Immobilization of enzymes and antibodies to radiation grafted polymers for therapeutic and diagnostic applications

Pre-irradiation and mutual radiation grafting were employed to produce poly(methacrylic acid) (MAAc) hydrogels on polypropylene/polyethylene (PP/PE) copolymer films, PP films and porous PP fibers of a plasma filter. A diphenyl picryl hydrazyl (DPPH) assay was developed to measure the surface peroxide concentration of the pre-irradiated PP/PE films prior to grafting. Mutually grafted porous PP fibers were used for subsequent immobilization of L-asparaginase while the mutually grafted PP/PE films were used to immobilize a schistosoma monoclonal antibody.     

Fabrication of shape-controllable polyaniline micro/nanostructures on organic polymer surfaces: obtaining spherical particles, wires, and ribbons

A novel strategy was developed in order to prepare various micro/nanostructured polyanilines (PANI) on polymer substrates. The strategy involved two main steps, i.e., a grafting polymerization of acrylate acid (AA) onto the surface of a polypropylene (PP) film and subsequently an oxidative polymerization of aniline on the grafted surface. By tuning the conformation of the surface-grafted poly acrylate acid (PAA) brushes, as well as the ratio of AA to aniline, the shape of the PANIs fixated onto the surfaces of the polymer substrate could be controlled to go from spherical particles to nanowires and eventually to nanoribbons. In these structures, the PAA brushes not only acted as templates but also as dopants of PANI, and thereby, the nanostructured PANIs could be strongly bonded with the substrate. In addition, the surface of the PP films grafted with polyaniline nanowires and nanoribbons displayed superhydrophobicity with contact angles for water of approxiamtely 145 and 151 degrees , respectively.     

Adsorption behavior of urokinase by polypropylene film modified with amino acids as affinity groups

In order to prepare a new-type adsorbent with an affinity ligand, polypropylene films modified with amino acid groups such as -phenylalanine (Phe), , -Phe, -cysteine (Cys), and , -tryptophane (Try), were prepared by radiation-induced grafting of glycidyl methacrylate (GMA) onto polypropylene (PP) films and subsequent amination of poly-GMA graft chains. The physical and chemical properties of the GMA-grafted PP film and the PP film modified with amino acid groups were investigated by IR and XPS. The adsorption of urokinase for the PP films modified with four kinds of amino acid groups were examined under various conditions, such as the contents of the amino acid group and pH value. The adsorption of urokinase increased with the increasing content of the amino acid group. The adsorption of the PP film modified with four kinds of amino acid groups was in the following order: -Phe> , -Phe> , -Try> -Cys. The adsorption amounts of urokinase by the PP film modified with four kinds of amino acid groups at pH 7.4 was higher than that at pH 9.0.     

Graft copolymers obtained by radiation grafting of methacrylic acid onto polypropylene films

Direct radiation grafting of methacrylic acid (MAA) onto polypropylene films (PP) was studied. The effect of different solvents such as benzene, distilled water, dimethyl formamide, isopropanol, isopropanol/water-mixture, on the swelling and the grafting process of MAA onto (PP) films was investigated. It was found that the grafting process was enhanced under vacuum irradiation in benzene as a diluent for MAA as compared with other solvents examined. The dependence of the grafting rate on such monomer concentrations was found to be 1.2 order. The relationship between the grafting rate and film thickness gave a negative first order dependence. This grafting system proceeded by a diffusion controlled process. Some selected properties of the grafted films such as mechanical and electrical properties, swelling behaviour, and gel determination, were also investigated.     

Accurate determination of individual lanthanides in biological materials by NAA with pre-and post-irradiation separation

An intelligent hydrogel with both pH and temperature sensitivity was obtained by grafting acrylic acid and dimethylaminoethylmethacrylate onto preirradiated polypropylene (PP) film by two-step reactions. The effect of first and second reactions on the degree of grafting was studied. The grafted sample films were checked by Fourier transform infrared spectrophotometry in the attenuated total reflectance mode. The morphology of the PP samples was observed by scanning electron microscope in different conditions before and after grafting, respectively.     

