Cell Adhesion and Proliferation on Plasma-Treated and Poly(ethylene glycol)-Grafted Polyethylene

Polyethylene (PE) was modified by an Ar plasma. The plasma-activated PE surface was grafted with poly(ethylene glycol) (PEG, molecular weight 300 and 20 000). The depth profiles of the oxygen in the modified PE samples were determined using Rutherford Backscattering Spectroscopy (RBS). The changes in the surface wettability were examined by goniometry, and Atomic Force Microscopy (AFM) was used to determine the surface roughness and morphology. The modified PE samples were seeded with rat vascular smooth muscle cells (VSMCs) and their adhesion and proliferation was studied. The plasma treatment and the subsequent PEG grafting leads to dramatic changes in the PE surface morphology, roughness and wettability. The PEG grafting of the plasma-treated PE does not increase VSMC adhesion but it results in dramatic increase of VSMC proliferation.     

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     

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     

Molecular markers of adhesion,maturation and immune activation of human osteoblast-like MG 63 cells on nanocrystalline diamond films

A semi-quantitative evaluation was made of the concentration of α_v- and β₁-integrins, integrin-associated proteins talin and vinculin, cytoskeletal protein β-actin, differentiation markers osteocalcin and osteopontin, and immunoglobulin adhesion molecule ICAM-1 (CD 54), using an enzyme-linked immunosorbent assay (ELISA), in human osteoblast-like MG 63 cells in 5-day-old cultures on hydrophilic oxygen-terminated nanocrystalline diamond (NCD) films with either nanoscale surface roughness (nano-NCD, RMS of 8.2 nm) or hierarchically organized submicron- and nanoscale roughness (RMS of 301.0 nm and 7.6 nm, respectively). The concentration of talin was significantly higher in cells on submicron-nano-NCD (by 36.0 ± 6.2% compared to the value on the polystyrene dishes). In addition, the concentration of vinculin increased on both nano-NCD and submicron-nano-NCD (by 19.8 ± 3.4% and 26.0 ± 6.1%, respectively). The concentration of integrins α_v and β₁, β-actin, osteocalcin, osteopontin and ICAM-1 were similar in the cells on both the NCD films and the control polystyrene surfaces. These results suggest that nanocrystalline diamond films give good support for colonization with osteogenic cells and could be used for surface modification of bone implants in order to improve their integration with the surrounding bone tissue, or for biosensor technology, where firm cell–substrate adhesion is also required.     

PAN超滤膜的常压介质阻挡放电等离子体亲水改性

利用常压介质阻挡放电（DBD）等离子体技术,在非对称聚丙烯腈（PAN）超滤膜的表面接枝含有亲水基团的丙烯酸（AA）和聚乙二醇甲基丙烯酸酯（PEG360OHMA）,采用衰减全反射傅立叶变换红外光谱仪（ATR-FTIR）、水接触角测定仪和扫描电镜（SEM）表征膜的表面性质,牛血清蛋白（BSA）溶液过滤实验考察膜的抗生物污染性能。结果表明,常压DBD等离子体亲水改性的超滤膜具有良好的抗生物污染性能。     

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     

Grafting of PEG400 onto the surface of LLDPE/SMA film

Linear low-density polyethylene (LLDPE) was melt and blended with styrene-maleic anhydride copolymer (SMA). The blending films were then immersed in poly(ethylene glycol)400 (PEG400) at room temperature. The surface composition of the blend films was determined by Fourier transform infra-red spectroscopy coupled with a variable incidence angle attenuated total reflection accessory (ATR-FTIR). Results show that PEG400 can be grafted onto the surface of the films via esterification with SMA. The immersion of PEG promotes the enrichment of SMA onto the surface of the films. The water contact angle data show that grafting of PEG400 onto PE can greatly improve the hydrophilicity of the PE surface. These experiments show that surface functionalization of polyethylene films by blending SMA and then surface grafting of PEG is feasible, which suggest an effective and simple route for PE surface modification via blending and grafting. Translated from Acta Polymerica Sinica, 2006, (6), 829–832 [译自: 高分子学报]     

