Block copolymers comprising poly(ethylene oxide) and poly(hydroxyethyl methacrylate) blocks: synthesis and characterization

Monofunctional poly(ethylene oxide) macroinitiators with a molecular weight of 2000, 5000, 10?000, 20?000 and bifunctional poly(ethylene oxide) macroinitiators with a molecular weight of 20?000 were used for the atom transfer radical polymerisation (ATRP) of hydroxyethyl methacrylate (HEMA) in ethylene glycol as a solvent. The polymerisation proceeds in a controlled way up to high conversions. The molecular weight of the obtained copolymers increases linearly with conversion. A high rate of polymerisation was observed for the ATRP of HEMA. The effect of the poly(ethylene oxide) moiety on the course of the reaction is limited to solvating effects. The surface analysis of poly(ethylene oxide)/poly(hydroxyethyl methacrylate) block copolymers by means of atomic force microscopy in tapping mode using phase imaging shows phase separated domains with characteristic features related to the volume fraction of the respective blocks.     

Nonporous monosize polymeric sorbents: Dye and metal chelate affinity separation of lysozyme

Lysozyme adsorption onto dye‐attached nonporous monosize poly(2‐hydroxyethyl‐methacrylate‐methylmethacrylate) [poly(HEMA‐MMA)] microspheres was investigated. Poly(HEMA‐MMA) microspheres were prepared by dispersion polymerization. The monochloro‐triazine dye, Cibacron Blue F3GA, was immobilized covalently as dye–ligand. These dye‐affinity microspheres were used in the lysozyme adsorption–desorption studies. The effect of initial concentration of lysozyme and medium pH on the adsorption efficiency of dye‐attached and metal‐chelated microspheres were studied in a batch reactor. Effect of Cu(II) chelation on lysozyme adsorption was also studied. The nonspecific adsorption of lysozyme on the poly(HEMA‐MMA) microspheres was 3.6 mg/g. Cibacron Blue F3GA attachment significantly increased the lysozyme adsorption up to 247.8 mg/g. Lysozyme adsorption capacity of the Cu(II) incorporated microspheres (318.9 mg/g) was greater than that of the Cibacron Blue F3GA‐attached microspheres. Significant amount of the adsorbed lysozyme (up to 97%) was desorbed in 1 h in the desorption medium containing 1.0M NaSCN at pH 8.0 and 25 mM EDTA at pH 4.9. In order to examine the effects of separation conditions on possible conformational changes of lysozyme structure, fluorescence spectrophotometry was employed. We conclude that dye‐ and metal‐chelate affinity chromatography with poly(HEMA‐MMA) microspheres can be applied for lysozyme separation without causing any significant changes and denaturation. Repeated adsorption/desorption processes showed that these novel dye‐attached monosize microspheres are suitable for lysozyme adsorption. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 76: 115–124, 2000     

New metal chelate sorbent for albumin adsorption: Cibacron Blue F3GA-Zn(II) attached microporous poly(HEMA) membranes

Poly(2-hydroxyethyl methacrylate) [poly(HEMA)] membranes were prepared by UV-initiated photopolymerization of HEMA in the presence of an initiator (α-α′-azobis-isobutyronitrile, AIBN). The triazine dye Cibacron Blue F3GA was attached as an affinity ligand to poly(HEMA) membranes, covalently. These affinity membranes with a swelling ratio of 58% and containing 10.7 mmol Cibacron Blue F3GA/m² were used in the albumin adsorption studies. After dye-attachment, Zn(II) ions were chelated within the membranes via attached-dye molecules. Different amounts of Zn(II) ions [650–1440 mg Zn(II)/m²] were loaded on the membranes by changing the initial concentration of Zn(II) ions and pH. Bovine serum albumin (BSA) adsorption on these membranes from aqueous solutions containing different amounts of BSA at different pH was investigated in batch reactors. The nonspecific adsorption of BSA on the poly(HEMA) membranes was negligible. Cibacron Blue F3GA attachment significantly increased the BSA adsorption up to 92.1 mg BSA/m². Adsorption capacity was further increased when Zn(II) ions were attached (up to 144.8 mg BSA m²). More than 90% of the adsorbed BSA was desorbed in 1 h in the desorption medium containing 0.5M NaSCN at pH 8.0 and 0.025M EDTA at pH 4.9. © 1998 John Wiley & Sons, Inc. J Appl Polym Sci 68: 657–664, 1998     

Radiation-induced graft copolymerization of 2-hydroxyethyl methacrylate onto chloroprene rubber membrane. II. Characterization of grafting copolymer

