Adsorption of fibrinogen onto macroporous,biocompatible sponges based on poly(2‐hydroxyethyl methacrylate)

Hydrophilic, spongy matrices of poly (2‐hydroxyethyl methacrylate) were synthesized by a redox polymerization method, and the adsorption of fibrinogen was carried out on their surfaces. The prepared sponges were characterized with Fourier transform infrared and environmental scanning electron microscopy and were assayed for their water‐sorption potential. The chemical architecture of the sponges had a pronounced impact on both the water sorption and the protein adsorption affinity of the sponge surface. The adsorption kinetics were investigated, and kinetic parameters such as the rate constants for adsorption and desorption and the penetrate rate constant were evaluated. The influence of experimental conditions such as the pH and temperature were observed on the adsorption profiles of fibrinogen. The prepared sponges were also judged for in vitro blood compatibility by methods such as blood‐clot‐formation and hemolysis‐percentage tests. An attempt was also made to correlate the fibrinogen adsorption capacity of the sponge to its antithrombogenic response to static blood. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 102: 1341–1355, 2006     

Rheological properties of homogeneous and heterogeneous poly(2‐hydroxyethyl methacrylate) hydrogels

The swelling and rheological behaviour of hydrogels of morphology varying from non‐porous to highly porous was investigated. The hydrogels were prepared by redox free radical copolymerization of 2‐hydroxyethyl methacrylate with 0.1 to 5 mol% of di(ethylene glycol) dimethacrylate in the presence of water varying from 40 to 80 wt%. Various compositions led to clear, turbid or macroporous gels. The morphology of the gels was characterized using optical microscopy and cryoscan electron microscopy. The oscillatory shear and creep of swollen gels revealed that there was a pronounced difference between homogeneous or microheterogeneous and macroporous gels with communicating pores. The achievement of optimum conditions for the correct determination of shear modulus was also analysed. Copyright © 2011 Society of Chemical Industry     

Preparation of collagen‐immobilized poly(ethylene glycol)/poly(2‐hydroxyethyl methacrylate) interpenetrating network hydrogels for potential application of artificial cornea

To enhance the mechanical strength of poly(ethylene glycol)(PEG) gels and to provide functional groups for surface modification, we prepared interpenetrating (IPN) hydrogels by incorporating poly(2‐hydroxyethyl methacrylate)(PHEMA) inside PEG hydrogels. Formation of IPN hydrogels was confirmed by measuring the weight percent gain of the hydrogels after incorporation of PHEMA, as well as by ATR/FTIR analysis. Synthesis of IPN hydrogels with a high PHEMA content resulted in optically transparent and extensively crosslinked hydrogels with a lower water content and a 6 ～ 8‐fold improvement in mechanical properties than PEG hydrogels. Incorporation of less than 90 wt % PHEMA resulted in opaque hydrogels due to phase separation between water and PHEMA. To overcome the poor cell adhesion properties of the IPN hydrogels, collagen was covalently grafted to the surface of IPN hydrogels via carbamate linkages to hydroxyl groups in PHEMA. Resultant IPN hydrogels were proven to be noncytotoxic and cell adhesion study revealed that collagen immobilization resulted in a significant improvement of cell adhesion and spreading on the IPN hydrogel surfaces. The resultant IPN hydrogels were noncytotoxic, and a cell adhesion study revealed that collagen immobilization improved cell adhesion and spreading on the IPN hydrogel surfaces significantly. These results indicate that PEG/PHEMA IPN hydrogels are highly promising biomaterials that can be used in artificial corneas and a variety of other load‐bearing tissue engineering applications. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Mechanical characteristics of poly(2‐hydroxyethyl methacrylate) hydrogels crosslinked with various difunctional compounds

