Effect of fluorinated hydrophobic monomer on the drug release behavior for the thermosensitive hydrogels

Three series of copolymeric gels based on N‐isopropylacrylamide (NIPAAm) and perfluoroalkyl methacrylate such as 2,2,3,3,4,4,5,5‐octafluoropentyl methacrylate (OFPMA), 4,4,5,5,6,7,7,7‐octafluoro‐2‐hydroxy‐6‐(trifluoromethyl)heptyl methacrylate (OFHHMA), and 3,3,4,4,5,6,6,6‐octafluoro‐5‐(trifluoromethyl)hexyl methacrylate (OFHMA), were prepared by emulsion polymerization. The effect of perfluoroalkyl methacrylate and sodium lauryl sulfate (SLS), which can act as a surfactant and a pore‐forming agent, on the equilibrium swelling ratio and mechanical properties of the present hydrogels was investigated. Results show that hydrophobic monomers made the swelling ratio of the gel decrease and the mechanical property of the gel increase; however, SLS exhibits a contrary result. In addition, the effect of perfluoroalkyl methacrylate on the drug release behavior was also investigated. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 100: 4661–4667, 2006     

Volume phase transition temperature tuning and investigation of the swelling–deswelling oscillation of responsive microgels

Temperature‐ and pH‐responsive polyampholyte microgels were prepared by an aqueous dispersion polymerization. Scanning electron microscopy and dynamic laser light scattering (DLS) were employed for the characterization of the morphology and size distribution of the microgels. Temperature‐ and pH‐dependent volume phase transitions of the polyampholyte microgels were also investigated using DLS. The microgels showed an interesting swelling–deswelling oscillatory behavior when the pH was varied. An interpretation was proposed for the phenomenon in terms of Coulombic repulsion and hydrophobic hydration. It is of great interest that the volume phase transition temperature (VPTT) of the polyampholyte microgels can be varied by changing the pH. This could be a convenient approach for tuning the VPTT of N‐isopropylacrylamide‐based hydrogels. Copyright © 2007 Society of Chemical Industry     

Thermoreversible hydrogels. IV. Effect of some factors on the swelling behavior of N-tetrahydrofurfurylacrylamide

A thermoreversible hydrogel, poly(N-tetrahydrofurfurylacrylamide) [poly-(NTHFAAm) gel], was prepared from N-tetrahydrofurfurylacrylamide, which was synthesized from N-tetrahydrofurfurylamine and acryloyl chloride (through acylation), with N,N′-methylenebisacrylamide, a crosslinker, in various aqueous solutions. The influences of temperature, gel thickness, and polymerization media on the swelling behaviors in water were investigated. The effect of the gel thickness on the swelling ratio for NTHFAAm gel indicated that the equilibrium swelling time and diffusion coefficient for the thinner gel were faster than those for the thicker gels. The effects of different polymerization media on the gel swelling ratio showed that the larger the solvent molecular size and the poorer the miscibility of the monomer and solvent, the higher the swelling ratio and diffusion coefficient. The drug release profiles in the various gels were also investigated. © 1998 John Wiley & Sons, Inc. J Appl Polym Sci 68: 1597–1603, 1998     

Swelling–deswelling behavior of poly(acrylamide‐co‐maleic acid) hydrogels

In this study the poly(acrylamide‐co‐maleic acid) hydrogels containing small amounts of maleic acid have been synthesized, and the effect of pH, ionic strength, and nature of counterions on the equilibrium water uptake has been investigated. The incorporation of small amount of maleic acid results in the transition of swelling mechanism from Fickian to non‐Fickian. The equilibrium mass swelling has been found to increase with pH of the swelling medium while increase in ionic strength causes a decrease in the swelling. The amount of maleic acid present in the hydrogel affects the swelling behavior in rather an unusual way. With lower acid contents, the equilibrium mass swelling increases while higher concentrations of maleic acid cause a decrease in the degree of swelling. The hydrogels have been found to undergo a number of swelling–deswelling cycles when pH of the swelling medium changes from 8.0 to 2.0. Hydrogels require more time to deswell compared to the time required for swelling, which has been explained on the basis of the fact that gels follow different mechanisms for the two processes. Various swelling parameters such as equilibrium mass swelling, diffusion coefficient, intrinsic diffusion coefficient, swelling exponent, etc., have been evaluated. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 80: 2782–2789, 2001     

pH–thermoreversible hydrogels. II. Synthesis and swelling behaviors of N-isopropylacrylamide-co-acrylic acid-co-sodium acrylate hydrogels