GRAFT COPOLYMERIZATION OF ACRYLAMIDE ONTO POLYPROPYLENE FILMS BY PLASMA TECHNIQUE

The graft copolymerization of acrylamide onto polypropylene (PP) Film was carried out by using a capacitively coupled rf plasma apparatus with external plate electrodes. The relationship between the surface structure of the Ar plasma-treated PP films and the extent of grafting of acrylamide on the films was studied through observing the effects of discharge power and exposure time on the relative content of free-radical on the film surface. Meanwhile, the wettability and surface energy of the PP film were measured.     

Gas transport in surface grafted polypropylene films with poly(acrylic acid) chains

This work describes the grafting reaction of poly(acrylic acid) (PA) onto the surface of polypropylene (PP) films carried out with ultraviolet radiation, using benzophenone as photoinitiator and water as solvent. By increasing the reaction time, graft percentages of 3.5, 6.5, 12.9, 19.8, 29.4, and 36.0% were obtained. Micrographs of the modified films show that grafting exclusively occurs on the PP films surface. The values of the permeability coefficient of oxygen, nitrogen, carbon dioxide, carbon monoxide, argon, methane, ethane, ethylene, and propane across the grafted films undergo a sharp drop. The interpretation of the permeation results suggest that radicals created in the tertiary carbons of the grafted chains by effect of UV light or by chain transfer reactions may highly crosslink the PA grafted layer. A rigid layer involving both strong hydrogen bonding and chains crosslinking is formed at grafting percentages of 3.5% that strongly hinders gas permeation across that layer. Destruction of hydrogen bonding by partially replacing protons of acrylic acid residues by sodium/silver cations increases the permeability of the surface grafted films. Finally, the films permselectivity is hardly affected by the grafted layer. © 2007 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 45: 2421–2431, 2007     

表面接枝改性纳米二氧化硅填充聚丙烯的结晶行为

应用差示扫描量热方法研究了纳米二氧化硅 (SiO2 )及其表面接枝改性对聚丙烯 (PP)结晶过程、等温与非等温结晶动力学的影响 ,并研究了上述等温结晶的熔融行为和平衡熔点 .研究发现纳米SiO2 具有明显的异相成核效应 ,能够提高PP的结晶温度、熔融温度、结晶度和结晶速率 ,但降低聚丙烯结晶的完善程度 .粒子的表面接枝处理 ,因改善了粒子与基体的亲和性而有利于粒子成核效应的提高 ,而且此效应尚与粒子的分散相关     

聚丙烯表面接枝改性络合金的研究

探索了一种通过聚丙烯(PP)改性来络合金金属的新途径.首先在PP膜上经紫外光引发实施丙烯酸的接枝聚合反应,得到表面带—COOH基团的改性PP膜;再用负离子开环聚合的方法在改性后的PP膜上接枝尼龙6.上述处理后的膜表面含有大量O、N的功能基团,故可将此膜用于对溶液中金的络合.利用ATR、SEM、XPS等技术对改性及络合进行了表征.实验结果表明,此方法制备的PP膜对金的络合效果明显.     

Plasma modification of polypropylene surfaces and grafting copolymerization of styrene onto polypropylene

The surface of polypropylene(iPP) is modified with glow discharge plasma of Ar,so that the modified surfaces of iPP films are obtained.The studies of scanning electron microscopy(SEM) show the surface etching pattern of iPP films. The chemical structures of iPP films are confirmed by X-ray photoelectron spectroscopy(XPS) and Fourier transform infrared(FTIR) spectroscopy.The wetting properties of modified surfaces of iPP films are characterized by contact angle, and the free energy of surfaces is calculated.The free radical of modification surfaces of iPP is measured by chemical method.The surfaces of iPP are achieved with Ar plasma treatment followed by grafting copolymerization with styrene(St) in St.The grafting polymer of St onto iPP is characterized by FTIR.The grafting rate is dependent on plasma exposure time and discharge voltage.The studies show that homopolymerization of St is undergone at the same time during the grafting-copolymerization of St onto iPP.     

