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1.
Thermosensitive hydrogels were prepared by free radical polymerization in aqueous solution from N‐isopropylacrylamide (NIPA) monomer and N,N‐methylenebis(acrylamide) (MBAAm) crosslinker. The swelling equilibrium of the hydrogels in deionized water was investigated as a function of temperature and MBAAm content. The results indicated that the swelling behavior and temperature sensitivity of the hydrogels were affected by the amount of MBAAm content. The average molecular mass between crosslinks and polymer–solvent interaction parameter (χ) of the hydrogels were determined from equilibrium swelling values. The swelling variations were explained according to swelling theory based on the hydrogel chemical structure. The swelling equilibrium of the hydrogels was also investigated as a function of temperature in aqueous solutions of the anionic surfactant sodium dodecyl sulfate (SDS) and the cationic surfactant dodecyltrimethylammonium bromide (DTAB). In deionized water, the hydrogels showed a discontinuous volume phase transition at 32°C. In SDS and DTAB solutions, the equilibrium swelling ratio and the volume phase transition temperature (lower critical solution temperature) of the hydrogels increased, which is ascribed to the conversion of nonionic PNIPA hydrogel into polyelectrolyte hydrogels because of binding of surfactant molecules through the hydrophobic interaction. Additionally, the amount of free SDS and DTAB ions was measured at different temperatures by a conductometric method; it was found that the electric conductivity of the PNIPA–surfactant systems depended strongly on both the type and concentration of surfactant solutions. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 101: 1756–1762, 2006  相似文献   

2.
pH‐sensitive anionic hydrogels composed of poly(vinyl alcohol) (PVA) and poly(γ‐glutamic acid) (γ‐PGA) were prepared by the freeze drying method and thermally crosslinked to suppress hydrogel deformation in water. The physical properties, swelling, and drug‐diffusion behaviors were characterized for the hydrogels. In the equilibrium swelling study, PVA/γ‐PGA hydrogels shrunk in pH regions below the pKa (2.27) of γ‐PGA, whereas they swelled above the pKa. In the drug‐diffusion study, the drug permeation rates of the PVA/γ‐PGA hydrogels were directly proportional to their swelling behaviors. The cytocompatibility test showed no cytotoxicity of the PVA/γ‐PGA hydrogels for the 3T3 fibroblast cell lines. The results of these studies suggest that hydrogels prepared from PVA and γ‐PGA could be used as orally administrable drug‐delivery systems. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008  相似文献   

3.
In the present work, a series of cross-linked LVCS/PVA hydrogels with various feed compositions were prepared using glutaraldehyde as cross-linking agent. The prepared hydrogels were used for dynamic and equilibrium swelling studies. The swelling behavior of these hydrogels was investigated as functions of effect of pH, polymeric compositions and degree of cross-linking. Swelling studies were performed in 0.05 M USP phosphate buffer solutions of varying pH 1.2, 5.5, 6.5 and 7.5. Results showed that swelling increased by increasing PVA contents in the structure of hydrogels in solutions of higher pH values. This is due to the presence of more hydroxyl groups (–OH) in the PVA structure. On the other hand, by increasing LVCS contents, swelling increased in a solution of acidic pH and it is due to ionization of amino groups (–NH2), but this swelling was not significant. Swelling of hydrogels was decreased with increase in cross-linking ratio due to tighter hydrogel structure. Porosity and sol–gel fraction were also investigated. It was found that with increase in LVCS and PVA contents porosity and gel fraction increased, whereas by increasing glutaraldehyde content gel fraction increased and porosity decreased. Diffusion coefficient (D) and network parameters, i.e., the average molecular weight between cross-links (M C), solvent interaction parameters (χ), polymer volume fraction in swollen state (V 2S) and cross-linked density (q) were calculated using Flory–Rehner theory. Selected samples were loaded with model drug diphenhydramine HCl. The release of diphenhydramine HCl was studied for 12 h period in 0.05 M USP phosphate buffer solutions of varying pH 1.2, 5.5 and 7.5. It was observed that drug release increased with increasing PVA contents in the hydrogels, while release of drug decreased as the ratio of cross-linking agent increased in the hydrogel structure owing to strong physical entanglements between polymers. The release mechanisms were studied by fitting experimental data to model equations like zero order, first order, Higuchi and Peppas. Results showed that the kinetics of drug release from hydrogels in buffer solutions of pH 1.2, 5.5 and 7.5 was mainly non-fickian diffusion. Hydrogels were characterized by Fourier transform infrared and X-ray diffraction to confirm the structure and study the crystallinity of hydrogel, respectively.  相似文献   

