Graft copolymerization of polyethylene glycol methacrylate onto polyethylene film and its blood compatibility

In an attempt to produce surfaces that show low levels of adsorption of protein and adhesion of platelets, different molecular weights of polyethylene glycol methacrylate (PEG‐MA) were grafted onto polyethylene film by a preirradiation grafting process. The extent of grafting was found to be dependent on the storage condition of the irradiated polyethylene film, the preirradiated dose, reaction time and temperature, molecular weight of PEG‐MA, and the type of solvent. The grafting yield was found to decrease rapidly with storage time for irradiated polyethylene film stored at room temperature. On the other hand, the grafting yield in the irradiated polyethylene stored at −130°C remained nearly constant up to 20 days after irradiation. The grafting yield decreased with an increased PEG‐MA molecular weight. Human plasma protein was adsorbed onto control and PEG‐MA‐grafted polyethylene film surfaces, and the relative adsorbed amount of proteins on the surfaces was evaluated by electron spectroscopy for chemical analysis. The adsorbed protein and platelet adhesion on the polyethylene film surface decreased rapidly with the grafting yield. © 1999 John Wiley & Sons, Inc. J Appl Polym Sci 71: 631–641, 1999     

Photo‐induced grafting of poly(ethylene glycol) onto polyamide thin film composite membranes

In this study, the surface grafting of poly(ethylene glycol) (PEG) onto commercial polyamide thin film composite (TFC‐PA) membranes was carried out, using ultraviolet photo‐induced graft polymerization method. The attenuated total reflection Fourier transform infrared spectra verify a successful grafting of PEG onto the TFC‐PA membrane surface. The scanning electron microscope and atomic force microscope analyses demonstrate the changes of the membrane surface morphology due to the formation of the PEG‐grafted layer on the top. The contact angle measurements illustrate the increased hydrophilicity of the TFC‐PA‐g‐PEG membrane surfaces, with a significantly reduced water contact angles compared to the unmodified one. Consequently, the separation performance of the PEG‐grafted membranes is highly improved, with a significant enhancement of flux at a great retention for removal of the different objects in aqueous feed solutions. In addition, the antifouling property of the modified membranes is also clearly improved, with the higher maintained flux ratios and the lower irreversible fouling factors compared to the unmodified membrane. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134, 45454.     

Hemocompatibility evaluation of polyurethane film with surface‐grafted poly(ethylene glycol) and carboxymethyl‐chitosan

To improve the hemocompatibility and biocompatibility of polyurethanes (PUs), PU surface was firstly modified by poly(ethylene glycol) PEG through acryloyl chloride and subsequently grafted on carboxymethyl‐chitosan (CMCS). Attenuated total reflection Fourier transform infrared spectroscopy and X‐ray photoelectron spectroscopy analysis confirmed that carboxyl‐chitosan was grafted onto PUs surface. The surface properties of unmodified and modified PU films were determined and compared by water contact angle assessment. After PEG and CMCS grafting, the surface energy of the PU film was increased. Furthermore, the hemocompatibility of the modified PU films was systematically evaluated by bovine serum albumin (BSA) adsorption, the dynamic blood clotting test, the platelet adhesion test, and the hemolytic test. It appears that BSA adsorption and platelet adhesion were significantly curtailed for the modified PU films. Therefore, the obtained results showed the modified PU film has better hemocompatibility. © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

Surface modification of polyurethane by plasma-induced graft polymerization of poly(ethylene glycol) methacrylate