The cobalt-60 radiation-induced graft copolymerization of 2-hydroxyethyl methacrylate (HEMA) onto a chloroprene rubber (CR) membrane has been studied in ethanol. The structure, morphology, crystallinity, thermal stability, and hydrophility of graft copolymer were characterized by means of Fourier transform infrared photoacoustic spectroscopy, scanning electron microscopy, wide-angle X-ray diffraction, differential thermal gravimetric analysis, and contact angle test methods, respectively. The permeabilities of urea, creatinine, and creatine through the CR and CR-g-HEMA membranes are investigated in a dialysis cell, and the permeation mechanism is also discussed. © 1998 John Wiley & Sons, Inc. J Appl Polym Sci 68: 1745–1750, 1998     

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     

Kinetics of radiation‐induced grafting of 2‐hydroxyethyl methacrylate onto chloroprene rubber membrane and computer verification

Grafting of 2‐hydroxyethyl methacrylate(HEMA) onto chloroprene rubber(CR) membrane was carried out in ethanol by direct cobalt‐60 gamma ray irradiation. The kinetics of the grafting reaction was studied in respect of concentration of monomer, dose rate and temperature. The experimental results show that the functional relationship equation is dg₀/dt = k[M]^1.5 Ḋ. The apparent activation energy and collision frequency factor of the grafting polymerization are 46.2 kJ mol⁻¹ and 4.98 × 10⁷ mg cm⁻² kGy⁻¹ mol^−1.5 litre^1.5, respectively. The work established the relationship of the initial grafting rate (dg₀/dt) with various effect factors: ln (dg₀ dt) = 17.7 − 5560(1/T) + 1.5 ln [M] + ln Ḋ. This equation is also verified for the first time by a software named SMR, which function is using multiple linear regression to calculate the regression coefficient of a linear equation. © 1999 Society of Chemical Industry     

甲基丙烯酸β-羟乙酯共聚水凝胶的合成及性能研究

以HEMA、AAM为共聚单体,采用溶液聚合法合成了HEMA/AAM共聚水凝胶,并对其溶胀动力学、离子强度、温度、pH值等性能进行了测定。实验表明:合成的水凝胶初始溶胀迅速,达到平衡溶胀比平衡约6h;在不同离子强度的水溶液中,随着离子强度I的增大,凝胶的ESR不断降低;在pH<7时,其EKR随pH值的增加而减少,在pH>7时,其ESR随pH值的增加而猛增,因为发生了水解反应;凝胶的ESR随温度的升高而降低。     

New hydrogels based on maleilated collagen with potential applications in tissue engineering

New hydrogels based on maleic anhydride (MA) modified collagen were prepared with the aim of overcoming the high degradation rate displayed by collagen that is not otherwise chemically crosslinked. Semi-interpenetrated matrices were obtained by free radical polymerization of maleilated collagen (CM) and 2-hydroxyethyl methacrylate (HEMA) in the presence of ammonium persulfate (APS) and N,N,N′,N′-tetramethylethylenediamine (TEMED) as initiating system. The resulting matrices (CMH) had a sharp decrease in degradation, when compared to pure collagen. FTIR and H¹ NMR spectroscopies were used to confirm the incorporation of MA on the collagen peptide chains. The final composition of CMH was found to be strongly dependent by the concentration of maleilated collagen. The morphology of the hydrogels was studied by Scanning electron microscopy (SEM) and the macro-gel structure was confirmed. Water uptake of the synthetised hydrogels is influenced by both composition and the porosity of the matrices.     

荧光磁性微球Fe_3O_4@PHEMA-Eu的制备、表征及其载药性研究

在亲水性Fe3O4磁流体中,以甲基丙烯酸-2-羟基乙酯(HEMA)为单体,N,N’-亚甲基双丙烯酰胺(MBA)为交联剂,采用光化学方法在水溶液体系中首先合成磁性聚甲基丙烯酸-2-羟基乙酯(PHEMA)微球,进而在60℃下PHEMA与Eu离子反应合成具有荧光特性的磁性微球(FMPMs),同时用丝裂霉素C(MMC)考查了其载药性。运用VSM、PCS、FTIR、TGA、SEM、FS、HPLC等技术对微球的性能进行了表征。结果表明,荧光磁性高分子微球有超顺磁性,荧光性,呈很好的球形,载药率和包裹率较高。     

Microwave assisted synthesis of poly(2-hydroxyethylmethacrylate) grafted agar (Ag-g-P(HEMA)) and its application as a flocculant for wastewater treatment

Poly(2-hydroxyethylmethacrylate) chains were grafted onto the backbone of agar using a microwave assisted method involving a combination of microwave irradiation and ceric ammonium nitrate to initiate the grafting reaction. The synthesized graft copolymers were characterized by intrinsic viscosity measurements, Fourier transform infrared spectroscopy, elemental analysis (C, H, N, O and S) and scanning electron microscopy. Ag-g-P(HEMA)-2 showed a much higher flocculation efficacy than agar. The optimized dosage of flocculation for Ag-g-P(HEMA)-2 in the wastewater was found to be 0.75 ppm. Compared to agar, Ag-g-P(HEMA)-2 was found to considerably reduce the pollutant load in the wastewater.