Poly(2‐hydroxyethyl methacrylate) hydrogels were prepared in the presence of 30 wt% water using two series of crosslinking agents including divinylic (ethyleneglycol dimethacrylate, 1,4‐butanediol dimethacrylate, 2,3‐dihydroxybutanediol 1,4‐dimethacrylate) and diallylic (1,5‐hexadiene‐3,4‐diol and 1,5‐hexadiene) compounds, over a concentration range between 0.1 and 5 mol%. The resulting polymers were swollen in water to yield homogeneous transparent hydrogels. These hydrogels were characterised in terms of equilibrium swelling in water, tensile properties and compression stress–strain measurements. The influences of the nature and the concentration of crosslinking agent on the swelling behaviour and the mechanical properties of these hydrogels were investigated. The crosslinking efficiency of two representative agents (ethyleneglycol dimethacrylate and 1,5‐hexadiene‐3,4‐diol) was quantified by compression experiments. A much lower crosslinking efficiency (0.013) was observed for 1,5‐hexadiene‐3,4‐diol than for ethyleneglycol dimethacrylate (0.336). It is suggested that the low crosslinking efficiency of diallylic agents is responsible for a trend in properties different from that displayed by the gels crosslinked with dimethacrylates. A comparison was made to the similar effect observed previously in heterogeneous PHEMA hydrogels. © 2001 Society of Chemical Industry     

Preparation and swelling behavior of macroporous poly(acrylamide‐co‐sodium methacrylate) superabsorbent hydrogels

Macroporous superabsorbent hydrogels (SAHs) composed of acrylamide (AAm) and sodium methacrylate (NMA) were prepared by aqueous solution polymerization in the presence of a glucose solution. Their swelling capacity was investigated as a function of the concentrations of the glucose solution, sodium methacrylate, crosslinker, initiator, and activator. The porosity of the poly(acrylamide‐co‐sodium methacrylate) superabsorbent hydrogels was confirmed using scanning electron microscopy. The SAHs were characterized by IR spectroscopy. To estimate the effect on the swelling behavior, three types of crosslinkers were employed: N,N′‐methylenebisacrylamide, 1,4‐butanediol diacrylate, and diallyl phthalate. Network structural parameters such as initial swelling rate, swelling rate constant, and maximum equilibrium swelling were evaluated by water absorption measurement. The equilibrium water content (EWC%) of the AAm–NMA macroporous SAHs was found to be in the range of 93.31–99.68, indicating that these SAHs may have applications as biomaterials in the medicinal, pharmaceutical, and veterinary fields. Most of the SAHs prepared in this investigation followed non‐Fickian‐type diffusion, and few followed a case II– or super–case II‐type diffusion. The diffusion coefficients of these macroporous SAHs were investigated. Further, the swelling behavior of these SAHs also was investigated at different pHs and in different salt solutions and simulated biological fluids. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 101: 3202–3214, 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     

Bioerodible hydrogels based on 2‐hydroxyethyl methacrylate: Synthesis and characterization

Biocompatible polymers with specific shape and tailored hydrogel properties were obtained by polymerization of mixtures of 2‐hydroxyethyl methacrylate (HEMA) with 1–8 wt % ethylene glycol dimethacrylate (EGDMA) or tetra(ethylene glycol) diacrylate (TEGDA) as crosslinking agents, by using a redox initiator. Introduction of charged positive and negative groups was easily achieved by direct polymerization of appropriate monomer mixtures and by chemical transformation of preformed hydrogels. Investigation of the swelling behavior of the prepared hydrogels evidenced an appreciable dependence on both solvent type and polymer chemical structure. Additionally, the solvation process resulted in being controlled by solvent diffusion, according to a Fickian II mechanism. The presence of several types of water with different melting behavior was observed in fully swollen hydrogels. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 85: 2729–2741, 2002     

Shape memory properties and unusual optical behaviour of an interpenetrating network of poly(ethylene oxide) and poly(2‐hydroxyethyl methacrylate)

An interpenetrating polymer network (IPN) with shape memory properties was prepared by using poly(2‐hydroxyethyl methacrylate) (PHEMA) and poly(ethylene oxide) (PEO). PHEMA acts as a fixed phase and PEO as a switching phase. The switching action of PEO is due to the reversible process of melting and crystallization. It was observed that the shape recovery of the IPN increases with increasing crosslinker concentration up to an optimum value and decreases thereafter. In addition to the shape memory property, the IPNs show a reversible change in optical properties from translucent to opaque. The change in optical properties is quite different from that observed in a semicrystalline polymer system where the transparency increases as a result of the melting of crystals. This behaviour of the IPN is explained in terms of H‐bonding of PEO with PHEMA. Fourier transform infrared spectroscopy was used to study the H‐bonding between PEO and PHEMA. © 2019 Society of Chemical Industry     

