Dynamic mechanical properties of polymer-fluid systems: characterization of poly(2-hydroxyethyl methacrylate) and poly(2-hydroxyethyl methacrylate-co-methyl methacrylate) hydrogels

The complex shear moduli of crosslinked poly(2-hydroxyethyl methacrylate) and poly(2-hydroxyethyl methacrylate-co-methyl methacrylate) hydrogels were measured as a function of water content, temperature and frequency using dynamic mechanical spectroscopy. The effect of increasing water content on both the storage and loss moduli is to lower the temperatures at which mechanical transitions occur. There is a significant decrease in the storage moduli and increase in the loss moduli dispersions with increasing water content. These data could be well correlated by a multiple-mechanism, time-temperature superposition procedure. Between 2% and 28% water content in the copolymer sample, the relaxation spectra and shift function characterizing the glassy-rubbery state transition become independent of water content when properly referenced to the observed transition temperature. At lower temperatures where the β transition occurs, the mechanical viscoelastic spectra depend much more strongly on water content although the shift factors collapse to a single curve when referenced to the observed β transition temperature.     

Poly(2-hydroxyethyl methacrylate-co-sulfobetaine) hydrogels. II. Synthesis and swelling behaviors of the [2-hydroxyethyl methacrylate-co-3-dimethyl(methacryloyloxyethyl)ammonium propane sulfonate] hydrogels

A series of the 2-hydroxyethyl methacrylate/3-dimethyl-(methacryloyloxyethyl)ammonium propane sulfonate (HEMA/DMAPS) copolymeric gels was prepared from various molar ratios of HEMA and the zwitterionic monomer DMAPS. The influence of the amount of the zwitterionic monomer in the copolymeric gels on the swelling behaviors in water, various saline solutions, and temperature was investigated. The results indicate that the PHEMA hydrogel (D0) and lower DMAPS content of the HEMA/DMAPS copolymeric gel (D1) exhibit overshooting phenomena in the dynamic swelling behavior. The maximum overshooting value decreases with increase in temperature. In the equilibrium swelling ratio, the PHEMA hydrogel exhibits a minimum swelling ratio at 55°C. Then, the minimum swelling ratio diminishes gradually with increasing of the DMAPS content in the HEMA/DMAPS copolymeric gels. In the saline solution, the swelling ratios of HEMA/DMAPS copolymeric gels increase rapidly with increasing of concentration of the salt with a smaller ratio of the charge/radius. © 1998 John Wiley & Sons, Inc. J Appl Polym Sci 69: 2021–2034, 1998     

The preparation of poly(2-hydroxyethyl methacrylate) and poly{(2-hydroxyethyl methacrylate)-co-[poly(ethylene glycol) methyl ether methacrylate]} by photoinitiated polymerisation-induced phase separation in water

This paper describes the application of a photoinitiated polymerisation-induced phase separation method to the preparation of PHEMA and P[HEMA-co-(MeO-PEGMA)] hydrogels. PHEMA sponges having a morphology of agglomerated polymer droplets and interconnected pores were easily prepared from aqueous mixtures containing HEMA, EDGMA (crosslinker) and DPAP (photoinitiator). P[HEMA-co-(MeO-PEGMA)] copolymers having similar morphologies could also be prepared, provided that the proportion of MeO-PEGMA in the copolymer was relatively small. When higher proportions of MeO-PEGMA were used, the resulting polymers were gels rather than sponges, and did not show the sought after droplet/pore morphology. P[HEMA-co-(MeO-PEGMA)] copolymers having higher proportions of MeO-PEGMA and having a morphology of agglomerated polymer droplets and interconnected pores were easily prepared by addition of NaCl to the polymerisation mixture. Thus, incorporation of MeO-PEGMA and adddition of NaCl to the photopolymerisation mixtures provides an easy way of tuning the hydrophilicity of PHEMA copolymer sponges without compromising the desired porous morphology.     