A series of pH–thermoreversible hydrogels are prepared from the three molar ratios of N-isopropylacrylamide (NIPAAm) and acrylic acid neutralized 50 mol % by sodium hydroxide (SA50) and N,N′-methylene bisacrylamide (NMBA). The influence of the environmental conditions, such as temperature and pH values, on the swelling behavior of these copolymeric gels is also investigated in this article. Results show that the hydrogels bearing negative charges exhibit different equilibrium swelling ratios under various pH media. The pH sensitivities of these gels also strongly depend on the molar ratio of SA50 in the copolymeric gels; thus, the more the SA50 content, the higher the gel pH sensitivity. These hydrogels exhibited thermosensitivity demonstrating a larger change of the equilibrium swelling ratio in aqueous media under temperature changes. An overshooting phenomenon is observed from the gel swelling kinetics under high-temperature conditions. The said hydrogels are also used to investigate the release of model drugs in this study. © 1999 John Wiley & Sons, Inc. J Appl Polym Sci 73: 1955–1967, 1999     

pH‐thermoreversible hydrogels. I. Synthesis and swelling behaviors of the (N‐isopropylacrylamide‐co‐acrylamide‐co‐2‐hydroxyethyl methacrylate) copolymeric hydrogels

A series of pH‐thermoreversible hydrogels that exhibited volume phase transition was synthesized by various molar ratios of N‐isopropylacrylamide (NIPAAm), acrylamide (AAm), and 2‐hydroxyethyl methacrylate (HEMA). The influence of environmental conditions such as temperature and pH value on the swelling behavior of these copolymeric gels was investigated. Results showed that the hydrogels exhibited different equilibrium swelling ratios in different pH solutions. Amide groups could be hydrolyzed to form negatively charged carboxylate ion groups in their hydrophilic polymeric network in response to an external pH variation. The pH sensitivities of these gels also depended on the AAm content in the copolymeric gels; thus the greater the AAm content, the higher the pH sensitivity. These hydrogels, based on a temperature‐sensitive hydrogel, demonstrated a significant change of equilibrium swelling in aqueous media between a highly solvated, swollen gel state and a dehydrated network response to small variations of temperature. pH‐thermoreversible hydrogels were used for a study of the release of a model drug, caffeine, with changes in temperature. © 1999 John Wiley & Sons, Inc. J Appl Polym Sci 71: 221–231, 1999     

Thermoreversible hydrogels. I. Synthesis and effect of a hydrophobic monomer on swelling behaviors of thermoreversible gels prepared by copolymerizing N-alkoxyalkylacrylamide with butyl acrylate

A series of copolymeric gels were prepared from N-alkoxyalkylacrylamide and n-butyl acrylate (BA) at various feed ratios. The effect of the content of BA in the copolymer on the gel behaviors is discussed. The respective crosslinked copolymer exhibits a gel transition behavior, collapsing and shrinking above gel transition temperature but swelling and reexpanding below gel transition temperature. By utilizing this character, these copolymeric gels could be used for drug release or drug delivery systems. The drug released from the copolymeric gels was plotted as M_t/M_∞ versus t, where M_t/M_∞ is the fraction of drug released at given time t. In this experiment, crystal violet and caffeine were chosen as model drugs. The deswelling-kinetics experiments with caffeine showed that a water pocket was formed within the gel matrix when the gel deswelled rapidly. © 1997 John Wiley & Sons, Inc. J Appl Polym Sci 64: 1477–1484, 1997     

Effect of porosigen on the swelling behavior and drug release of porous N‐isopropylacrylamide/poly(ethylene glycol) monomethylether acrylate copolymeric hydrogels