4.
Poly (acrylamide‐co‐methyl methacrylate) hydrogels of different ratios were prepared by using chemical and physical crosslinks to study the effect of nature of crosslinks on swelling behavior of hydrogels. The chemically crosslinked gels were prepared by using NN′‐methylene bis acrylamide, while physically crosslinked hydrogels were prepared by precipitation polymerization method, using dioxane as solvent. Detailed swelling kinetics such as swelling ratio, transport exponent n, diffusion coefficient D and the effect of pH on equilibrium swelling studies. The study revealed that the nature of crosslinks alter the swelling characteristics of the hydrogel. In chemically crosslinked hydrogels the water transport is Fickian in nature, while in the case of the physically crosslinked hydrogels the water transport mechanism is anomalous indicating major change in relaxation mechanism due to nature of crosslinks. The results also indicate that with increasing acrylamide content the swelling ratio of the hydrogels were also increased, but the transport exponent n remains nearly constant. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 89: 779–786, 2003  相似文献   

5.
Novel pH‐sensitive chitosan‐poly(acrylamide‐co‐itaconic acid) hydrogels were prepared by free radical copolymerization of acrylamide and itaconic acid (IA) in chitosan solution. The hydrogels were characterized using Fourier transform infrared spectroscopy, scanning electron microscopy, thermogravimetric analysis, differential scanning calorimetry and the swelling ratios of the hydrogels in water (pH 6.8) and pH 1.2. The influence of composition on the thermal properties of the hydrogels was assessed. The glass transition temperatures of the samples increased with IA content, ranging from 110 to 136 °C. Swelling of the hydrogels was found to obey second‐order kinetics with respect to the remnant swelling, indicating that diffusion is controlled by the relaxation of chains. The equilibrium swelling degree was strongly dependent on pH and composition. At both pH values the highest water uptake was obtained for the IA‐free sample M1. From the equilibrium swelling results the average molar mass between crosslinks, Mc, and the crosslink density of the chitosan‐poly(acrylamide‐co‐itaconic acid) samples were calculated. The results evidenced the reinforcing effect of IA on the hydrogel structure. It is concluded that these highly swellable pH‐sensitive hydrogels can be useful for applications in biomedicine and pharmacy. © 2013 Society of Chemical Industry  相似文献   

6.
Temperature‐sensitive poly[(2‐diethylaminoethyl methacrylate)‐co‐(N,N‐dimethylacrylamide)] [P(DEAEMA‐co‐DMAAm)] hydrogels with five different DMAAm contents were synthesized with and without the addition of sodium carbonate as porosity generator. The synthesized hydrogels were characterized with dry gel density measurements, scanning electron microscopy observation and the determination of swelling ratio. The influence of the pore‐forming agent and content of DMAAm on swelling ratio and network parameters such as polymer–solvent interaction parameter (χ), average molecular mass between crosslinks (M?c) and mesh size (ζ) of the cryogels are reported and discussed. The swelling and deswelling rates of the porous hydrogels are much faster than for the same type of hydrogels prepared via conventional methods. At a temperature below the volume phase transition temperature, the macroporous hydrogels also absorbed larger amounts water compared to that of conventional hydrogels and showed obviously higher equilibrated swelling ratios in aqueous medium. In particular, the unique macroporous structure provided numerous water channels for water diffusion in or out of the matrix and, therefore, an improved response rate to the external temperature changes during the deswelling and swelling processes. These properties are attributed to the macroporous and regularly arranged network of the porous hydrogels. Scanning electron micrographs reveal that the macroporous network structure of the hydrogels can be adjusted by applying porosity generation methods during the polymerization reaction. Copyright © 2007 Society of Chemical Industry  相似文献   