Surface modification of polymers. III. Grafting of stabilizers onto polymer films

Polypropylene, polystyrene, and polyethylene have been grafted with glycidyl acrylate and glycidyl methacrylate. After 5 min of grafting with UV irradiation, polystyrene was extensively grafted to 91% coverage of glycidyl acrylate according to ESCA, while polypropylene was grafted to only 50% coverage. With glycidyl acrylate the grafting depth is estimated to be 0.1 μm for PP and 0.23 μm for PS. Glycidyl methacrylate is grafted in a thinner layer than glycidyl acrylate. The stabilizers 2,4-dihydroxybenzophenone, phenyl 4-aminosalicylate, and 4-amino-2,2,6,6-tetramethylpiperidine were attached to LDPE surfaces containing grafted glycidyl acrylate by opening of the epoxide bond. The reaction between epoxide and stabilizer is diffusion controlled at high concentrations of stabilizer. UV spectroscopy on an LDPE film grafted and reacted with 2,4-dihydroxybenzophenone showed that 227 nmol stabilizer/cm² was bound to the surface.     

CaCO_3表面包覆改性及其对填充PP力学性能的影响

先用丙烯酸(AA)处理CaCO3,在其表面引入活性双键基团后,再通过固相包覆反应将聚丙烯蜡(PPW)固定在CaCO3表面.实验发现改性CaCO3可经受甲苯、稀盐酸处理而不发生溶解,结合红外及热重分析结果,证明PPW已经通过化学键合而成功地包覆在CaCO3表面.将该改性CaCO3填充聚丙烯(PP)后,发现PP的冲击性能及拉伸性能均有不同程度的提高,当改性CaCO3的填充量为15份时,体系的缺口冲击强度达到最大值,为基体树脂的1.68倍;当改性CaCO3的填充量10份时拉伸强度达到峰值,为同等添加量的未改性CaCO3的1.22倍.     

PP熔融接枝改性研究进展

聚丙烯作为一种非极性聚合物,其亲水性、染色性、粘结性及与其它极性聚合物和无机填料的相容性都很差,这大大限制了它的应用。因此,往往采用官能化的方法赋予聚丙烯以极性、反应活性和功能性。通过熔融接枝的方法,在聚丙烯链段上接枝极性单体,可以显著提高聚丙烯的极性,改善表面亲水性及染色性等。本文简要介绍了聚丙烯熔融接枝改性及其影响因素,并按接枝单体分类,综述了熔融接枝聚丙烯的研究进展、性能与应用,展望了其发展趋势。     

Grafting of glycidyl methacrylate onto polypropylene using supercritical carbon dioxide

Free-radical grafting of glycidyl methacrylate (GMA) onto polypropylene (PP) films has been studied using supercritical carbon dioxide (SC-CO₂) as a solvent and a swelling agent. As the reaction temperature was below the melting point, PP was modified in the solid phase. The PP film was first soaked with the monomer GMA and benzoyl peroxide (BPO) as an initiator using SC-CO₂ at different experimental conditions of pressure, temperature, and thermal treatment time. After releasing CO₂, film GMA molecules were grafted onto PP in different times. Using this method, the degree of grafting and the morphology could be controlled through the combination of pressure, temperature, and soaking time. FTIR spectra confirmed that GMA had been grafted onto PP and that polypropylene-graft-glycidyl methacrylate (PP-g-GMA) presented a high surface reactivity for conductive polyaniline anchoring. DSC measurements and TG analyses showed that the thermal profiles of the graft copolymer and virgin PP are quite similar and that the graft PP does not exhibit changes in terms of thermal degradation profile and melting temperature, respectively. X-ray data showed that a high degree of grafting leads to a lower degree of crystallinity of polypropylene.     

PEROXIDE GRAFTING OF POWDERED POLYPROPYLENE BY BUTYL ACRYLATE

The efficiency of the grafting of powdered polypropylene (PP) by butyl acrylate (BA) initiated by tert.-butylperoxy-2-ethylhex-as a ratio of the grafted and polymerized monomer was relatively high during the whole course of the reaction and it does not decrease under 0.5. The relatively high polymerization rate and also grafting efficiency at the beginning of the reaction is refered to the gel effect - the monomer is absorbed in the amorphous part of the powdered PP. With increasing the content of monomer in the reaction feed, the content of unsoluble cross-linked polymer increased as the consequence of the radical cross-linking of polybutylacrylate chains. The mechanism of grafting of powdered PP by BA is discussed.     