A series of porous thermoreversible hydrogels were prepared from N‐isopropylacrylamide (90 mol %) and poly(ethylene glycol) methylether acrylate (10 mol %), which was derived from poly(ethylene glycol) monomethylether, N,N′‐methylenebisacrylamide, and porosigen, or poly (ethylene glycol) (PEG) with different molecular weights (MWs). The influence of pore volume in the gel on the physical properties, swelling kinetics, and solute permeation from these porous gels was investigated. The results show that the surface areas, pore volumes, and equilibrium swelling ratios for the porous gels increased with increasing MW of PEG, but the shear moduli and effective crosslinking densities decreased with increasing MW of PEG. The results from the dynamic swelling kinetics show that the transport mechanism was non‐Fickian. The diffusion coefficients of water penetrating into the gels increased with increasing pore volume of the gels. In addition, we also studied solute permeation through the porous gel controlled by temperature. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 102: 5490–5499, 2006     

pH‐sensitive swelling and release behaviors of anionic hydrogels for intelligent drug delivery system

The pH‐sensitive swelling and release behaviors of the anionic P(MAA‐co‐EGMA) hydrogels were investigated as a biological on–off switch for the design of an intelligent drug delivery system triggered by external pH changes. There was a drastic change of the equilibrium weight swelling ratio of P(MAA‐co‐EGMA) hydrogels at a pH of around 5, which is the pK_a of poly (methacrylic acid) (PMAA). At a pH below 5, the hydrogels were in a relatively collapsed state but at a pH higher than 5, the hydrogels swelled to a high degree. When the molecular weight of the pendent poly(ethylene glycol) (PEG) of the P(MAA‐co‐EGMA) increased, the swelling ratio decreased at a pH higher than 5. The pK_a values of the P(MAA‐co‐EGMA) hydrogels moved to a higher pH range as the pendent PEG molecular weight increased. When the feed concentration of the crosslinker of the hydrogel increased the swelling ratio of the P(MAA‐co‐EGMA) hydrogels decreased at a pH higher than 5. In release experiments using Rhodamine B (Rh‐B) as a model solute, the P(MAA‐co‐EGMA) hydrogels showed a pH‐sensitive release behavior. At low pH (pH 4.0) a small amount of Rh‐B was released while at high pH (pH 6.0) a relatively large amount of Rh‐B was released from the hydrogels. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 2007     

Swelling,compression and tribological behaviors of bentonite‐modified polyacrylate‐type hydrogels

Hydrogel was synthesized from acrylamide and 2‐acryloylamido‐2‐methylpropanesulfonic acid monomers (ratio: 50/50 wt %) and crosslinked with 0.25 wt % of methylene‐bisacrylamide. This hydrogel was also modified by adding 4 wt % of sodium bentonite (NB). Selected properties of the hydrogels with and without NB were investigated and compared. Their water uptake was measured gravimetrically; the compression and compression creep were assessed by dynamic‐mechanical and thermo‐mechanical analysis (DMA and TMA, respectively) techniques. The friction and wear of the hydrogels were determined in a shaft(metal)‐on‐plate(hydrogel) type testing configuration under water lubrication. The hydrogel was transparent and exhibited very high equilibrium water content (>99 wt %). The latter was less affected; however, the hydrogel became slightly more hazy after NB incorporation. The crosslink density of the hydrogels was deduced from swelling and compression tests and compared with the theoretical values. Modification by NB enhanced the ultimate compression strength and reduced the related compression strain. The compression creep response under both loading and deloading strongly depended on the level of the initial load. A very low friction coefficient (～ 0.003) and a relatively high specific wear rate (～ 0.05 mm³/N m) were registered under water lubricated sliding wear using a metallic counterpart with high surface roughness. Scanning electron microscopy combined with energy dispersive spectroscopy delivered additional information on the NB dispersion and surface structure of the hydrogels. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

pH‐reversible hydrogels. IV. Swelling behavior of the 2‐hydroxyethyl methacrylate‐co‐acrylic acid‐co‐sodium acrylate copolymeric hydrogels