Swelling–deswelling kinetics of ionic poly(acrylamide) hydrogels and cryogels

A series of ionic poly(acrylamide) (PAAm) gels was prepared by free‐radical crosslinking copolymerization of acrylamide and N,N′‐methylenebisacrylamide in aqueous solutions. The gels were prepared both below and above the bulk freezing temperature of the polymerization solvent water, which are called as the cryogels and the hydrogels, respectively. The deswelling behavior of swollen gels in acetone as well as the reswelling behavior of the collapsed gels in water were investigated. It was shown that the cryogels respond against the external stimuli much faster than the hydrogels. The interior morphology of the cryogel networks exhibits a discontinuity and a two‐phase structure, compared to the continuous morphology of the hydrogel networks. Introduction of the ionic units in the network chains further increased the response rate of the cryogels. In contrast to these advantages of cryogels, they exhibit lower swelling capacities than the conventional hydrogels. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 99: 319–325, 2006     

Radiation crosslinking and sorption properties of hydrogels based on 1‐vinyl‐2‐pyrrolidone,hydroxyethyl methacrylate,and their copolymers

This work has been concerned with the synthesis of the hydrogels of poly (vinyl pyrrolidone) (NVP), poly (hydroxy ethylmethacrylate) (HEMA), and their copolymer under the effect of gamma radiation in the presence of N,N‐methylenebisacryl‐amide (MBAm) as a crosslinking agent. The effect of the different factors that may affect the gelation and yield product, such as solvent composition and irradiation dose, was investigated. The formed hydrogels were characterized in terms of swelling in water and different organic solvents, X‐ray diffraction (XRD), and IR spectroscopic analysis. The sorption capability of these hydrogels towards some commercial basic and acid dyesstuffs was also studied. The results showed that a solvent mixture composed of equal contents of water and methanol is the most suitable to afford the minimum sol fraction and the highest yield product at a minimal irradiation dose of 10 kGy. It was observed that NVP hydrogel displayed the highest swelling in water, alcohols, and dimethyformamide of ～1300% and a lower tendency to swell in nonpolar solvents. The results showed that HEMA hydrogel has a high affinity to absorb basic dyes while NVP has a tendency for acid dyes. Also, the sorption of either the basic or acid dyes by the different hydrogels was found to greatly depend on the concentration of dye in solution and the mass of the used hydrogel. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 91: 3274–3280, 2004     

Preparation and characterizations of interpenetrating polymer network hydrogels of poly(ethylene oxide) and poly(methyl methacrylate)

Interpenetrating polymer network (IPN) hydrogels based on poly(ethylene oxide) and poly(methyl methacrylate) were prepared by radical polymerization using 2,2‐dimethyl‐2‐phenylacetophenone and ethylene glycol dimethacrylate as initiators and crosslinkers, respectively. The IPN hydrogels were analyzed for sorption behavior at 25°C and at a relative humidity of 95% using dynamic vapor sorption. The IPN hydrogels exhibited a relatively high equilibrium water content in the range of 13–68%. The state of water in the swollen IPN hydrogels was investigated using differential scanning calorimetry. The free water in the hydrogels increased as the hydrophilic content increased. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 89: 258–262, 2003     

Poly(hexylacrylate)Core‐poly(ethyleneglycol methacrylate)Shell nanogels as fillers for poly(2‐hydroxyethyl methacrylate) nanocomposite hydrogels

The preparation of poly(hexylacrylate)_core‐poly(ethyleneglycol methacrylate)_shell (PHA‐co‐PEGMA) nanogels, to be used as fillers in nanocomposite hydrogels, is reported. Stable nanogels with particle sizes between 90–300 nm were obtained varying the conditions of synthesis. The synthesis recipe of the nanogels could be easily scaled up. Purified and dispersed nanogels in aqueous solution were used as soft fillers for poly(2‐hydroxyethyl methacrylate) (PHEMA) hydrogels, crosslinked with ethylene glycol dimethacrylate (EGDMA). The obtained nanocomposite hydrogels exhibit a larger swelling capacity and a higher thermal stability in comparison with the non‐filled PHEMA hydrogels. Young, storage, and lost moduli, increase largely, in the better case up to 72.5% in the swollen state; while in the dry state the storage modulus increase up to 4.7 fold with a very low load on nanogels (0.64 wt%); resulting in biomaterials with improved properties with potential applications in medical devices. POLYM. ENG. SCI., 59:170–181, 2019. © 2018 Society of Plastics Engineers     

