to 100/1) of the monomer (N‐isopropylacrylamide) to the crosslinker (N,N′‐methylenebisacrylamide). The hydrogels were characterized by determination of the equilibrium degree of swelling, the dynamic shear modulus and the effective crosslinking density, as well as tensile strength and elongation at break. Furthermore, the deswelling kinetics of the hydrogels was studied by measuring their water retention capacity. The inclusion of the linear hydrophilic PVP in the PNIPA networks increased the equilibrium degree of swelling. The tensile strength of the semi‐interpenetrating networks (SIPNs) reinforced with linear PVP was higher than that of the PNIPA networks. The elongation at break of these SIPNs varied between 22% and 55%, which are 22 – 41% larger than those for pure PNIPA networks. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Preparation and Characterization of Porous Poly (N-isopropylacrylamide) /Clay Nanocomposite Hydrogels

Summary  A novel porous PNIPA/Clay nanocomposite hydrogel (NC hydrogel) was prepared by in situ free-radical polymerization using inorganic clay as a crosslinker and calcium carbonate (CaCO₃) particle as a pore-forming agent and subsequent extraction of CaCO₃ with acid. The structure and morphology of the hydrogels were characterized by means of FTIR, TEM and SEM. The temperature responsive behaviors, the deswelling behaviors and the mechanical properties of the NC hydrogels were investigated in detail. The results showed that the swelling ratios below VPTT and the deswelling rates of the NC hydrogels were significantly improved as compared with the hydrogels without introduction of CaCO₃. Moreover, the NC hydrogels thus prepared also exhibited good mechanical properties.     

Fabrication and characterization of microgel-impregnated, thermosensitive PNIPAAm hydrogels

Poly(N-isopropylacrylamide)/poly(ethylene glycol) diacrylate (PNIPAAm/PEG-DA) microgels were used as an additive during the polymerization and/or crosslinking of PNIPAAm hydrogels to improve their thermosensitive properties. The influence of this additive on the property of resulting PNIPAAm hydrogels was investigated and characterized. The interior morphology by scanning electron microscopy (SEM) revealed that microgel impregnated PNIPAAm hydrogels have tighter and constrained porous network structures, although large cavities of 30-40 μm in diameter, occupied by the microgels were sporadically distributed in this constrained network. Differential scanning calorimetry (DSC) studies did not show apparent difference in lower critical solution temperature (LCST) between normal and microgel-impregnated PNIPAAm hydrogels. The incorporating of PNIPAAm/PEG-DA microgels, however, significantly improved mechanical properties of modified hydrogels when comparing with a normal PNIPAAm hydrogel, although the tendency was not strictly proportional to the microgel amount. Based on the temperature-induced swelling ratio data as well as response kinetics, microgel-impregnated hydrogels exhibited improved thermosensitive characteristics in terms of higher equilibrium swelling ratio as well as faster response rates and the level of improvement depended on the amount of microgel impregnated.     

pH- and thermo-sensitive semi-IPN hydrogels composed of chitosan, <Emphasis Type="Italic">N</Emphasis>-isopropylacrylamide,and poly(ethylene glycol)-<Emphasis Type="Italic">co</Emphasis>-poly(ε-caprolactone) macromer for drug delivery

In this study, semi-IPN chitosan/poly(N-isopropylacrylamide) (PNIPAAm) hydrogels have been prepared via in situ UV-photo-crosslinking of N-isopropylacrylamide monomer using poly(ethylene glycol)-co-poly(ε-caprolactone) (PEG-co-PCL) macromer as a crosslinker in the presence of chitosan. Swelling properties of the resultant hydrogels were studied by investigating pH- and temperature dependence of equilibrium swelling ratio and oscillatory swelling–deswelling kinetics. It was found that semi-IPN hydrogels responded to both temperature and pH changes, and such stimuli-responsiveness was rapidly reversible. The rheological measurements demonstrated that the incorporation of chitosan greatly improved the mechanical strength of the hydrogels prepared. The release profiles of bovine serum albumin (BSA) from the hydrogels were also evaluated. The results showed that the release rate of BSA was higher in pH 2.0 buffer solution than in pH 7.4 buffer solution at 37 °C. Such double-sensitive hydrogels have the potential to use as smart carriers for drug delivery systems.     

Biocompatible and biodegradable alginate/poly(N‐isopropylacrylamide) hydrogels for sustained theophylline release

Mixed‐interpenetrated polymeric networks based on sodium alginate (ALG) and poly(N‐isopropylacryl amide) (PNIPAAm) covalently cross‐linked with N,N'‐methylenebisacrylamide are studied for their biocompatibility, nontoxicity, and biodegradability aiming their application in drug delivery. The presence of drug‐polymeric matrix interactions and the distribution of the drug in the polymeric network for theophylline‐loaded ALG/PNIPAAm hydrogels are also investigated by spectroscopic and microscopic methods. The quantitative evaluation of theophylline loaded hydrogels performed by NIR‐CI technique shows a better drug entrapment and a higher homogeneity of the samples with increased alginate content. The thermal behavior of the hydrogels is significantly modified by theophylline presence. The application of the ALG/PNIPAAm hydrogels as carriers for sustained drug release formulations was assessed by the theophylline release tests performed both by in vitro and in vivo studies. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 40733.     

