SI-ATRP Decoration of Magnetic Nanoparticles with PHEMA and Post-Polymerization Modification with Folic Acid for Tumor Cells’ Specific Targeting

Targeted nanocarriers could reach new levels of drug delivery, bringing new tools for personalized medicine. It is known that cancer cells overexpress folate receptors on the cell surface compared to healthy cells, which could be used to create new nanocarriers with specific targeting moiety. In addition, magnetic nanoparticles can be guided under the influence of an external magnetic field in different areas of the body, allowing their precise localization. The main purpose of this paper was to decorate the surface of magnetic nanoparticles with poly(2-hydroxyethyl methacrylate) (PHEMA) by surface-initiated atomic transfer radical polymerization (SI-ATRP) followed by covalent bonding of folic acid to side groups of the polymer to create a high specificity magnetic nanocarrier with increased internalization capacity in tumor cells. The biocompatibility of the nanocarriers was demonstrated by testing them on the NHDF cell line and folate-dependent internalization capacity was tested on three tumor cell lines: MCF-7, HeLa and HepG2. It has also been shown that a higher concentration of folic acid covalently bound to the polymer leads to a higher internalization in tumor cells compared to healthy cells. Last but not least, magnetic resonance imaging was used to highlight the magnetic properties of the functionalized nanoparticles obtained.     

Synthesis and functionalization of nanoengineered materials using click chemistry

The synthesis of nanoengineered materials with precise control over material composition, architecture and functionality is integral to advances in diverse fields, including biomedicine. Over the last 10 years, click chemistry has emerged as a prominent and versatile approach to engineer materials with specific properties. Herein, we highlight the application of click chemistry for the synthesis of nanoengineered materials, ranging from ultrathin films to delivery systems such as polymersomes, dendrimers and capsules. In addition, we discuss the use of click chemistry for functionalizing such materials, focusing on modifications aimed at biomedical applications.     

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.     

Construction of a choline biosensor through enzyme immobilization on a poly(2‐hydroxyethyl methacrylate)‐grafted Teflon film

An amperometric choline biosensor was constructed by immobilizing choline oxidase (ChO) on poly(2‐hydroxyethyl methacrylate) (PHEMA)‐grafted Teflon (polytetrafluoroethylene, PTFE) film. Grafting was achieved by γ irradiation. PHEMA‐grafted Teflon films were activated with epichlorohydrin or glutaraldehyde to achieve covalent immobilization of enzyme onto the film. To decrease the diffusional barrier caused by the enzyme‐immobilized film, the film was stretched directly on the electrode. The PHEMA‐grafted Teflon film, therefore, had to have appropriate mechanical properties. Glucose oxidase (GOD) was used in the determination of optimum immobilization conditions, then these were applied to ChO. With GOD, the effect of activation type and film position in electrode on enzyme activity was studied and the highest catalytic activity was obtained when the enzyme was immobilized using glutaraldehyde and the film was stretched over the electrode surface. Further studies revealed that the films activated with glutaraldehyde, immobilized in 2 mg/mL ChO concentration, and stretched directly on the electrode were suitable (specific activity, 0.427 ± 0.068 U mg^?1) for use in the choline biosensor. The linear working range of this biosensor was found to be 52–348 μM, with a 40 ± 5 μM minimum detection limit. The response of the sensor, however, decreased linearly upon repeated use. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci, 2007     

Dye derived and metal incorporated affinity poly(2-hydroxyethyl methacrylate) membranes for use in enzyme immobilization

Microporous poly(2-hydroxyethyl methacrylate) (PHEMA) membranes were prepared by UV-initiated photopolymerization of HEMA in the presence of an initiator (α,α′-azobisisobutyronitrile, AIBN). An affinity dye Cibacron Blue F3GA (CB) was attached covalently and then Fe³⁺ ions incorporated. The PHEMA-CB and PHEMA-CB-Fe³⁺ membranes derived were used for adsorption of glucose oxidase (GOD). The adsorption capacities of these membranes were determined under conditions of different pH and with different concentrations of the adsorbate in the medium. The adsorption phenomena appeared to follow a typical Langmuir isotherm. The glucose oxidase adsorption capacity of the Fe³⁺ incorporated membrane (87μgcm^-2) was greater than that of the dye-derived membrane (66μgcm^-2). Non-specific adsorption of the glucose oxidase on the PHEMA membranes was negligible. The K_m values for both immobilized glucose oxidase PHEMA-CB-GOD (8·3) and PHEMA-CB-Fe³⁺-GOD (7·6) were higher than that of the free enzyme (6·2mM). Optimum reaction pH was 5·5 for the free and 6·0 for both immobilized preparations. The optimum reaction temperature of the adsorbed enzymes was 5°C higher than that of the free enzyme and was significantly broader. After 15 successive uses the retained activity of the adsorbed enzyme was 87%. It was observed that enzymes could be repeatedly adsorbed and desorbed on the derived PHEMA membranes without significant loss in adsorption capacity or enzymic activity. © 1998 SCI.     