Tuning the optical properties of poly(o-phenylenediamine-co-pyrrole) via template mediated copolymerization

Tailoring of conjugated monomers via copolymerization is a facile method to obtain tunable spectral, morphological and optical properties. To investigate the effect of copolymerization of pyrrole with o-phenylenediamine on the optoelectronic properties of the synthesized copolymers, the present work reports the synthesis of copolymers of o-phenylenediamine with pyrrole with varying mol ratios via chemical polymerization in methylene blue (MB) medium. Copolymerization was confirmed by Fourier transform infrared spectroscopy and ultraviolet-visible studies. Ultraviolet-visible spectroscopy revealed variation in the optical properties with the change in the monomer ratio. Fluorescence studies showed that the copolymer containing 80% poly(o-phenylenediamine) revealed highest quantum yield among all the copolymers. The emission color could therefore be tuned by careful selection of narrow band co-monomers, which could help in designing tunable fluorescence emitting materials for potential application in OLED devices.     

Poly(2-hydroxyethyl methacrylate) (PHEMA)/poly(styrene-co-acrylamide) (PSAm) blends: miscibility and hydrogel properties

The blend miscibility of poly(2-hydroxyethyl methacrylate) (PHEMA) and poly(styrene-co-acrylamide) (PSAm) was studied by DSC. A ‘miscible window’ was found in the range 47–57 mol% of acrylamide in blending PSAm with PHEMA (1:1 w/w) and was analysed by the mean-field theory. The water content and permeability coefficients of proteins were measured. The results show that the water content of the blends depends on the composition of PSAm and the blends, and the behaviour of blends swollen in water in Fickian type. However, the permeability of the solutes not only related to water content, but was also affected by phase behaviour. Controlled release of somatotropin from a cylindrical device coated with PHEMA/PSAm was achieved.     

Synthesis and characterization of glucosamine modified poly(ethylene glycol) hydrogels via photopolymerization

This study presented the synthesis and characterization of glucosamine (GlcN) modified poly (ethylene glycol) (PEG) hydrogels. The chemical structure was characterized by Fourier transform infrared (FTIR) and proton nuclear magnetic resonance (¹H NMR) spectroscopy. The morphology of hydrogels was observed by scanning electron microscopy (SEM). The results indicated that GlcN was successfully incorporated into PEG hydrogel network. Moreover, the data of the swelling ratio showed that the ratio of GlcN‐modified PEG hydrogels was lower than that of pure poly(ethylene glycol) diacrylated (PEGDA). Biocompatibility of unreacted GlcN monomer and GlcN‐modified hydrogels was also evaluated in vitro. Compared with glucosamine hydrochloride, 2 and 5 mM N‐acroloyl‐glucosamine monomer exhibited no toxicity against bone marrow stromal cells (BMSCs), while with the concentration increased to 10 mM, cell viability appeared to decrease. However, when BMSCs were encapsulated in GlcN‐modified hydrogels via photopolymerization method, cells remained vigorous viability. Metabolic activity of the encapsulated cells demonstrated GlcN‐modified hydrogels was favorable for cell proliferation. Compared with free GlcN, covalent binding GlcN showed lower cytotoxicity and higher cell proliferation properties. As a result, GlcN‐modified PEGDA hydrogels could be used as safe and injectable cell carriers for in situ tissue engineering applications. © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

Synthesis of thermoresponsive poly(N-isopropylmethacrylamide) and poly(acrylic acid) block copolymers via post-functionalization of poly(N-methacryloxysuccinimide)

Polymers exhibiting a thermoresponsive, lower critical solution temperature (LCST) phase transition have proven to be useful for many applications as “smart” or “intelligent” materials. A series of poly(N-isopropylmethacrylamide) (PNIPMAM) polymer, poly(N-isopropylmethacrylamide)-b-poly(acrylic acid) (PNIPMAM-b-PAA) diblock, and poly(acrylic acid)-b-poly(N-isopropylmethacrylamide)-b-poly(acrylic acid) (PAA-b-PNIPMAM-b-AA) triblock copolymer samples were synthesized via ATRP. A facile post-functionalization route was developed that uses an activated ester functionality to convert poly(N-methacryloxysuccinimide) (PMASI) blocks to LCST capable polyacrylamide, while poly(t-butyl acrylate) (PtBA) blocks were converted to water-soluble poly(acrylic acid) (PAA). The post-functionalization was monitored via ¹H NMR and ATR-FTIR. The aqueous solution properties were explored and the PNIPMAM polymers were shown to have a LCST phase transition varying from 35 to 60 °C. The ability to synthesize block copolymers that are thermoresponsive and water-soluble will be of great benefit for broader applications in drug delivery, bioengineering, and nanotechnology.     