A series of 2‐hydroxyethyl methacrylate (HEMA) and sodium acrylate (SA50) copolymeric gels were prepared from HEMA and the anionic monomer SA50 with various molar ratios. The influence of SA50 on the copolymeric gels on their swelling behavior in deionized water at different temperatures and various pH buffer solutions was investigated. Results indicated that the poly(2‐hydroxyethyl methacrylate) (PHEMA) hydrogels exhibited an overshooting phenomenon in their dynamic swelling behavior. The maximum overshooting value decreased with increasing of the temperature. The same results were also found in the HEMA/SA50 copolymeric gels with a lower SA50 content. On the contrary, the overshooting phenomenon for HEMA/SA50 copolymeric gels with a higher content of SA50 was exhibited only under higher temperature (over 35°C). These copolymer gels were used to assess drug release and drug delivery in this article. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 81: 1360–1371, 2001     

Effect of the sodium dodecyl sulfate/monomer ratio on the network structure of hydrophobic association hydrogels with adjustable mechanical properties

The study of gel‐network structure is not as extensive as the study of the application of hydrogels. However, the distribution of the inner structure is crucial for designing hydrogels with tunable mechanical properties to meet certain kinds of demands. In this study, a series of hydrophobic association hydrogels (HA‐gels) were synthesized by free‐radical micellar copolymerization in a sodium dodecyl sulfate (SDS) surfactant solution. The hydrophobic monomer was palmityl alcohol poly(oxyethylene acrylate) (AEO–AC), which is an ecofriendly alternative to the traditional octyl phenol poly(oxyethylene acrylate). Interestingly, we found that the molar ratio [or ratio point (R)] of SDS to AEO–AC played a key role in tuning the mechanical properties. All series HA‐gels denominated a similar down–up–down tendency with increasing R, and the best R is 3. This result was consistent with the microscopic network structure number of the hydrophobic monomer (N_H = 21–24), and this indicated that each hydrophobic monomer associated three SDS monomers in its internal networks. The resulting AEO–AC–acrylamide gels exhibited the best mechanical strength (yield maximum broken stress = 218 kPa) and the maximum effective crosslink density. Moreover, the relationship between the network structure and the mechanical properties of the HA‐gels was investigated with various Rs. Two different interaction effects of distribution between SDS and AEO–AC are discussed in detail. The HA‐gels exhibited self‐healing properties and maintained their shape in water over 160 days. The results indicate that changing R is an effective method for tuning the mechanical properties of HA‐gels as a type of prospective biomedical material. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134, 45196.     

Thermal behaviors and flame‐retardancy of styrene–ethylene–butadiene–styrene–block copolymer containing various additives

The thermal behaviors and the flame‐retardancy of styrene–ethylene–butadiene–styrene–block copolymer containing various additives were studied. The combustion was measured by the Underwriter laboratory (UL) test and cone calorimeter test and thermogravimetric analysis and program‐mass spectroscopy were applied to analyze the thermal behaviors. The blend with halogen additives showed the best result in the UL test. However, the blend with red‐phosphorous was the best in the cone calorimeter test. As the styrene sequence in the copolymer tended to degradate at a lower temperature, the major scission products spouted out from the polymer surface originated from polystyrene. The shorter the ignition times of the blends with red‐phosphorous were, the lower the peak heat release rates were. It was an interesting phenomenon because it suggested that the chemical structure of the residue changed to more stable polymers. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 104: 156–161, 2007     

Synthesis,characterization, and in vitro release of ibuprofen from poly(MMA‐HEMA) copolymeric core–shell hydrogel microspheres for biomedical applications