7.
In this study, a random copolymer of acylamide and acrylic acid [poly(AAm‐co‐AA)] was prepared by a redox copolymerization method of their aqueous solutions. The effects of initial AAm/AA mole ratio, PEG 4000 content, and N,N′‐methylenebisacrylamide concentration on swelling behavior were investigated in water. Average molecular weights between crosslinks, percentage swelling, swelling equilibrium values, and diffusion/swelling characteristics (i.e., the structure of network constant, the type of diffusion, the initial swelling rate, swelling rate constant) were evaluated for every hydrogel systems. The hydrogels showed mass swelling capabilities in the range 789–1040% (for AAm/AA hydrogels), 769–930% (for AAm/AA hydrogels in the presence of PEG 4000), and 716–1040% (for AAm/AA hydrogels containing different concentrations of the crosslinker). The swelling capabilities of the hydrogels decreased with the increasing AA, PEG 4000, and crosslinker concentrations. The diffusion of water into AAm/AA hydrogels was found to be a non‐Fickian type. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 91: 1289–1293, 2004  相似文献   

8.
The objective of the present work was to synthesize interpenetrating networks (IPNs) of acrylic acid/polyvinyl alcohol (AA/PVA) by free radical polymerization using N,N-methylenebisacrylamide (MBAAm) and glutaraldehyde as cross-linkers. The IPNs were evaluated for swelling, diffusion coefficient and network parameters by using Flory–Huggins theory, i.e., the average molecular weight between cross-links (M c), polymer volume fraction in swollen state (V 2,s), number of repeating units between cross-links (M r) and cross-linking density (N). It was found that the degree of swelling of AA/PVA interpenetrating network increases greatly within the pH range 5–7 depending on composition. The gel fraction and porosity increased by increasing the concentration of AA or PVA, while by increasing the degree of cross-linking, porosity decreased and gel fraction increased. Selected samples were loaded with chlorpheniramine maleate as a model drug. Drug release was studied in USP, hydrochloric acid buffer solution of pH 1.2 and phosphate buffer solutions of pH 5.5 and 7.5. Drug release data were fitted into various kinetics models, e.g., zero-order, first-order, Higuchi and Peppas models. The results of the kinetics investigation showed that the drug release from IPNs followed non-Fickian diffusion. Fourier transform infrared spectra confirmed the formation of cross-linked IPNs as there was a shifting to lower frequency of 1,713–1,718 cm?1 with reduced intensity, while scanning electron microscopy revealed uniform distribution of drug in IPNs.  相似文献   

9.
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  相似文献   

10.
The aim of the present exploration was to develop novel pH-sensitive cross-linked Gelatin/Polyvinyl pyrrolidone hydrogels using different ratios of both the polymers and to investigate the effect of polymers and degree of crosslinking on dynamic, equilibrium swelling and invitro release pattern of the model drug (captopril). Grafting polymerization technique was used for the preparation of these hydrogels using glutaraldehyde as crosslinking agent. These polymeric materials were then used as model systems to envisage various important characterizations like FTIR (Fourier transform infrared spectroscopy), XRD (X-ray diffraction) and scanning electron microscopy (SEM). Phosphate buffers of pH 1.2, 6.5 and 7.5 were used for swelling and invitro drug release profile investigation. Different parameters like swelling analysis, porosity, sol-gel analysis, average molecular weight between crosslinks (Mc), solvent interaction parameter (χ), volume fraction of polymer (V2,s) and diffusion coefficient that affects the drug release behavior were also determined. Higher swelling and release was observed at lower pH values. FTIR spectra showed interaction between gelatin and polyvinyl pyrrolidone and successful formation of cross-linked structure. Pulsatile drug release study showed the controlled delivery of model drug. The release of drug occurred through non-fickian diffusion or anomalous mechanism. Aforementioned characterizations reveal successful formation of copolymer. pH sensitive swelling ability and drug release behavior suggest that the rate of polymer chain relaxation and the rate of drug diffusion from these hydrogels are comparable which also predicts their possible use for site specific captopril delivery.  相似文献   