A new approach, plasma-induced graft polymerization of poly(ethylene glycol) methacrylate (PEGMA), was used to introduce PEG graft chains with hydroxyl end groups onto a polyurethane (Tecoflex) surface. After argon plasma treatment and subsequent exposure to air, graft polymerization onto Tecoflex films was allowed to proceed in deaerated aqueous solutions of PEGMA at 60°C. The virgin, plasma-treated, and grafted films were characterized comparatively by means of attenuated total reflection infrared spectroscopy, X-ray photoelectron spectroscopy, atomic force microscopy, measurement of contact angle, and protein adsorption. The Tecoflex film undergoes etching during argon plasma treatment, surface oxidation when exposed to air after plasma treatment, and surface restructuring in response to environment upon storage in air. The plasma-induced graft polymerization of PEGMA proved to be successful in introducing PEG graft chains with reactive hydroxyl end groups onto the surface. Grafted films with different surface grafting density of PEG were prepared. Grafted films with higher PEG content exhibit higher hydrophilicity, smoother topography, and lower fibrinogen adsorption. The hydroxyl end groups built onto the surface offer further possibilities of improving its biocompatibility by immobilizing bioactive molecules. © 1996 John Wiley & Sons, Inc.     

Surface structure and adhesive properties of biaxially oriented polypropylene film grafted with poly(acrylic amide) using corona discharge

Corona discharge was explored as a means of forming chemically active sites on the surface of biaxially oriented polypropylene (BOPP) film. The active species formed in air was used to induce graft copolymerization of acrylic amide (AAM) in aqueous solution. The surface structure, hydrophilicity and adhesion of the grafted BOPP film were characterized by the extent of grafting, electron spectroscopy for chemical analysis (ESCA), scanning electron microscopy (SEM), peel strength and contact angle measurements. Surface graft‐copolymerization of AAM onto BOPP film by corona discharge in air can be carried out with high efficiency. With increasing copolymerization time, the degree of grafting of AAM onto BOPP increases. The degree of grafting achieved a relatively high value of 2.13 wt% for the conditions of 1 min corona discharge and a copolymerization reaction time of 2.5 hr in 20% AAM aqueous solution at 70°C. After corona discharge grafting, the contact angle of water on the BOPP film decreased and the peel strength increased compared with those for ungrafted BOPP film. The hydrophilicity and adhesion of BOPP were improved by surface graft copolymerization with AAM induced by corona discharge.     

Penetration behavior and subsurface grafting of dansyl cadaverine and polyethylene glycol (PEG) derivatives in poly(ethylene-co-acrylic acid) (EAA) film

Dansyl cadaverine and polyethylene glycol (PEG) derivatives were grafted on the surface of EAA film and in its subsurface region through formation of amides and esters, respectively. A two-step reaction was conducted. First, EAA film was activated with PCl₅ at room temperature. Second, the acid chloride was reacted with dansyl cadaverine or a PEG derivative to form a modified film. ATR-FTIR spectroscopy and fluorometry were employed to analyze the modified films after each step. It was found that dichloromethane yielded the highest grafting efficiency, with the dansyl cadaverine penetrating throughout the ATR-FTIR analysis region (∼400 nm) in a few minutes. As the grafting depth increased with time, so did the amount of fluorescence intensity of grafted dansyl cadaverine. ATR-FTIR spectra for PEG grafting indicated that the acid chloride peak decreased with time, while the ester peak increased. However, hydrolysis occurred at later times, consuming the acid chloride groups within the film. A marked decrease of static water contact angle was observed for EAA grafted with PEG99 (PEG that contains 99 ethylene glycol repeat units), almost 40° lower than that of neat EAA (∼99°). For other PEG-grafted films, the surface hydrophilicity was also improved.     

Grafting sulfobetaine monomer onto silicone surface to improve haemocompatibility