Kinetics and thermodynamics of the water sorption of 2‐hydroxyethyl methacrylate/styrene copolymer hydrogels

A series of polymer hydrogels based on 2‐hydroxylethyl methacrylate and styrene were synthesized by bulk polymerization. The kinetic and thermodynamic swelling properties of these hydrogels were studied. The swelling mechanism of the hydrogels followed Fickian behavior. The diffusion coefficients, initial swelling rate, and maximum water uptake all decreased with the styrene content increasing because of the hydrophobicity of styrene. The swelling process was exothermic from 278 to 315 K, and the greater the styrene content was, the lower the enthalpy of mixing was in magnitude. The polymer–water interaction parameter, reflecting thermodynamic interactions, increased with increasing styrene content in the polymers. The negative values and trend of the actual partial molar enthalpy and entropy of dilution could be explained by the structuring of water through enhanced hydrogen bonding and hydrophobic interactions. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Entrapment of urease in poly(1‐vinyl imidazole)/poly(2‐acrylamido‐2‐methyl‐1‐propanesulfonic acid) network

In this article, urease was immobilized in a conducting network via complexation of poly(1‐vinyl imidazole) (PVI) with poly(2‐acrylamido‐2‐methyl‐1‐propanesulfonic acid) (PAMPS). The preparation method for the polymer network was adjusted by using Fourier transform infrared (FTIR) spectroscopy. A scanning electron microscope (SEM) study revealed that enzyme immobilization had a strong effect on film morphology. The proton conductivity of the PVI/PAMPS network was measured via impedance spectroscopy, under humidified conditions. The basic characteristics (Michealis‐Menten constants, pH_opt, pH_stability, T_opt, T_stability, reusability, and storage stability) of the immobilized urease were determined. The obtained results showed that the PAA/PVI polymer network was suitable for enzyme immobilization. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Preparation and characterization of sepiolite‐poly(ethyl methacrylate) and poly(2‐hydroxyethyl methacrylate) nanocomposites

Poly(ethyl methacrylate) (PEMA) and poly(2‐hydroxyethyl methacrylate) (PHEMA) nanocomposites with sepiolite in pristine and silylated form were prepared using the solution intercalation method and characterized by the measurements of XRD, TEM, FTIR‐ATR, TG/DTG, and DSC. The TEM analysis indicated that the volume fraction of fibers in sepiolite decreased and the fiber bundles dispersed in PEMA and PHEMA at a nanometer scale. These results regarding TEM micrographs were in agreement with the data obtained by XRD. The increase in thermal stability of nanocomposites of PEMA is higher than that of PHEMA according to the data obtained from TG curves. The DTG analysis revealed that sepiolite/modified sepiolite caused some changes, as confirmed by FTIR in the thermal degradation mechanism of the polymers. T_g temperatures of PEMA and PHEMA usually increased upon the addition of sepiolite/modified sepiolite. In addition, modification of sepiolite with 3‐APTS had a slight influence on thermal properties of the nanocomposites. POLYM. COMPOS., 2009. © 2008 Society of Plastics Engineers     

Poly[(N‐isopropylacrylamide)‐co‐(itaconic acid)] hydrogels with poly(ethylene glycol)

The aim of the work reported here was to investigate temperature‐ and pH‐sensitive hydrogels of N‐isopropylacrylamide (NIPAM) and itaconic acid (IA) and their semi‐interpenetrating polymer networks (semi‐IPNs) with varying contents of poly(ethylene glycol) (PEG). The stimuli responsiveness, swelling behaviour and mechanical properties of the hydrogels and semi‐IPNs were studied in order to investigate the effect of various amounts of PEG. Pulsed‐gradient spin‐echo NMR experiments were carried out to investigate the diffusion process. The pH sensitivity increased with an increasing amount of PEG in the semi‐IPNs, while the overall rate of water uptake was diffusion‐controlled (n < 0.5). For certain PEG contents (5 and 10 wt%), the semi‐IPNs exhibited better mechanical properties than the poly(NIPAM‐co‐IA) copolymer. The calculated values of the self‐diffusion coefficients of water indicated facilitated diffusion of water through the system with increased amounts of PEG, while the self‐diffusion coefficients of a model compound, metoprolol tartrate, showed no significant dependence on the amount of PEG. According to the results obtained and compared to results reported in the literature, the investigated semi‐IPNs may have potential applications in the controlled release of macromolecular active agents such as proteins and peptides. Copyright © 2009 Society of Chemical Industry     