Physico-chemical characterization of hybrid polymers obtained by 2-hydroxyethyl(methacrylate) and alkoxides of zirconium

Hybrid monolithic materials were prepared through polymerisation of 2-hydroxyethyl methacrylate (HEMA) mixed with zirconium alkoxides (Zr(OBuⁿ)₄, Zr(OPrⁿ)₄ and Zr(OEt)₄), modified by acetylacetonate groups. The molar ratio HEMA/Zr varied between 1 and 4. Thermo-Gravimetry coupled with Mass Spectroscopy (TG-MS) analyses, ¹³C MAS NMR and Dynamical Mechanical Thermal Analysys (DMTA) indicated the polymeric chains were interconnected by the inorganic component.The presence of zirconium alkoxides modified substantially the poly-HEMA properties. Glass transition temperature of hybrid materials derived from butoxy and propoxy was found in the range 50-80 °C, depending on the composition. The typical swelling of p-HEMA in the water, was suppressed by the presence of zirconium compounds. After immersion in distilled water, hybrid polymers showed an initial slight weight increase, followed by a small mass loss, which increases proportionally to the length of alkoxyl group (ethoxide(propoxide(butoxide) and reaches a constant value after about 40 days. The hybrids remained always rigid and transparent. Flexural modulus and strength of about 400-900 and 4-8 MPa were measured.     

Effect of the crosslinking with 1,1,1-trimethylolpropane trimethacrylate on 5-fluorouracil release from poly(2-hydroxyethyl methacrylate) hydrogels

The aim of this study is to examine the influence of crosslinking density on 5-Fluorouracil release from poly(2-hydroxyethyl methacrylate) (PHEMA) hydrogels crosslinked with 1,1,1-trimethylolpropane trimethacrylate (TPT). PHEMA hydrogels were synthesized by bulk polymerization with different proportions of TPT (1 – 10 wt%) as crosslinker agent and ammonium persulphate as initiator, enabling polymerization in the feed mixture in the presence of water. As a result, 5-FU could be trapped by including it as a sodium salt in the feed mixture of polymerization. Discs with 5-FU loads between 1 – 16 mg/disc were obtained. Swelling and 5-FU release kinetics studies were carried out in saline solution at 310 K. The diffusion studies were in accordance with Fick's second law during the initial stages, enabling the diffusion coefficients of the process to be determined. The time required for discs to reach total 5-FU release was between 35 h and 160 h and was a function of crosslinking density of the gels and 5-FU load of the discs. Received: 12 July 1996/Revised version: 8 October 1996/Accepted: 15 October 1996     

Biocompatible and bioadhesive hydrogels based on 2-hydroxyethyl methacrylate, monofunctional poly(alkylene glycol)s and itaconic acid

Summary Novel poly(Bisomer/HEMA/IA) hydrogels were prepared by radical copolymerization of poly(alkylene glycol) (meth)acrylates, i.e. short chains Bisomers, 2-hydroxyethyl methacrylate (HEMA) and itaconic acid (IA) in a mixture of water/ethanol as solvent. These hydrogels were characterized in terms of swelling in conditions similar to the biological fluids (pH range 2.20–7.40 buffer solutions), compression-strain measurements, thermal properties and morphology. The influence of the type of Bisomer and of the itaconic acid on swelling and mechanical properties, as well as on morphology and thermal behavior of the resulting hydrogels, were investigated. The in vitro study of biocompatibility, carried out with the hydrogels containing different types of Bisomers, showed no evidence of cell toxicity nor any considerable hemolytic activity. All hydrogels showed satisfactory bioadhesive properties, so these materials have potential as drug carriers or biological glue and sealants.     