Silicone rubber has been used as a biomaterial for more than two decades and displays good mechanical and optical properties, but its chemical nature, poor antithrombogenicity, as well as its hydrophobicity, prevents its use in many demanding biomedical applications. In order to provide modified silicone with enhanced haemocompatibility, surface modification techniques were used. Ozonization was used to introduce active peroxide groups onto the silicone film surface and, subsequently, graft polymerization of N,N′‐dimethyl‐N‐methacryloyloxyethyl‐N‐(3‐sulfopropyl) ammonium (DMMSA), a zwitterionic sulfobetaine structure, onto the ozone activated silicone surface was conducted. Surface analysis was accomplished by means of attenuated total reflectance‐Fourier‐transform infrared (ATR‐FTIR), and X‐ray photoelectron spectra (XPS), and scanning electron microscopy (SEM) and contact angle measurement. ATR‐FTIR and XPS investigation confirmed the graft polymerization. The grafted film possessed a relatively hydrophilic surface as indicated by contact angle measurement. The blood compatibility of the grafted films was evaluated by platelet adhesion in platelet‐rich plasma (PRP) and protein adsorption in bovine fibrinogen using silicone film as the reference. No platelet adhesion was observed for the grafted films incubated in PRP for 120 min. The protein adsorption was reduced on the grafted films after incubated in bovine fibrinogen for 120 min. These results confirmed that the improved blood compatibility was obtained by grafting this new zwitterronic sulfobetaine structure onto silicone film. Copyright © 2003 Society of Chemical Industry     

Characterization of Surface Modification of Polyethersulfone Membrane

Surface modification of polyethersulfone (PES) membrane surfaces using UV/ozone pretreatment with subsequent grafting and interfacial polymerization on membrane surface was investigated in order to improve the resistance of membrane surface to protein adsorption. The surface modifications were evaluated in terms of hydrophilicity, chemical composition of the surface and static protein adsorption. In both methods, poly(vinyl alcohol) (PVA), poly(ethylene glycol) (PEG) and chitosan were chosen as hydrophilic polymers to chemically modify the commercial virgin PES membrane to render it more hydrophilic as these materials have excellent hydrophilic property. Modified PES membranes were characterized by contact angle and XPS. Contact angles of modified PES membranes were reduced by 19 to 58% of that of the virgin PES membrane. PES membrane modified with PEG shows higher wettability than other hydrophilic materials with the highest contact angle reduction shown for UV/ozone pretreated, PEG grafted PES membrane surface. In general, XPS spectra supported that the PES membranes were successfully modified by both grafting with UV/ozone pretreatment and interfacial polymerization methods. The results of the static protein adsorption experiments showed all surface modifications led to reduction in protein adsorption on PES membranes; the highest protein adsorption reduction occurred with membrane modified by UV/ozone pretreatment followed by PES grafting, which corresponded to the highest contact angle reduction. However, there seems to be no clear correlation between contact angle reduction and reduction in protein adsorption in the case that involved chitosan. Nevertheless, membranes modified with chitosan do show higher reduction in protein adsorption than membranes modified with other materials under the same conditions.     

Modification of polycarbonateurethane surface with poly (ethylene glycol) monoacrylate and phosphorylcholine glyceraldehyde for anti-platelet adhesion

Poly(ethylene glycol) monoacrylate (PEGMA) is grafted onto polycarbonateurethane (PCU) surface via ultraviolet initiated photopolymerization. The hydroxyl groups of poly(PEGMA) on the surface react with one NCO group of isophorone diisocyanate (IPDI) and another NCO group of IPDI is then hydrolyzed to form amino terminal group, which is further grafted with phosphorylcholine glyceraldehyde to establish a biocompatible hydrophilic structure on the surface. Fourier transform infrared spectroscopy and X-ray photoelectron spectroscopy confirm the successful grafting of both PEG and phosphorylcholine functional groups on the surface. The decrease of the water contact angle for the modified film is caused by synergic effect of PEG and phosphorylcholine, which both have the high hydrophilicity. Furthermore, the number of platelets adhered is relative low on the synergetically modified PCU film compared with the PCU film modified only by poly(PEGMA). Our synergic modification method using both PEG and phosphorylcholine may be applied in surface modification of blood-contacting biomaterials and some relevant devices.     