11.
A series of pH‐responsive hydrogels were studied as potential drug carriers for the protection of insulin from the acidic environment of the stomach before releasing in the small intestine. Hydrogels based on poly(vinyl alcohol) networks grafted with acrylic acid or methacrylic acid were prepared by a two‐step process. Poly(vinyl alcohol) hydrogels were prepared by gamma ray irradiation (50 kGy) and then followed by grafting either acrylic acid or methacrylic acid onto these poly(vinyl alcohol) hydrogels with subsequent irradiation (5–20 kGy). These graft hydrogels showed pH‐sensitive swelling behavior and were used as carriers for the controlled release of insulin. The in vitro release of insulin was observed for the insulin‐loaded hydrogels in a simulated intestinal fluid (pH 6.8) but not in a simulated gastric fluid (pH 1.2). The release behavior of insulin in vivo in a rat model confirmed the effectiveness of the oral delivery of insulin to control the level of glucose. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 91: 636–643, 2004  相似文献   

12.
Two series of pH‐responsive biodegradable interpolymeric (IPN) hydrogels based on chitosan (Ch) and poly(vinyl alcohol) (PVA) were prepared for controlled drug release investigations. The first series was chemically crosslinked with different concentrations of glutaraldehyde and the second was crosslinked upon γ‐irradiation by different doses. The equilibrium swelling characteristics were investigated for the gels at 37°C in buffer solutions of pH 2.1 and 7.4 as simulated gastric and intestinal fluids, respectively. 5‐Fluorouracil (FU) was entrapped in the hydrogels, as a model therapeutic agent, and the in vitro release profiles of the drug were established at 37°C in pH 2.1 and 7.4. FTIR, SEM, and X‐ray diffraction analyses were used to characterize and investigate the structural changes of the gels with the variation of the blend composition and crosslinker content before and after the drug loading. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 103: 2864–2874, 2007  相似文献   

13.
In this study, we have synthesized dextran hydrogels by the crosslinking reactions of dextran with some selective Cl‐, and N‐containing functional monomers, such as epichlorohydrin (ECH), N,N′‐methylenebisacrylamide (MBAm), and glutaraldehyde (GA). Crosslinking reactions were carried out in the basic aqueous solutions (2.8NNaOH) at 25–50°C. The optimum conditions for effective crosslinking, i.e., temperature, crosslinking time, and amount of crosslinker, were determined for each system. The hydrogel discs of 3 mm diameter and 1.5 mm thickness were subjected to a number of Tris‐buffer solutions of desired pH (2.0–9.0) at 37°C. Swelling kinetics of the hydrogels were evaluated with second–order swelling model. The pH‐dependent swelling of hydrogels was strongly influenced by the functional group of crosslinker and crosslinker content. While the hydrogels prepared with ECH and MBAm shows higher swelling ability at basic medium than that of acidic medium, GA‐containing hydrogels exhibited just the opposite behavior. Mesh sizes (ξ) and average molecular weights between crosslinks (Mc) were estimated from swelling data using the Flory‐Rehner theory. Characterization studies were completed by Fourier transform infrared spectroscopy and thermal gravimetric analysis. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 102:4213–4221, 2006  相似文献   