Water structure in poly(2-hydroxyethyl methacrylate): Effect of molecular weight of poly(2-hydroxyethyl methacrylate) on its property related to water

Low molecular weight poly(2-hydroxyethyl methacrylate) (polyHEMA) with a number average molecular weight (Mn) <22,600, were prepared by atom transfer radical polymerization. The molecular weight and end groups of the polyHEMA were varied, and the water content equilibrium moisture sorption and water structure were analyzed using differential scanning calorimetry (DSC) and X-ray diffractometry (XRD). Higher water content was observed for polyHEMA with Mn < 10,000. DSC revealed that the amounts of nonfreezing water are affected neither by the molecular weight nor by the end groups of the polyHEMA. On the other hand, the amount of freezing water was affected by both the molecular weight and end groups of polyHEMA, especially for polyHEMA with Mn < 20,000. The XRD-DSC measurements showed that water in polyHEMA form hexagonal ice and that the direction of crystal growth is dependent on the molecular weight. These findings indicate that the molecular weight of polyHEMA plays a significant role in the water structure in polyHEMA. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

A poly(2-hydroxyethyl methacrylate)-based immobilized metal affinity chromatography adsorbent for protein purification

Poly(HEMA) microbeads were prepared by suspension polymerization of 2-hydorxyethylmethacrylate and ethyleneglycoldimethacrylate (EGDMA). The water content, ligand density, and selectivity for poly(His)-tagged d-hydantoinase of the poly(HEMA)-based adsorbents were affected by the concentration of EDGMA used during polymerization. The Ni(II)-loaded poly(HEMA) adsorbent exhibited an adsorption capacity of 1.0 mg/g for poly(His)-tagged d-hydantoinase under optimal conditions with buffer containing 100-300 mM NaCl at pH 6.0. One-step purification protocol with the adsorbent gave a purity of at least 92%. The adsorption capacity of adsorbent declined by 54% after 7 cycles, due to the leaching of Ni(II) from the adsorbent. However, upon regeneration the adsorption capacity can be restored. Given the ease of preparation and the chemical and microbial resistance, the poly(HEMA)-based IMAC adsorbent could be a promising substitute for the polysaccharide-based IMAC adsorbents.     

Entrapping of acid phosphatase in poly(2-hydroxyethyl methacrylate) matrices: Preparation and kinetic properties

The present work was undertaken to determine the influence of immobilization of acid phosphatase by entrapment in poly(2-hydroxyethyl methacrylate) (poly-HEMA) gels on the rate and duration of p-nitrophenyl phosphate hydrolysis. This enzyme was selected as model system for the sake of comparison with other immobilization techniques studied previously making use of natural polymers. Under certain conditions, catalyst inactivation induced by chemical agents employed during polymerization was very low. Activity recovery in the enzymatically filled hydrogels depends on acid phosphatase loading and attains a maximum at 2 mg per gram of support. The use of low molecular weight linear polymers as matrix fillers is advisable. The best results were achieved with poly(ethylene oxide) PEG 1500, but PEG 6000 and poly(N-vinylpyrrolidone) PVP 10 000 are also effective. Bovine serum albumin (BSA) is useless. The highest value of activity recovery obtained was 24% that of free enzyme. Roughly 30% of enzyme is retained in active form in the hydrogel and works with an efficiency ranging from 97% to 90% depending on average particle size. The kinetic parameters K_m and E_a suggest the presence of a combined diffusive and enzymatic reaction-controlling mechanism. Only a minor shift of optimum pH was observed. Both operational and storage stability are largely improved upon entrapping in hydrogels.     