Which is more effective for protein adsorption: surface roughness,surface wettability or swelling? Case study of polyurethane films prepared from castor oil and poly(ethylene glycol)

In order to investigate the effects of surface roughness, surface wettability and swelling on protein adsorption, polyurethane films were prepared from castor oil (CO) and poly(ethylene glycol)‐3000 (PEG) using one‐shot bulk polymerization. Hexamethylene diisocyanate and 1,4‐butanediol were used as isocyanate and chain extender, respectively. The hydrophilicity of the polyurethane films was adjusted by varying the ratio of CO to PEG. The surface of the polyurethane films was treated using plasma polymerization in the presence of acrylic acid vapour. Therefore, the polyurethane films could be obtained with the same hydrophilicity but with different roughness. The hydrophilicity of untreated and treated polymer films was examined using contact angle measurements. The surface topology of the polymer films was investigated using scanning electron microscopy and atomic force microscopy. Adsorption of bovine serum albumin and bovine serum fibrinogen on treated and untreated polymer films was determined and the performance of the films was compared. After evaluation of all results it is found that surface roughness and swelling are as important as hydrophilicity for protein adsorption in the case of CO/PEG‐based polyurethanes. © 2012 Society of Chemical Industry     

One simple and stable coating of mixed‐charge copolymers on poly(vinyl chloride) films to improve antifouling efficiency

An antifouling surface is highly desirable for many biomedical applications. In this study, poly(vinyl chloride) (PVC) films were endowed with the improved properties of resisting nonspecific protein adsorption and platelet adhesion simply through being coated with a kind of mixed‐charge zwitterionic polymer, poly(3‐sulfopropyl methacrylate–methacrylatoethyl trimethyl ammonium chloride–glycidyl methacrylate) (PSTG), with random moieties of negatively charged 3‐sulfopropyl methacrylate potassium, positively charged [2‐(methacryloyloxy)‐ethyl] trimethylammonium chloride, and glycidyl methacrylate. The PSTG‐grafted PVC films were formed by the simple immersion of an amino‐functionalized PVC film into a PSTG solution. A grafting density of 220.84 µg/cm² of PSTG4‐grafted PVC film was successfully obtained. The PSTG4‐grafted PVC film showed a lower contact angle (37.5 °) than the ungrafted PVC film (98.3 °). The in vitro protein adsorption results show that the bovine serum albumin adsorption amount decreased 6.72 µg/cm² in the case of the PSTG4‐grafted PVC film, whereas that on the ungrafted PVC film was 28.54 µg/cm². So, PSTG‐grafted PVC films could be promising materials for medical devices. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134, 44632.     

Surface functionalization of polypropylene by entrapment of polypropylene‐grafted‐poly(ethylene glycol)

A surface functionalization polypropylene was prepared by entrapment a copolymer of polypropylene‐grafted‐poly(ethylene glycol) into polypropylene. The effects of structure of copolymer, contact dies, and content of modifiers were studied. The results of attenuated total reflection infrared spectroscopy(ATR‐FTIR) and contact angle measurements indicated that PP‐g‐PEG could preferably diffuse onto the surface and effectively increase the hydrophilicity of PP. PPw‐g‐PEG with lower PEG contents, lower molecular weight of PPw and PEG had better selective enrichment on the surface of PP blend film. By grafting of PEG‐OH onto the MPP, PP macromolecular surface modifier with better solvent‐resistance than that of PEG can be achieved. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Enhanced hydrophilic polysulfone hollow fiber membranes with addition of iron oxide nanoparticles

Membranes are at the heart of hemodialysis treatment functions to remove excess metabolic waste such as urea. However, membranes made up of pure polymers and hydrophilic polymers such as polyvinylpyrrolidone suffer problems of low flux and bio‐incompatibility. Hence, this study aimed to improve polysulfone (PSf ) membrane surface properties by the addition of iron oxide nanoparticles (IONPs ). The membrane surface properties and separation performance of neat PSf membrane and membrane filled with IONPs at a loading of 0.2 wt% were investigated and compared. The membranes were characterized in terms of morphology, pure water permeability (PWP ) and protein rejection using bovine serum albumin (BSA ). A decrease in contact angle value from 66.62° to 46.23° for the PSf /IONPs membrane indicated an increase in surface hydrophilicity that caused positive effects on the PWP and BSA rejection of the membrane. The PWP increased by 40.74% to 57.04 L m^?2 h^?1 bar^?1 when IONPs were incorporated due to the improved interaction with water molecules. Furthermore, the PSf /IONPs membrane rejected 96.43% of BSA as compared to only 91.14% by the neat PSf membrane. Hence, the incorporation of IONPs enhanced the PSf hollow fiber membrane hydrophilicity and consequently improved the separation performance of the membrane for hemodialysis application. © 2017 Society of Chemical Industry     

