Effect of hydrotalcite on the physical properties and drug‐release behavior of nanocomposite hydrogels based on poly[acrylic acid‐co‐poly(ethylene glycol) methyl ether acrylate] gels

A series of nanocomposite hydrogels used for bioadhesive were prepared from acrylic acid, poly(ethylene glycol) methyl ether acrylate, and intercalated hydrotalcite (HT) by photopolymerization. The microstructures of the intercalated HT and sample gels were identified by X‐ray diffraction (XRD). The results showed that the swelling ratio for these nanocomposite hydrogels increased with an increase in HT, but the gel strength and adhesive force for these gels decreased with an increase in HT. The XRD results indicated that the exfoliation of intercalated HT was achieved in the xerogels and swollen gels. Finally, the drug‐release behaviors for these gels were also examined. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 94: 692–699, 2004     

Effect of the intercalation agent content of montmorillonite on the swelling behavior and drug release behavior of nanocomposite hydrogels

A series of novel dual functional nanocomposite hydrogels were prepared from N‐isopropylacrylamide (NIPAAm), acrylic acid (AA) that is neutralized 50 mol % by sodium hydroxide (SA50), and montmorillonite (MMT). MMT was intercalated with three different contents of intercalation agent of (3‐acrylamidopropyl) trimethyl ammonium chloride (TMAACl). Investigation of the effect of intercalated MMT with three contents of intercalation agent (TMAACl) in the present nanocomposite hydrogels on the swelling and drug release behaviors is the main purpose in this study. The microstructure was identified by X‐ray diffraction (XRD). Results showed that the swelling ratio for the present nanocomposite hydrogels decreased with an increase in the content of the intercalation agent. The gel strength of the present gels did not change obviously with an increase in the content of intercalation agent. XRD results indicated that exfoliation of MMT was achieved in the dry and swollen gel state. Finally, the drug release behaviors for these gels were accessed also. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 94: 74–82, 2004     

Effect of montmorillonite on the swelling behavior and drug‐release behavior of nanocomposite hydrogels

A series of nanocomposite hydrogels were prepared from various ratios of N‐isopropylacrylamide (NIPAAm) and organic montmorillonite (MMT). The influence of the extent of MMT in the NIPAAm/MMT nanocomposite hydrogels on the physical properties and drug‐release behavior was the main purpose of this study. The microstructure and morphology were identified by X‐ray diffraction (XRD) and scanning electronic microscopy (SEM). The results showed that the swelling ratios for these nanocomposite hydrogels decreased with increase in the content of MMT. The gel strength and Young's modulus of the gels also increased with increase in the content of MMT. XRD results indicated that the exfoliation of MMT was achieved in the swollen state. Finally, the drug‐release behavior for the gels was also assessed. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 89: 3652–3660, 2003     

Semi‐IPN carrageenan‐based nanocomposite hydrogels: Synthesis and swelling behavior

Inclusion of nano‐clays into hydrogels is an efficient approach to produce nanocomposite hydrogels. The introduction of nano‐clay into hydrogels causes an increase in water absorbency. In the present work, Nanocomposite hydrogels based on kappa‐carrageenan were synthesized using sodium montmorillonite as nano‐clay. Acrylamide and methylenebisacrylamide were used as monomer and crosslinker, respectively. The structure of nanocomposite hydrogels was investigated by XRD and SEM techniques. Swelling behavior of nanocomposite hydrogels was studied by varying clay and carrageenan contents as well as methylenebisacrylamide concentration. An optimum swelling capacity was achieved at 12% of sodium montmorilonite. The swollen nanocomposite hydrogels were used to study water retention capacity (WRC) under heating. The results revealed an increase in WRC due to inclusion of sodium montmorilonite clay. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Swelling and drug‐release behavior of the poly(AA‐co‐N‐vinyl pyrrolidone)/chitosan interpenetrating polymer network hydrogels

A series of novel hydrogels were prepared from acrylic acid (AA), N‐vinyl pyrrolidone (NVP), and chitosan by photopolymerization. The swelling behavior, gel strength, and drug release behavior of the poly(AA/NVP) copolymeric hydrogels and corresponding interpenetrating polymer network hydrogels were investigated. Results showed that the swelling ratios for the present hydrogels decreased with an increase of NVP content in the gel, but the gel strength increased with an increase of NVP content in the gel. Results also showed that the drug‐release behavior for the gels is related to the ionicity of drug and the swelling ratio of the gel. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 91: 2135–2142, 2004     