PolyHIPEs: Recent advances in emulsion-templated porous polymers

Porous polymers with well-defined porosities and high specific surface areas in the form of monoliths, films, and beads are being used in a wide range of applications (reaction supports, separation membranes, tissue engineering scaffolds, controlled release matrices, responsive and smart materials) and are being used as templates for porous ceramics and porous carbons. The surge in the research and development of porous polymer systems is a rather recent phenomenon. PolyHIPEs are porous emulsion-templated polymers synthesized within high internal phase emulsions (HIPEs). HIPEs are highly viscous, paste-like emulsions in which the major, “internal” phase, usually defined as constituting more than 74% of the volume, is dispersed within the continuous, minor, “external” phase. This review focuses upon the recent advances in polyHIPEs involving innovations in polymer chemistry, macromolecular structure, multiphase architecture, surface functionalization, and nanoparticle stabilization. The effects of these innovations upon the natures of the resulting polyHIPE-based materials (including bicontinuous polymers, nanocomposites, hybrids, porous ceramics, and porous carbons) and upon the applications involving polyHIPEs are discussed. The advances in polyHIPEs described in this review are now being used to generate new families of porous materials with novel porous architectures and unique properties.     

Initiated chemical vapor deposition of poly(2-hydroxyethyl methacrylate) hydrogels

Initiated chemical vapor deposition (iCVD), a low temperature variant of hot-wire chemical vapor deposition (HWCVD) is a solvent-free polymerization technique. It was used to synthesize thick, free-standing films of the hydrogel poly(2-hydroxyethyl methacrylate) (PHEMA). In this work, we show that the iCVD technique can yield PHEMA which is free from residual entrained monomer, has low non-specific protein adsorption and is capable of supporting good cell adhesion and proliferation.     

Cibacron Blue F3GA‐attached magnetic poly(2‐hydroxyethyl methacrylate) beads for human serum albumin adsorption

An affinity dye ligand, Cibacron Blue F3GA, was covalently attached onto magnetic poly(2‐hydroxyethyl methacrylate) (mPHEMA) beads for human serum albumin (HSA) adsorption from both aqueous solutions and human plasma. The mPHEMA beads, in the size range of 80 to 120 µm, were prepared by a modified suspension technique. Cibacron Blue F3GA molecules were incorporated on to the mPHEMA beads. The maximum amount of Cibacron Blue F3GA attachment was obtained as 68.3 µmol g^?1. HSA adsorption onto unmodified and Cibacron Blue F3GA‐attached mPHEMA beads was investigated batchwise. The non‐specific adsorption of HSA was very low (1.8 mg g^?1). Cibacron Blue F3GA attachment onto the beads significantly increased the HSA adsorption (94.5 mg g^?1). The maximum HSA adsorption was observed at pH 5.0. Higher HSA adsorption was observed from human plasma (138.3 mg HSA g^?1). Desorption of HSA from Cibacron Blue F3GA‐attached mPHEMA beads was obtained by using 0.1 M Tris/HCl buffer containing 0.5 M NaSCN. High desorption ratios (up to 98% of the adsorbed HSA) were observed. It was possible to re‐use Cibacron Blue F3GA‐attached mPHEMA beads without any significant decreases in their adsorption capacities. Copyright © 2004 Society of Chemical Industry     

阳离子季铵型表面活性剂对PVDF/PHEMA共混微滤膜的成膜性能研究

采用凝胶相转化法,以聚偏二氟乙烯(PVDF)/聚甲基丙烯酸-2-羟基乙酯(PHE-MA)共混合金为膜材料,N,N-二甲基乙酰胺(DMAc)为溶剂,阳离子季铵型表面活性剂(TM)为添加剂制备微滤膜.考察了添加剂浓度对铸膜液相容性、铸膜液黏度、铸膜液凝胶速度、膜结构和性能的影响.对PVDF/PHEMA/DMAc铸膜液体系中TM添加剂的作用规律进行了研究.实验发现:TM添加质量分数小于5.0%时,铸膜液中组分的相容性得到很大改善,制备出的微滤膜表面孔径均一、孔密度高.随着TM添加浓度的增大,铸膜液黏度先减小后增大,凝胶速度逐渐增大,膜的纯水通量先增大后减小,截留率则始终上升.