Enhancing the Interfacial Properties of Composites by Grafting Polyethylene Glycol and Polyvinyl Alcohol Onto a CF Surface

In this study, a carboxy esterification reaction was used to graft the hydrophilic polymers polyethylene glycol (PEG) and polyvinyl alcohol (PVA) onto the surface of carbon fibers (CFs). The properties of the grafted CFs were investigated by scanning electron microscopy (SEM), atomic force microscopy (AFM), X‐ray photoelectron spectroscopy (XPS), thermogravimetric analysis (TG) and through the measurement of interlaminar shear strength (ILSS). SEM enabled the graft morphology on CF surfaces to be determined. In comparisons of grafted and non‐grafted CFs, AFM indicated that the roughness was significantly improved; XPS showed that the concentration of oxygen‐containing functional groups increased by 186.1%; TG showed that the grafting rate of CF‐grafted PEG (CF‐g‐PEG) was 0.5%, and that of CF‐grafted PVA (CF‐g‐PVA) was 2.0%; and the ILSS of CF‐g‐PEG and CF‐g‐PVA increased by 22.7% and 43.0%, respectively. We conclude that esterification grafting is an effective method for modifying the physicochemical properties of CFs and improving the interfacial adhesion of composites. POLYM. ENG. SCI., 59:1043–1050, 2019. © 2019 Society of Plastics Engineers     

Preparation and characterization of novel hyperbranched poly(amine‐ester) films crosslinked by glutaraldehyde

Novel films based on hydroxyl terminated hyperbranched poly (amine‐ester) (HPAE‐OH) of different generation were prepared by crosslinking the terminal hydroxyl groups of HPAE with glutaraldehyde (GA). The progress of crosslinking reaction was characterized by Fourier transform infrared (FTIR) and viscosity measurement. The surface morphology of the crosslinked HPAE films was characterized by field emission scanning electron microscope (FE‐SEM) and atomic force microscopy. The results suggested that the films have homogenously dense interior matrices and smooth surface. The hydrophilicity/hydrophobicity of the crosslinked HPAE films was characterized by the water contact angle measurement. Variable swelling behavior in different solvents was also studied. The in vitro biocompatibility of the film was investigated by the bovine hemoglobin (Hb) adsorption measurement. And these results showed that these crosslinked HPAE films had excellent hydrophilicity, variable swelling behavior in different solvents, and relative low protein absorption. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Investigation of radiation‐grafted and radiation‐modified N‐vinyl‐2‐pyrrolidone onto polypropylene film

The radiation‐induced graft copolymerization of N‐vinyl‐2‐pyrrolidone (NVP) onto polypropylene films was investigated using the mutual method. The grafted polymer was modified with prepared α,β‐unsaturated nitrile (Scheme 1 ). The water uptake of the grafted and modified grafted films was found to increase with the degree of grafting. It was observed that the swelling behavior of the modified grafted films with α‐cyano‐β‐phenyl crotononitrile improved more than that of the film grafted and modified grafted with α‐cyano‐β‐(2‐thienyl)crotononitrile or α‐cyano‐β‐(2‐pyridyl)crotononitrile. The modification process for the grafted substrate was confirmed by IR spectroscopy. No significant improvement was observed in thermal stability for the modified grafted films compared to the grafted films. Scanning electron microscopy (SEM) of the grafted and modified grafted membranes heated to 150°C showed change in the structure and morphology. Improvement in the hydrophilicity and morphology of these membranes with carbonitriles may increase the permeability of those membranes for some practical applications.     