Tough hyperbranched epoxy/poly(amido‐amine) modified bentonite thermosetting nanocomposites

A tough and highly flexible hyperbranched epoxy and poly(amido‐amine) modified bentonite based thermosetting nanocomposite was demonstrated. The FTIR, XRD, and TGA analyses confirmed the modification of bentonite. The formation of partially exfoliated structure of the nanocomposite with good physicochemical interactions among the hyperbranched epoxy, poly(amido‐amine) hardener and modified clay was investigated by the FTIR, XRD, SEM, and TEM analyses. Significant improvements of 750% toughness, 300% elongation at break, 50% tensile strength, 300% modulus, and 250% adhesive strength of the pristine epoxy were achieved by the formation of nanocomposites with 3 wt % of modified clay. The experimental modulus values of the nanocomposites were compared with three theoretical models to account the interactions between filler and matrix. Thus, the studied epoxy nanocomposite has great potential to be used as an advanced epoxy thermoset. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 40327.     

Effect of intercalated hydrotalcite on swelling and mechanical behavior for poly(acrylic acid‐co‐N‐isopropylacrylamide)/hydrotalcite nanocomposite hydrogels

A series of nanocomposite hydrogels were prepared from acrylic acid (AA), N‐isopropylacrylamide (NIPAAm), and intercalated hydrotalcite (IHT) by photopolymerization. The influence of the intercalating content of 2‐acrylamido‐2‐methyl propane sulfonic acid (AMPS) in HT on the swelling and mechanical properties for poly(AA‐co‐NIPAAm)/IHT nanocomposite hydrogels was investigated. The results showed that the higher the content of the AMPS‐HT was, the higher the swelling ratio of the gels and the higher the content of the intercalating agent was, the lower swelling ratio. It was also demonstrated that the swelling ratio of the gel was not affected by the counterion in HT. The gel strength and crosslinking density were not enhanced by adding AMPS‐HT into the gel composition, but the maximum effective crosslink density and shear modulus of the nanocomposite hydrogels were increased with an increase of the content of the intercalating agent in HT. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 98: 1572–1580, 2005     

Development and characterization of gelatin–polysaccharide based phase‐separated hydrogels for prevention of sexually transmitted diseases

Bacterial vaginosis is a sexually transmitted vaginal infection prevalent in sexually active women. Gelatin–polysaccharide phase‐separated hydrogels were prepared and characterized as vaginal delivery systems for the treatment of bacterial vaginosis. Sodium carboxymethyl cellulose, maltodextrin, and dextran were used as the representative polysaccharides. The developed gels were characterized by impedance spectrometer, X‐ray diffraction (XRD) studies, and differential scanning calorimetry. The mucoadhesivity, water absorption, and hemocompatibility of the gels were also studied. The gels were electrically conductive in nature and showed a concentration‐dependent behavior. XRD study suggested the amorphous nature of the hydrogels. An increase in the polysaccharide content increased the water holding capacity of the gels. The gels were found to possess mucoadhesive property and were hemocompatible. Metronidazole, a commonly used drug for treating bacterial vaginosis, loaded gels showed diffusion‐mediated drug release. The drug‐loaded hydrogels showed good antimicrobial activity. In gist, the developed hydrogels may be tried as matrices for vaginal delivery of antimicrobials. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 41785.     

Effect of hydrotalcite on the swelling and mechanical behaviors for the hybrid nanocomposite hydrogels based on gelatin and hydrotalcite

A series of hybrid nanocomposite hydrogels, based on gelatin and intercalated hydrotalcite (IHT), crosslinked with glutaraldehyde, was prepared in this study. The microstructures of the IHT and sample gels were identified by X‐ray diffraction (XRD). Swelling behaviors and physical properties of these hybrid gels were investigated. XRD results indicated that exfoliation of IHT was achieved in the hybrid nanocomposite gels. The results indicated that adding a small amount of IHT could effectively decrease the swelling ratio of the hybrid gels, but adding excess IHT could increase the swelling ratio of the nanocomposite hybrid gels. The crosslinking densities (ρ_x) of the present gels varied with IHT content and swelling ratio of the gels. The drug release behaviors of these gels were also investigated. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 100: 500–507, 2006     

Effect of borax addition on the structural modification of bentonite in biodegradable alginate‐based biocomposites