14.
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.  相似文献   

15.
The multifunctional double network (DN) soft hydrogels reported here are highly swellable and stretchable pH‐responsive smart hydrogel materials with sufficient strength and self‐healing properties. Such multifunctional hydrogels are achieved using double crosslinking structures with multiple physical and chemical crosslinks. They consist of a copolymer network of acrylamide (AM) and sodium acrylate (Na‐AA) and other reversible network of poly(vinyl alcohol)–borax complex. They were characterized by Fourier transform IR analysis and studied for their hydrogen bonding and ionic interaction. The degree of equilibrium swelling was observed to be as high as 5959% (at pH 7.0) for a hydrogel with AM/Na‐AA = 25/75 wt% in the network (GS‐6 sample). The highest degree of swelling was observed to be 6494% at pH 8.5. The maximum tensile strength was measured to be 1670, 580 and 130 kPa for a DN hydrogel (GS‐2 sample: AM/Na‐AA =75/25 wt% with 20, 40 and 60 wt% water content, respectively). The self‐healing efficiency was estimated to be 69% for such a hydrogel. These multifunctional DN hydrogels with amalgamation of many functional properties are unique in hydrogel materials and such materials may find applications in sensors, actuators, smart windows and biomedical applications. © 2018 Society of Chemical Industry  相似文献   

16.
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  相似文献   

17.
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.  相似文献   


18.
The swelling properties of different chitosan–poly(vinyl alcohol) (PVA) hydrogels were investigated as functions of the medium pH and salt concentration. The maximum swelling ability of the hydrogels was at a buffer pH of approximately 3, regardless of the PVA content in the hydrogels. The maximum mass of the swollen hydrogels was about 13 times that of their contracted counterparts. The cyclical swelling and contraction between pH 3 and pH 7 buffers and pH 3 and pH 3 buffers with salt confirmed the Donnan swelling mechanism of these hydrogels. The swelling mechanism was considered the transfer of water molecules driven by a concentration gradient. This was represented by a simplified mass‐balance model, which neglected the effect of the ionization reaction, for the initial swelling period. The effective mass‐transfer coefficient of water molecules during swelling, estimated with this model, gradually decreased with increasing PVA content in the hydrogels. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 102: 4665–4671, 2006  相似文献   

19.
To improve equilibrium water content, dehydrothermally crosslinked poly(vinyl alcohol) (PVA) hydrogel was grafted with N‐vinyl pyrrolidone (NVP) or acrylic acid (AA) monomer using γ‐radiation. Swelling behavior of the grafted hydrogels was studied in phosphate‐buffered saline, and cell viability was evaluated using fibroblast cells from mouse connective tissue. Equilibrium water content of AA‐ and NVP‐grafted PVA hydrogel ranged between 40–60% and 60–80%, respectively, depending on radiation dose and monomer concentration. For maximum degree of swelling, the optimum monomer concentration and radiation dose were 20% by weight and 20 kGy, respectively. Fibroblast cells seeded on NVP‐grafted hydrogel had an extended oval morphology while those seeded on AA‐grafted PVA had a rounded spherical morphology. These results support the use of NVP for grafting PVA to increase swelling and improve cell viability. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 91: 2862–2868, 2004  相似文献   

20.
Hydrogels, composed of poly(N‐vinyl‐2‐pyrrolidone) and crosslinked polyacrylamide, were synthesized and the release of vitamin B12 from these hydrogels was studied as a function of the degree of crosslinking and pH of the external swelling media. The three drug‐loaded hydrogel samples synthesized with different crosslinking ratios of 0.3, 0.7, and 1.2 (in mol %) follow different drug‐release mechanisms, that is, chain relaxation with zero‐order, non‐Fickian and Fickian, or diffusion‐controlled mechanisms. To establish a correlation between their swelling behavior and drug‐release mechanism, the former was studied by the weight‐gain method and, at the same time, the concentration of the drug released was studied colorimetrically. Various swelling parameters such as the swelling exponent n, gel‐characteristic constant k, penetration velocity v, and diffusion coefficient D were evaluated to reflect the quantitative aspect of the swelling behavior of these hydrogels. Finally, the drug‐release behavior of the hydrogels was explained by proposing the swelling‐dependent mechanism. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 76: 1706–1714, 2000  相似文献   

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