Temperature‐responsive properties of poly(acrylic acid‐co‐acrylamide)‐graft‐oligo(ethylene glycol) hydrogels

A series of temperature‐ and pH‐responsive hydrogels were prepared from acrylic acid (AAc), acrylamide (AAm), oligo(ethylene glycol)monoacrylate (OEGMA), and oligo(ethylene glycol)diacrylate by varying the AAc:AAm molar ratio and the OEGMA content. Phase‐transition temperatures and swelling ratios of the obtained poly(AAc‐co‐AAm)‐graft‐OEG gels were measured as a function of temperature and pH. At pH < 5, the obvious transition temperatures ranging from 5 to 35°C were obtained as the AAc : AAm molar ratio was varied. The highest transition temperature was obtained at the AAc : AAm ratios of 5 : 5 and 6 : 4, and the sharp transition curves were observed at the AAc : AAm ratios from 5 : 5 to 8 : 2. The transition temperature further increased with increasing OEGMA content. It was suggested that OEG graft chains with a large mobility played an important role for the formation of hydrogen bonding in the hydrogels. The gels prepared here showed obvious reproducibility of the phase transition in response to temperature changes, which suggests the feasibility of their practical applications. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 80: 798–805, 2001     

Evaluation of redox-responsive disulfide cross-linked poly(hydroxyethyl methacrylate) hydrogels

Poly(2-hydroxyethyl methacrylate) (PHEMA) hydrogels were prepared with a disulfide containing cross-linker bis(2-methacryloxyethyl) disulfide (DSDMA) that exhibited enhanced release in the presence of glutathione (GSH), a biologically available reducing agent. Varying concentrations of the DSDMA cross-linker were incorporated into the prepolymer before the radical polymerization, enabling the cross-link density to be easily tuned. Dye release studies were performed using rhodamine B and rhodamine 6G dyes, and the UV response of the dyes released into the supernatant measured with the addition of GSH. Using ether-based cross-linkers as a control, the disulfide cross-linkers exhibited a substantial increase in release rates, confirming the responsive nature of the hydrogels to biological reducing agents. The polymers were also tested in a cell culture system for their ability to release the anti-fibroproliferative agent, mitomycin C (MMC). Polymers cross-linked with DSDMA delivered MMC over a slightly longer time period than control polymers prepared with a conventional ether cross-linker.     

温度及pH敏感共聚/粘土纳米复合水凝胶的合成与性能研究

以无机粘土为交联剂制备了具有温度、pH双重敏感性的聚（N-异丙基丙烯酰胺-co-甲基丙烯酸-β-羟乙酯）/粘土纳米复合水凝胶（P（NIPA-co-HEMA）/clay）,并用红外和X衍射对其结构和形态进行了表征。在弱碱性（pH=7.4）和25℃条件下,分别研究了温度和不同pH缓冲溶液对该凝胶溶胀度的影响,测定了纳米复合水凝胶的力学性能。结果表明：水凝胶的粘土已被剥离成单片层,且均匀分散在凝胶网络中,起交联作用;P（NIPA-co-HEMA）/clay具有良好的温度、pH双重敏感特性;凝胶的断裂伸长率〉1000%。     

Glucose recognition capabilities of hydroxyethyl methacrylate‐based hydrogels containing poly(ethylene glycol) chains

A configurational biomimetic imprinting technique was used to prepare recognition sites for glucose in copolymers of 2‐hydroxyethyl methacrylate (HEMA) and methacrylic acid (MAA) prepared with crosslinking agents containing poly(ethylene glycol) (PEG). We report on the structure, diffusive, and recognition characteristics of these gels, the effect of the type and ratio of crosslinking agent, as well as the template/comonomer ratios on glucose binding ability. The highest equilibrium glucose binding was found as 2.67 mg/g dry polymer when PEG monomethacrylate (PEGMMA) was used in combination with tetra ethylene glycol dimethacrylate (TEGDMA) (50%) as a crosslinking agent. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 103: 432–441, 2007     

Dielectric analyses of a series of poly(2-hydroxyethyl methacrylate-co-2,3-dihydroxypropyl methacylate) copolymers