Reactive red 120 and NI(II) derived poly(2‐hydroxyethyl methacrylate) nanoparticles for urease adsorption

Non‐porous poly(2‐hydroxyethyl methacrylate) [p(HEMA)] nanoparticles were prepared by surfactant free emulsion polymerization. The p(HEMA) nanoparticles was about 200 nm diameter, spherical form, and non‐porous. Reactive Red 120 (RR 120) was covalently attached to the p(HEMA) nanoparticles and Ni(II) ions were incorporated to attach dye molecules. Urease was immobilized onto RR120‐Ni(II) attached p(HEMA) nanoparticles via adsorption. The maximum urease adsorption capacity of RR120‐Ni(II) attached p(HEMA) nanoparticles was 480.01 mg g^?1 nanoparticles at pH 7.0 in phosphate buffer. It was observed that urease could be repeatedly adsorbed and desorbed without significant loss in adsorption amount. K_m values were 21.50 and 34.06 mM for the free and adsorbed enzyme. The V_max values were 4 U for the free enzyme and 3.3 U for the adsorbed enzyme. The optimum pH was 25 mM pH 7 phosphate buffer for free and adsorbed enzyme. The optimum temperature was determined at 35°C and 55°C for the free and adsorbed enzyme, respectively. These findings show considerable promise for this material as an adsorption matrix in biotechnological applications. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 39757.     

Preparation and properties of stereoregular poly(hydroxyethyl methacrylate) polymers and hydrogels

Linear poly(hydroxyethyl methacrylate) (PHEMA) has been synthesized in highly syndiotactic and highly isotactic configurations. The high syndiotactic PHEMA prepared by u.v. photolysis at ?40° C was found by ¹³C n.m.r. to have a tactic triad content of 84% syndio, 16% hetero and 0% iso. High isotactic PHEMA was prepared by anionic polymerization of benzoxyethyl methacrylate in toluene followed by selective hydrolysis of the benzoate ester, and was observed by ¹³C n.m.r. to have a 5% syndio, 15% hetero and 80% isotactic triad content. A linear PHEMA polymer formed by radical polymerization at 60°C in ethanol solvent was found to have a tactic triad content of 58% syndio, 42% hetero and 0% iso. These polymers have been crosslinked with hexamethylene diisocyanate and their water swelling properties determined as functions of temperature and crosslinker concentration. Isotactic PHEMA exhibited greater aqueous swelling below 30° C than the syndiotactic PHEMA samples. The stereochemistry of the polymer chain is shown to be a factor in determining the swelling behaviour of hydrophilic methacrylate gels.     

Investigation of thermal behavior of poly(2‐hydroxyethyl methacrylate‐co‐itaconic acid) networks

The thermal behavior of poly(2‐hydroxyethyl methacrylate) [PHEMA] homopolymer and poly(2‐hydroxyethyl methacrylate‐co‐itaconic acid) [P(HEMA/IA)] copolymeric networks synthesized using a radiation‐induced polymerization technique was investigated by differential scanning calorimetry, thermogravimetric analysis, and Fourier transform infrared spectroscopy. The glass‐transition temperature (T_g) of the PHEMA homopolymer was found to be 87°C. On the other hand, the T_g of the P(HEMA/IA) networks increased from 88°C to 117°C with an increasing amount of IA in the network system. The thermal degradation reaction mechanism of the P(HEMA/IA) networks was determined to be different from the PHEMA homopolymer, as confirmed by thermogravimetric analysis. It was observed that the initial thermal degradation temperature of these copolymeric networks increased from 271°C to 300°C with IA content. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 103: 1602–1607, 2007