Functionalized next generation biodegradable polymeric systems (bioplastics) that have better compatibility, enhanced relaxation, and thermal properties were designed using bentonite‐added alginate biocomposite films in the presence of borax. A series of bentonite‐added biocomposite films crosslinked with CaCl₂ were characterized by using methods like XRD, FTIR, TGA, DTA/DSC, DMA, and AFM. A plausible structural mechanism with Ca²⁺ crosslinking gel formation known as egg‐box and borate ion complexes was proposed to elucidate the interactions between borax and bentonite/alginate biocomposites. Enhanced compatibility and hybrid properties of raw fillers were confirmed by mineral processing steps involving hydrocyclone purification for bentonite and recrystallization steps for borax. The structure of bentonite and also bentonite hybrid biocomposites were clearly improved upon small additions of borax into the matrix. The presence of borax was found to provide a more intercalated or exfoliated morphology for a given hybrid biocomposite structure. Borate ions dissociated in aqueous solution provided a better effect on the intercalation of bentonite by imparting new hydrogen bonding sites, diol‐complexes, and didiol‐crosslinking gels. © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

Carboxylmethylcellulose/bentonite composite gels: Water sorption behavior and controlled release of herbicide

The composite gels were prepared by adding bentonite or its acid‐activated derivative into the carboxylmethylcellulose (CMC) gel, and the resulted products were characterized with infrared spectroscopy. Different from ordinary swellable hydrogels, the CMC/bentonite hydrogel beads shrinked in water. The water sorption of dried gels was limited below 120% of their own weight, and a sorption equilibrium reached quickly within 20–40 min. The water of swollen gels exists mainly in bound status according to the DSC analysis. The release experiments in water were carried out to evaluate the release of herbicide metolachlor from gel formulations. The release mechanism dominated by a Fickian diffusion might be related to the quick and limited swelling of dried gels. Addition of bentonites in CMC gel is beneficial for slowing the release of metolachlor, especially when the acid‐activated bentonite was added. The time taken for 50% of metolachlor to be released, t₅₀ was prolonged to 158 h for the composite gel formulation based on acid‐activated bentonite from the 61.1 h for pure CMC gel formulation. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Synthesis and thermal behavior of poly(methyl methacrylate)/Maghnia bentonite nanocomposite prepared at room temperature via in situ polymerization initiated by a new Ni(II)α‐benzoinoxime complex

Poly(methyl methacrylate) (PMMA) and poly(methyl methacrylate)/clay nanocomposite (PMMA/OBT) were successfully prepared in dioxan at room temperature via in situ radical polymerization initiated by a new Ni(II)α‐ Benzoinoxime complex as a single component in presence of 3% by weight of an organically modified bentonite (OBT) (originated from Maghnia, Algeria) and characterized by FTIR, ¹H‐NMR and viscometry. Mainly intercalated and partially exfoliated PMMA/OBT nanocomposite was elaborated and evidenced by X‐Ray diffraction (XRD) and transmission electron microscopy (TEM). The intrinsic viscosity of PMMA/OBT nanocomposite is much higher than the one of pure PMMA prepared under the same conditions. Differential scanning calorimetry (DSC) displayed an increase of 10°C in the glass transition temperature of the elaborated PMMA/OBT nanocomposite relative to the one of pure PMMA. Moreover, the TGA analysis confirms a significant improvement of the thermal stability of PMMA/OBT nanocomposite compared to virgin PMMA: the onset degradation temperature of the nanocomposite, carried out under nitrogen atmosphere, increased by more than 45°C. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Enzymatically degradable and pH‐sensitive hydrogels for colon‐targeted oral drug delivery. I. Synthesis and characterization

Cylindrical hydrogels, composed of starch and poly(acrylic acid), were synthesized, and their swelling behavior was studied as a function of the pH of the medium. The gels underwent a sharp transition from Fickian swelling behavior (swelling exponent n = 0.30) to non‐Fickian swelling behavior (n = 0.96) as the pH of the swelling medium changed from 2.0 to 7.4. The hydrogels also underwent partial enzymatic degradation in an amylase‐containing medium of pH 7.4 at 37°C. The effects of the enzyme concentration in the swelling media, the amount of starch present in the gel, the initial water content, the degree of crosslinking, and the diameter of cylindrical hydrogels on the degradation behavior were studied. The degradation of the gels followed Michaelis–Menten kinetics, and the value of the Menten constant was 41.62 × 10^?2. The gels exhibited minimum swelling in an acidic pH medium through the formation of a complex hydrogen‐bonded structure and underwent enzymatic degradation in a medium of pH 7.4 (i.e., simulating intestinal fluid) along with chain‐relaxation‐controlled swelling. Therefore, the gels have potential for colon‐targeted drug delivery. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 92: 3630–3643, 2004     