This article describes the development of a new crosslinked poly(methyl methacrylate‐2‐hydroxyethyl methacrylate) copolymeric core–shell hydrogel microsphere incorporated with ibuprofen for potential applications in bone implants. Initially poly(methyl methacrylate) (PMMA) core microspheres were prepared by free‐radical initiation technique. On these core microspheres, 2‐hydroxyethyl methacrylate (HEMA) was polymerized by swelling PMMA microspheres with the HEMA monomer by using ascorbic acid and ammonium persulfate. Crosslinking monomers such as ethylene glycol dimethacrylate (EGDMA) has also been included along with HEMA for polymerization. By this technique, it was possible to obtain core–shell‐type microspheres. The core is a hard PMMA microsphere having a hydrophilic poly(HEMA) shell coat on it. These microspheres are highly hydrophilic as compared to PMMA microspheres. The size of the hydrogel microspheres almost doubled when swollen in benzyl alcohol. These microspheres were characterized by various techniques such as optical microscopy, scanning electron microscopy, Fourier‐transformed infrared spectroscopy, thermogravimetric analysis, and differential scanning calorimetry. The particle size of both microspheres was analyzed by using Malvern Master Sizer/E particle size analyzer. The in vitro release of ibuprofen from both microspheres showed near zero‐order patterns. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 83: 3045–3054, 2002; DOI 10.1002/app.10310     

Effects of argon plasma treatment on surface characteristic of photopolymerization PEGDA–HEMA hydrogels

The aim of this research was to determine the influence of argon plasma treatment condition on the surface properties of poly(ethylene glycol) diacrylate (PEGDA)–hydroxyethly methacrylate hydrogel films, a kind of scaffold materials for tissue engineering. The changes of surface properties have been evaluated by contact angles, X‐ray photoelectron spectra (XPS), and scanning electron microscopy (SEM). From the contact angle measurements of different liquids, the surface free energy of the hydrogel was calculated according to approaches by Owens–Wendt–Kaelble. Results showed that the contact angle of the hydrogel to water decreased remarkably after argon plasma treatment, which was caused by the changes in morphology (SEM images) and chemical composition (XPS results) of the argon plasma‐treated surface. The surface free energy increased with the increase of the argon plasma treated time and power, and these increasing was mainly due to the increase of polar component. The XPS results confirmed that plasma oxidation reaction produced oxygen‐containing functional groups onto the surface. This functional group played an important role in increasing the hydrophilic properties of the hydrogel. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

Influence of interlayer cations on the water sorption and swelling–shrinkage of MX80 bentonite

The potential of water sorption and swelling–shrinkage in the expansive clays is practically defined by the nature of interlayer cations. The purpose of this paper is to estimate the effects of the cation saturation (Mg⁺, Ca⁺, Li⁺, Na⁺, and K⁺) on the swelling–shrinkage behaviour of the MX80 bentonite.The MX80 bentonite (a “commercial clay”) was treated with concentrated solutions (1 N) of sodium, calcium, magnesium, potassium, and lithium chlorides. This treatment was made three times with constant agitation for 1 h. Then, the clay was washed three times with distilled water. The scanning transmission electron microscopy (STEM) and inductively coupled plasma atomic emission microscopy (ICP-AES) analyses were used to verify the efficiency of the cation saturation.Finally, two techniques were employed to estimate the effect of the cation saturation on the swelling–shrinkage behaviour of the bentonite: the first one uses an isothermal system of water adsorption, where the water activity is controlled by a supersaturated salt solution. In the second, environmental scanning electron microscopy (ESEM), coupled with a digital image analysis (DIA) program, was used to estimate the swelling–shrinkage potential at different water activities. The swelling–shrinkage isotherms were always estimated on isolated aggregates.The isotherms of water adsorption and swelling–shrinkage of the bentonite MX80 show that the amount of adsorbed water and the swelling–shrinkage potential depend directly on the interlayer cation. For example, the sodium bentonite presents an excellent capacity to swell while the lithium bentonite does not swell significantly at the aggregate scale. In addition, other textural properties may be modified by the cation saturation, such as the specific surface, the particle size, porosity, etc.     