Protein‐grafted carboxylic poly(ether sulfone) membranes: Preparation and characterization

Carboxylic poly(ether sulfone) membranes were prepared by a controlled acetylating and surface‐oxidating reaction followed by the grafting of bovine serum albumin (BSA) and bovine serum fibrinogen (BFG) onto the surfaces. Attenuated total reflection–Fourier transform infrared spectroscopy, X‐ray photoelectron spectroscopy, and Micro BCA Protein Assay Kits confirmed that the proteins were successfully grafted onto the surfaces of the membranes. The protein grafting degrees were measured at different time intervals and under different conditions. The modified membranes showed higher hydrophilicity, lower protein (BSA and BFG) adsorption, and suppressed platelet adhesion values. Because of the binding of calcium ions in blood, the modified membranes showed longer plasma recalcification times, activated partial thromboplastin times, prothrombin times, and whole blood clotting times. The results indicate that the blood compatibility of the poly (ether sulfone) membranes could be improved after surface carboxylic modification and protein immobilization and that the modified membranes could be used in the blood purification field. © 2012 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

Ozone‐induced grafting of a sulfoammonium zwitterionic polymer onto low‐density polyethylene film for improving hemocompatibility

Ozone‐induced grafting was developed to improve the hemocompatibility of biomaterials based on low‐density polyethylene (LDPE). An LDPE film was activated with ozone and graft‐polymerized with N,N′‐dimethyl(methacryloylethyl)ammonium propane sulfonate (DMAPS). The existence of sulfobetaine structures on the grafted film was confirmed by X‐ray photoelectron spectroscopy and attenuated total reflection/Fourier transform infrared (ATR–FTIR). More DMAPS was grafted onto the LDPE film as the DMAPS concentration increased, as determined by ATR–FTIR. Static contact‐angle measurements indicated that the DMAPS‐grafted LDPE film had a significant increase in hydrophilicity. The blood compatibility of the grafted film was preliminarily evaluated with a platelet‐rich‐plasma (PRP) adhesion study. No platelet adhesion was observed on the grafted film incubated with PRP at 37°C for 180 min. This new sulfoammonium zwitterionic‐structure‐grafted biomaterial might have potential for biomedical applications. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 101: 3697–3703, 2006     

Reactivity of glycidyl methacrylate grafted cellulose film prepared by grafting under ultrasonic irradiation

Ultrasonic irradiation largely accelerated ceric salt initiated grafting of glycidyl methacrylate (GMA) on regenerated cellulose film (cellophane thickness = 20 μm) at 60°C in air. The grafting under ultrasonic irradiation was characterized by a higher percent of grafting and graft efficiency and a lower density of GMA‐grafted chains in the surface layer of the grafted films compared to the unirradiated system, which was obtained by attenuated total reflectance IR measurements. The grafted films were subjected to amination with ethylenediamine (En) at 70°C for 3 h in N,N‐dimethylformamide. The amount of epoxy groups in the grafted films, which participated in the reaction with En, reached about 50–60 mol % and was slightly lower for the grafted film prepared in the irradiated system than that prepared in the unirradiated one. Adsorption of cupric ions with the aminated samples was performed at pH 5.0 using Clark–Lubs buffer solution and cupric chloride. The adsorption was extremely retarded for the aminated sample prepared using the unirradiated sample compared to that prepared using the irradiated one. The retarded adsorption phenomenon is discussed in terms of a larger formation of crosslinked structures on the surface layer of the former sample during the amination. © 1999 John Wiley & Sons, Inc. J Appl Polym Sci 74: 2462–2469, 1999     

聚醚醚酮表面壳聚糖的固定

通过紫外光接枝和湿化学法连用在聚醚醚酮 （PEEK）表面固定上具有抑菌杀菌作用的壳聚糖。结果表明,相比未改性的PEEK表面,改性后材料表面亲水性提高;通过扫描电子显微镜和X射线光电子能谱分析证明壳聚糖成功接枝在了PEEK薄膜表面;随着壳聚糖浓度的提高,材料表面的壳聚糖接枝率增加。