Preparation of antibacterial temperature‐sensitive silver‐nanocomposite hydrogels from N‐isopropylacrylamide with green tea

This article reports the temperature‐sensitive, green tea (GT)‐based silver‐nanocomposite hydrogels for bacterial growth inactivation. The temperature‐sensitive hydrogels were prepared via free‐radical polymerization using temperature‐sensitive N‐isopropylacrylamide (NIPAM) monomer with GT as the hydrogel matrix. The nanocomposite hydrogels were encapsulated with silver ions via swelling method, which was later reduced to silver nanoparticles using Azadirachta indica leaf extract. The temperature‐sensitive silver nanocomposite hydrogels were analyzed by using Fourier transforms infrared, UV–visible spectroscopy, differential scanning calorimetry–thermogravimetric analysis, X‐ray diffraction, scanning electron microscopy, and transmission electron microscopy. The prepared hydrogels exhibited higher phase volume transition temperature than the NIPAM. The inhibition zone study of the inactivation of bacteria on the developed hydrogels was carried out against Gram negative (Escherichia coli) and Gram positive (Staphylococcus aureus), which revealed that the prepared hydrogels are helpful for the inactivation of these bacteria due to the high stabilization of antibacterial properties of the silver nanoparticles. The developed hydrogels are promising for biomedical applications. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018 , 135, 45739.     

Nanoclay Reinforced Self‐Cross‐Linking Poly(N‐Hydroxyethyl Acrylamide) Hydrogels with Integrated High Performances

Despite recent significant progress in fabricating tough hydrogels, it is still a challenge to realize high strength, large stretchability, high toughness, rapid recoverability, and good self‐healing simultaneously in a single hydrogel. Herein, Laponite reinforced self‐cross‐linking poly(N‐hydroxyethyl acrylamide) (PHEAA) hydrogels (i.e., PHEAA/Laponite nanocomposite [NC] gels) with dual physically cross‐linked network structures, where PHEAA chains can be self‐cross‐linked by themselves and also cross‐linked by Laponite nanoplatelets, demonstrate integrated high performances. At optimal conditions, PHEAA/Laponite NC gels exhibit high tensile strength of 1.31 MPa, ultrahigh tensile strain of 52.23 mm mm^?1, high toughness of 2238 J m^?2, rapid self‐recoverability (toughness recovery of 79% and stiffness recovery of 74% at room temperature for 2 min recovery without any external stimuli), and good self‐healing properties (strain healing efficiency of 42%). The work provides a promising and simple strategy for the fabrication of dual physically cross‐linked NC gels with integrated high performances, and helps to expand the fundamentals and applications of NC gels.     

Mesua ferrea L. seed oil based amido‐amine modified nanoclay/epoxy nanocomposites

Hydrophilic bentonite and organo‐montmorillonite (OMMT) have been modified by using a vegetable oil based amido‐amine compound. The modified nanoclays were characterized by using X‐ray diffraction (XRD) and FTIR techniques. Increase in the basal spacing after the modification was observed in both the cases. Further, Mesua ferrea L. seed oil based sulfonated epoxy resin nanocomposites have been prepared by using these modified nanoclays [3 (w/w) of clay in each case]. The XRD, TEM, SEM, FTIR, and rheological studies confirmed the formation of partially exfoliated nanocomposites. The study also confirmed that hydrophilic bentonite is not suitable nanofiller for the system, though modified bentonite slightly improves the performance characteristics of the pristine polymer. Modified OMMT based nanocomposite shows significant improvement in tensile strength (～ 1.7 times), scratch hardness (～ 2 times), gloss (14 units), and thermal stability (18°C) compared to the pristine system. This nanocomposite also exhibit better performance than OMMT based analogous nanocomposite. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

Effect of intercalant content of mica on the various properties for the charged nanocomposite poly(N‐isopropyl acrylamide) hydrogels