Rapid swelling and deswelling of semi‐interpenetrating network poly(acrylic acid)/poly(aspartic acid) hydrogels prepared by freezing polymerization

Hydrogels with semi‐interpenetrating networks composed of poly(acrylic acid) (PAAc) and poly(aspartic acid) (PASP) have great potential for pharmaceutical and biomedical applications. In this study, we aimed to synthesize semi‐interpenetrating PAAc/PASP hydrogels with improved swelling–deswelling properties via two‐step polymerization, in which the first step of polymerization was performed at 37 °C for 15 min and the second step, the freezing polymerization, was performed at ?20 °C for 24 h. The synthesized hydrogels were characterized with field emission scanning electron microscopy, Fourier transform infrared spectroscopy, and thermogravimetric analysis. The swelling and deswelling behaviors of the hydrogels in response to the ionic strength of the buffer solution were investigated. The Schott's swelling kinetic model was used to elucidate the swelling behavior of the hydrogels. The swelling and deswelling rates of the hydrogels prepared via freezing polymerization were faster than those of the hydrogels prepared via conventional polymerization. This was attributed to the large mean pore size of the freeze‐polymerized hydrogels. The PAAc/PASP hydrogels that underwent freezing polymerization had better swelling–deswelling characteristics than the PAAc hydrogels. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 43515.     

A study on water and dye sorption capacities of novel ternary acrylamide/sodium acrylate/PEG semi IPN hydrogels

Here, a novel ternary semi interpenetrating polymer networks (semi IPNs) have been synthesized. An effective role to develop mechanically strong polymeric materials has been through the preparation of interpenetrating polymer networks (IPNs). The highly swelling superabsorbent semi IPNs were prepared by introducing poly(ethylene glycol), (PEG) into an acrylamide/sodium acrylate, (AAm/SA) hydrogels. For swelling characterization, swelling experiments were performed in water at 25 °C, gravimetrically. Water uptake and dye sorption properties of AAm/SA hydrogels and AAm/SA/PEG semi IPNs were investigated as a function of chemical composition of the hydrogels. AAm/SA hydrogels and AAm/SA/PEG semi IPNs were used in experiments on sorption of water-soluble cationic dye such as “Janus Green B” (JGB). For sorption of JGB into AAm/SA hydrogels and AAm/SA/PEG semi IPNs were studied by batch sorption technique at 25 °C. For the analysis of sorption mechanism and for calculation of some binding parameters of JGB from aqueous solutions, some linearization methods such as Klotz, Scatchard, and Langmuir linearization methods have been used.     

Synthesis,characterization and,swelling behavior of semi‐IPN nanocomposite hydrogels of alginate with poly(N‐isopropylacrylamide) crosslinked by nanoclay

pH and temperature responsive nanocomposite hydrogels were synthesized with sodium alginate (NaAlg), N‐isopropylacrylamide (NIPA), and nanoclay. The structure, morphology, thermal behavior, and swelling and deswelling behaviors of the hydrogels were studied. The NaAlgm/PNIPA/Clayn hydrogels revealed a highly porous structure in which the pore sizes decreased and the amount of pores increased with increasing the nanoclay content in the hydrogels. PNIPA retained its own characteristics regardless of the amount of NaAlg and nanoclay. The effect of pH and nanoclay content on the swelling and effect of temperature on the deswelling behavior were investigated. The equilibrium swelling ratios of the nanocomposite hydrogels increased with increasing the pH from 2 to 6. The maximum swelling was attained at pH 6. Deswelling increased with increasing the nanoclay content in the hydrogels. The hydrogels were found to be pH and temperature responsive. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 43222.     

Effect of hydrophobic polystyrene microphases on temperature-responsive behavior of poly(N-isopropylacrylamide) hydrogels

Reversible addition-fragmentation chain transfer polymerization was employed to prepare the crosslinked poly(N-isopropylacrylamide)-graft-polystyrene networks (PNIPAAm-g-PS). Due to the immiscibility of PNIPAAm with PS, the crosslinked PNIPAAm-g-PS copolymers displayed the microphase-separated morphology. While the PNIPAAm-g-PS copolymer networks were subjected to the swelling experiments, it is found that the PS block-containing PNIPAAm hydrogels significantly exhibited faster response to the external temperature changes according to swelling, deswelling, and reswelling experiments than the conventional PNIPAAm hydrogels. The improved thermo-responsive properties of hydrogels have been interpreted on the basis of the formation of the specific microphase-separated morphology in the hydrogels, i.e., the PS blocks pendent from the crosslinked PNIPAAm networks were self-assembled into the highly hydrophobic nanodomains, which behave as the microporogens and thus promote the contact of PNIPAAm chains and water. The self-organized morphology in the hydrogels was further confirmed by photon correlation spectroscopy (PCS). The PCS shows that the linear model block copolymers of PNIPAAm-g-PS networks were self-organized into micelle structures, i.e., the PS domains constitute the hydrophobic nanodomains in PNIPAAm-g-PS networks.     

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.     

Swelling behavior of thermoreversible poly(N‐isopropylacrylamide‐co‐N‐vinylimidazole) hydrogels

Thermoresponsive hydrogels based on N‐isopropylacrylamide and N‐vinylimidazole were synthesized, and their swelling–deswelling behavior was studied as a function of the total monomer concentration. For copolymeric structures with better thermoresponsive properties with respect to poly(N‐isopropylacrylamide‐co‐N‐vinylimidazole) hydrogels, these hydrogels were protonated with HCl and HNO₃, and the copolymer behaviors were compared with those of the unprotonated hydrogels. The temperature was changed from 4 to 70°C at fixed pHs and total ionic strengths. The equilibrium swelling ratio, dynamic swelling ratio, and dynamic deswelling ratio were evaluated for all the hydrogels. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 94: 1619–1624, 2004