The dielectric spectra of a series of copolymers of 2-hydroxyethyl methacrylate (HEMA) and 2,3-dihydroxypropyl methacrylate (DHPMA) were investigated. Recently, the full range dielectric spectrum of poly(2-hydroxyethyl methacrylate) was reported. This study looks at the effects on the dielectric behavior as a result of 2,3-dihydroxypropyl methacrylate addition. The dielectric permittivity, ε′, and the loss factor, ε″, were measured using a dielectric analyzer in the frequency range of 0.6 Hz to 100 kHz and between the temperature range of −150 and 275 °C. The electric modulus formalism was used to reveal the viscoelastic and conductivity relaxations present in the polymers. Several notable changes were observed as 2,3-dihydroxypropyl methacrylate concentration increased. It was observed through DSC and DEA that the glass transition temperature decreased as DHPMA content increased. The secondary dielectric relaxations were also affected as it was recorded that the activation energy for the γ transition increased and the β relaxation decreased with DHPMA content. Ionic conductivity data prove that DHPMA facilitates ionic mobility more efficiently than HEMA.     

Ultrasonic characterization of water sorption in poly(2-hydroxyethyl methacrylate) hydrogels

A complex mechanism characterizes the water uptake kinetics in hydrogels, as a consequence of the strong structural changes occurring in the material during the sorption process. The water sorption involves the transformation of a glassy, moderately crosslinked polymer in a rubbery material. In this study, the changes in the ultrasonic attenuation and velocity in crosslinked poly(2-hydroxyethyl methacrylate) [poly-(HEMA)] hydrogel films during water sorption are measured by scanning laser acoustic microscopy (SLAM) and a pulse–echo system. In particular, the pulse–echo technique provides additional valuable information, thanks to its capability for monitoring the position of the swollen/unswollen fronts during water sorption. The evolution of the attenuation observed by SLAM is analyzed in terms of reflections on macroscopic discontinuities and absorption mechanisms. Finally, the propagation of ultrasonic waves acts as a dynamic mechanical test of the material; and, therefore, the measured longitudinal velocity and ultrasonic attenuation are applied to the calculation of the storage bulk longitudinal modulus of the poly(HEMA) hydrogels during water sorption. © 1998 John Wiley & Sons, Inc. J Appl Polym Sci 67:823–831, 1998     

Photopolymerization synthesis of poly(N-isopropylacrylamide) hydrogels

Poly(N-isopropylacrylamide) (NIPAAm) gels were formed by photopolymerization of NIPAAm in the absence of a crosslinker using a water solvent at 25°C. Factors affecting formation were the wavelength region of irradiated light, the type of photoinitiators, and the concentrations of the photoinitiator and monomer. A high-pressure mercury lamp (400 W) was used as a light source. An NIPAAm concentration of 10 wt % and irradiation time of 15 h was used for the photopolymerization. The gel (68% yield) was formed when the quartz glass system was used, but no gelation was observed for the Pyrex glass system that transmits light with π > 290 nm. The gel (100% yield) was easily formed, even in the latter system, when 30 mmol/L of hydrogen peroxide and potassium persulfate were used as the photoinitiator. Water soluble photoinitiators such as ferric chloride and sodium anthraquinone-2,7-disulfonate were not effective for the gel formation. Yield of the gel increased with increasing the potassium persulfate concentration (1–30 mmol/L), but it decreased when a high concentration of hydrogen peroxide (60 mmol/L) was used. The gel yield increased with the NIPAAm concentration (5–20 wt %). The degree of swelling of the resultant poly(NIPAAm) gels, which was measured by immersing the gels in water at various temperatures (0–50°C) for 24 h, steeply decreased at about 30°C with increasing temperature, exhibiting a temperature-responsive character. The gels swelled and shrank in water below and above the temperature, respectively. The extent of the character depended on the concentrations of hydrogen peroxide and monomer. The formation mechanism of the gel in the photopolymerization of NIPAAm using hydrogen peroxide photoinitiator was discussed. © 1997 John Wiley & Sons, Inc. J Appl Polym Sci 65:1313–1318, 1997