In this study, we intend to adjust the charge properties of the poly(N‐isopropylacrylamide) [Poly(NIPAAm)] gel by using anionic clay and cationic monomer. Hence, two series of nanocomposite hydrogels bearing different charges were designed from NIPAAm, intercalated mica (IM) (NIM‐series) and NIPAAm, IM, trimethyl (acrylamido propyl) ammonium iodide (TMAAI) (NTIM‐series), respectively. The mica was first intercalated with different contents of intercalant, trimethyl (acrylamido propyl) ammonium chloride (TMAACl), based on the cationic exchange capacity (CEC) of mica. The effect of the CEC value of IM and IM content on the charge property, swelling behaviors, mechanical properties, and drug‐release behaviors of the present gels were investigated. Results showed that the negative charges for NIM series gels decrease with increase in CEC values of the IM (from ?11 to ?6 mV), the positive charges for NTIM series gels also decrease with increase in CEC values of the IM (from +36 to +18 mV). The swelling behaviors and mechanical properties for the NTIM gels were significantly enhanced by IM content and CEC values of the IM. The microstructures, morphologies, and drug‐release behaviors in these two series gels are also investigated. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 104: 2277–2287, 2007     

Thermoreversible hydrogel. XVII. Investigation of the drug release behavior for [N‐isopropylacrylamide‐co‐trimethyl acrylamidopropyl ammonium iodide‐co‐3‐dimethyl (methacryloyloxyethyl) ammonium propane sulfonate] copolymeric hydrogels

A series of copolymeric hydrogels were prepared from various molar ratios of N‐isopropylacrylamide (NIPAAm), trimethyl acrylamidopropyl ammonium iodide (TMAAI), and 3‐dimethyl (methacryloyloxyethyl) ammonium propane sulfonate (DMAPS). Results showed that the swelling ratios of these copolymeric hydrogels increased with an increase of TMAAI content. The drug release behavior of the ionic thermosensitive hydrogels related to their ionicity and drug types. Results indicated that the release ratio of caffeine in the hydrogels was not affected by the ionicity of hydrogels, but increased with increasing of the swelling ratio. The anionic solute (phenol red) strongly interacted with cationic hydrogel (very large K_d), so the phenol red release ratio in cationic gels was very low. On the other hand, CV was adsorbed only on the skin layer of the cationic hydrogel because of the charge repulsion, and released rapidly. Therefore the release ratio was highest for cationic hydrogel to cationic drug. In addition, the partition coefficients (K_d) and the drug delivery behavior of the present gels were also investigated. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 86: 1592–1598, 2002     

Development of nanocomposites of bentonite with polyaniline and poly(methacrylic acid)

Nanocomposites of bentonite with polyaniline (PANI), poly(methacrylic acid) (PMAA), and poly(aniline‐co‐methacrylic acid) (PANI‐co‐PMAA) were prepared by in situ intercalative polymerization technique. The nanocomposites were characterized by FTIR and UV–visible spectroscopies, XRD, SEM, TEM, as well as TG‐DTA studies. The in situ intercalative polymerization of PANI, PMAA, and PANI‐co‐PMAA within bentonite layers was confirmed by FTIR, XRD, SEM, as well as TEM studies. XRD confirmed the intercalation of polymers and copolymer in bentonite. The average particle size of the nanocomposites was found to be in the range of 250–500 nm. The thermal stability was found be the highest for PANI‐co‐PMAA‐bentonite. The swelling behavior studies suggest that these nanocomposites hold potential for their utilization in absorption of toxic materials from waste water. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 103: 3299–3306, 2007     

Thermoreversible hydrogels X: Synthesis and swelling behavior of the (N‐isopropylacrylamide‐co‐sodium 2‐acrylamido‐2‐methylpropyl sulfonate) copolymeric hydrogels

A series of thermosensitive hydrogels were prepared from various molar ratios of N‐isopropylacrylamide (NIPAAm) and sodium‐2‐acrylamido‐2‐methylpropyl sulfonate (NaAMPS). Factors such as temperature and initial total monomer concentration and different pH solutions were investigated. Results indicated that the more the NaAMPS content in hydrogel system, the higher the swelling ratio and the gel transition temperature; the higher the initial monomer concentration, the lower the swelling ratio. The result also indicated that the NIPAAm/NaAMPS copolymeric hydrogels had different swelling ratios in various pH environments. The present gels showed a pH‐reversible property between pH 3 and pH 10 and thermoreversibility. The swelling ratios of copolymeric gels were lower in a strong alkaline environment because the gels were screened by counterions. Finally, the drug release behavior of these gels was also investigated in this article. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 77: 1760–1768, 2000