Facile Fabrication of Monolayered Hollow Submicrospheres of PANI on Surfaces of Modified Polymer Films

Summary: A novel strategy was developed in order to prepare monolayered polyaniline (PANI) submicrospheres on polymer substrates. The strategy involved two main steps, i.e., photografting of acrylate acid (AA) onto the surface of a polypropylene (PP) film, and subsequent oxidative polymerization of aniline on the grafted surface. It was found that the PANI monolayered hollow submicrospheres were immobilized on the surface of the PP film when the molar ratio of AA to aniline was about 1:1.6. A possible formation mechanism of the hollow PANI submicrosphere iss discussed.     

聚丙烯表面接枝PNIPAAm膜Ⅰ.光接枝反应和表面形态结构研究

以氧杂蒽酮或二苯甲酮为引发剂 ,通过紫外光引发表面接枝聚合的方法在聚丙烯薄膜表面引入了具有温度敏感特性的聚异丙基丙烯酰胺 (PNIPAAm)接枝聚合物层 .提高紫外光强度和接枝反应温度均有利于接枝率增大 ,而单体浓度对接枝率的影响存在最佳值 ,为 0 1 8mol L .在引发剂预浸渍引发接枝和休眠基引发接枝这两种方式中 ,后者能够实现更高的接枝率 .红外光谱 (FTIR)、X射线光电子能谱化学分析 (ESCA)和扫描电子显微镜 (SEM)等对接枝层组成的表征结果证实了接枝层的存在 .在不同温度下 ,接枝膜的FTIR谱图中酰胺I带和酰胺II带特征吸收峰发生位移 ,表明它具有温度敏感特性 .同时 ,SEM研究发现由于接枝膜的温度敏感特性而导致的球状表面形态结构     

Grafting copolymerization of polyethylene glycol methacrylate (PEGMA) onto preirradiated PP films

Polyethylene glycol methacrylate (PEGMA) with different polyethylene oxide units were grafted onto polypropylene (PP) films by a preirradiation grafting method. The effect of co-solvent system on the degree of grafting and water contact angle were determined, respectively. The grafted sample films were verified by Fourier Transform Infrared (FTIR) spectroscopy in the attenuated total reflectance mode (ATR). The biocompatibility and blood compatibility of the grafted PP films were evaluated by the determination of protein adsorption, platelet adsorption and thrombus.     

A facile method to prepare polypropylene/poly(butyl acrylate)alloy via water–solid phase suspension grafting polymerization

Polypropylene/poly(butyl acrylate) alloy is produced by water–solid phase suspension grafting polymerization with a submicrometer microdomain where graft polymerization occurs within micropores of polypropylene particles prepared by reactor granule technology(RGT). The results show that the grafting percentage(GP) of butyl acrylate(BA) increases with the increase of the monomer concentration, which could reach 32.6% while the grafting efficiency(GE) is up to 98%. The addition of the crosslinking agent, triethylene glycol diacrylate(TEGDA), could improve GP up to 36.3%. Transmission electron microscopic(TEM) micrographs demonstrate that PBA microdomains distributed in PP matrix increase in size less than 500 nm. Moreover, TEM images show that the grafting phase exhibits a singlephase behavior with the addition of TEGDA, which implies that the ratio of graft copolymer increased.     

A novel photoadditive for polyolefin photostabilization: hindered amine light stabilizer

Hindered‐amine light stabilizers were surface anchored to polyethylene and polypropylene thin films by: i) direct photo‐grafting of 1,2,2,6,6‐pentamethyl piperidinyl‐4‐acrylate onto the surface and ii) by reacting of 1,2,2,6,6‐pentamethyl‐4‐piperidinol with succinic anhydride functionalized polyolefin surface. The samples were exposed to UV irradiation in air and the oxidative‐degradation of the polymers was studied with FT‐IR spectroscopy. The photo‐stability of surface anchored Hindered‐amine stabilizers (HAS) was compared with films stabilized with commercial HAS by melt blending. The results of the study evince superiority of surface anchored HAS over that of melt blended polyolefins.