Influence of polyvinylpyrrolidone on the hydrophobic properties of partially porous poly(styrene–divinylbenzene) particles for biological applications

For the preparation of polymer particles by free radical, stabilizers are usually present in the reaction mixture to maintain the separation of particles from each other. Polyvinylpyrrolidone (PVP) is one the hydrophilic polymers that has been extensively used as the stabilizer in the polymerization system employing a polar solvent or solvent mixture as the continuous phase. As shown in the present study, the presence of PVP in the later steps could significantly influence the hydrophobic property of partially porous poly(styrene–divinylbenzene) (PS–DVB) particles, prepared by the method of multistep swelling and polymerization involving the use of polymeric porogens. The association of PVP molecules on the particle surface reduced the hydrophobicity and consequently the capability of particles for biological applications. For the reversed‐phase liquid chromatography of penicillin G and its enzymatic hydrolysis product, particles prepared without PVP led to an enhancement in both retention and resolution, compared with particles resulting from the use of PVP. Results from lipase immobilization on these particles also showed that the presence of PVP could shield the hydrophobic groups on the particle surface and then reduce the efficiency of enzyme immobilization. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 87: 1818–1824, 2003     

Water‐swellable hydrophobic porous copolymer resins based on divinylbenzene and acrylonitrile. I. Water‐swelling behavior

Hydrophobic porous copolymer resins based on divinylbenzene (DVB) and acrylonitrile (AN) could be prepared as directly swellable in water by using purified DVB (98.8%) and technical DVB (79.3%) in the presence of 1,2‐dichloroethane as porogen. Compared with the resins based on DVB and methyl acrylate (MA/DVB resins), the AN/DVB resins thus obtained are water‐swellable over a wider range of copolymer compositions, and the swelling ability of the AN/DVB resins in water was further confirmed by investigating the water‐swelling behavior of the AN/DVB resins undergoing solvent treatment. The copolymer composition (AN and DVB contents) of the resins and the property of the porogen affect the water‐swellable behavior of the AN/DVB resins profoundly. The results in this paper provide additional evidence to support the hypothesis that the swelling ability of a hydrophobic porous copolymer in water originates from the existence of the inner stresses in the strained polymer network of the resins and the weak interaction between polymer and water that is negligible in the case of a conventional hydrophobic polymer. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 94: 2041–2049, 2004     

Water‐swellable hydrophobic porous copolymer resins based on divinylbenzene and acrylonitrile. II. Pore structure and adsorption behavior

By using purified divinylbenzene (DVB, 98.8%) or technical DVB (79.3%), the hydrophobic, but water‐wettable or swellable porous copolymer resins based on DVB and acrylonitrile (AN) could be prepared with a wide range of pore structures under certain conditions. The specific surface area for the resulting AN/DVB resin, with an AN/DVB ratio of 40/60 (by mole), could reach a value of 704 m²/g, while such a resin is still water wettable or swellable by direct contact with water. The adsorption behavior of the AN/DVB resins was investigated by focusing on the comparison between the resins with and without prewetting, using caffeine and phenol as model adsorbates. Adsorption behavior of the AN/DVB resins, without prewetting, correlates well with the wetting ability of the resins in water, suggesting that a well water‐wettable hydrophobic porous AN/DVB resin could be directly applied, in a dry state, to the adsorption in an aqueous medium, almost without diminishing the ability of the resin to adsorb the solutes. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 94: 2050–2056, 2004     

Effect of crosslinking concentration on mechanical and thermodynamic properties in acrylic acid–co–methyl methacrylate hydrogels

The mechanical and thermodynamic properties of poly(acrylic acid‐co‐methyl methacrylate) hydrogels with varying crosslinker N,N′‐methylenebisacrylamide (NMBA) content are reported. A higher NMBA content generally led to a stronger and harder gel with lower water content. Swelling capacity decreased as the NMBA concentration increased between 0.5% and 2%, remaining constant beyond this range. The temperature changes of the partial molar Gibbs free energy of dilution and enthalpic and entropic contributions were examined. The thermodynamic parameters showed that swelling was an unfavorable and endothermic process. The freezing and nonfreezing water in the hydrogel was determined by differential scanning calorimetry (DSC). Freezing water content decreased with increasing crosslinker (NMBA) content, whereas the ratio of nonfreezing water to total water content increased with NMBA content because of the promoting of hydrophobic interactions in the hydrogels. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 102: 4016–4022, 2006