Synthesis of polyethylene glycol-polystyrene core-shell structure particles in a plasma-fluidized bed reactor

Particles with core-shell structure with polystyrene (PS) core and polyethylene glycol (PEG) grafted on the surface were synthesized in a plasma-fluidized bed reactor. The virgin, plasma-treated, and grafted powders were characterized by the DPPH method, UV-vis spectrophotometer, NMR, FT-IR and SEM. The plasma-treated PS powders have well formed peroxide on the surface. By PEG grafting polymerization, PEG is well grafted and dispersed on the surface of the plasma-treated PS powders. The PEG-g-PS powder exhibits the core shell structure in the cross-sectional SEM image, and it can be claimed that well dispersed PEG grafting polymerization on PS surface can be achieved in the plasma fluidized bed reactor.     

Autoadhesion of high density polyethylene (HDPE) to HDPE by ultraviolet grafting of methacrylates and acrylates

A study has been made on the effect of the presence of grafted acrylic layers on the autoadhesion of polyethylene. Methyl methacrylate (MMA), ethyl methacrylate (EMA), methyl acrylate (MA), ethyl acrylate (EA), and butyl methacrylate (BMA) were grafted onto high density polyethylene (HDPE). The grafting reaction was faster at higher temperature and methacrylates graft more easily than acrylates. For methacrylates and acrylates, the grafted amount increases with increasing length of the pendant alkyl chain. The grafting temperature is a crucial factor affecting the adhesion of grafted PE samples. For the samples grafted at lower temperature (in a room temperature water bath), the adhesion is very low (less than 50 N/m), even for very thick grafted layers. But for the samples grafted at higher temperature, much higher adhesion can be obtained. The presence of homopolymer was another factor affecting the adhesion of PE samples. When homopolymer is removed from the surface of the grafted sample, higher adhesion can be obtained. For some samples, the highest peel strength of more than 1000 N/m has been obtained. The low adhesion of the samples grafted at low temperature is attributed to the high branching of grafted chains.     

AUTOADHESION OF HIGH DENSITY POLYETHYLENE (HDPE) TO HDPE BY ULTRAVIOLET GRAFTING OF METHACRYLATES AND ACRYLATES

A study has been made on the effect of the presence of grafted acrylic layers on the autoadhesion of polyethylene. Methyl methacrylate (MMA), ethyl methacrylate (EMA), methyl acrylate (MA), ethyl acrylate (EA), and butyl methacrylate (BMA) were grafted onto high density polyethylene (HDPE). The grafting reaction was faster at higher temperature and methacrylates graft more easily than acrylates. For methacrylates and acrylates, the grafted amount increases with increasing length of the pendant alkyl chain. The grafting temperature is a crucial factor affecting the adhesion of grafted PE samples. For the samples grafted at lower temperature (in a room temperature water bath), the adhesion is very low (less than 50 N/m), even for very thick grafted layers. But for the samples grafted at higher temperature, much higher adhesion can be obtained. The presence of homopolymer was another factor affecting the adhesion of PE samples. When homopolymer is removed from the surface of the grafted sample, higher adhesion can be obtained. For some samples, the highest peel strength of more than 1000 N/m has been obtained. The low adhesion of the samples grafted at low temperature is attributed to the high branching of grafted chains.     

Growth of muscle cells on plasma-treated and gold nanoparticles-grafted polytetrafluoroethylene

Polytetrafluoroethylene (PTFE) was modified by Ar plasma with different exposure times. The plasma-activated surface was immersed in biphenyldithiol and subsequently in colloidal solution of Au nanoparticles. The changes in the surface wettability contact angle were examined by goniometry. Atomic force microscopy was used to determine the surface roughness and morphology. Changes in the chemical structure of the modified PTFE were studied using X-ray photoelectron spectroscopy (XPS) and electrokinetic analysis. The interaction of plasma-treated and grafted samples with vascular smooth muscle cell derived from the rat aorta was also studied. Specifically, the number and morphology of the adhered and proliferated cells on the PTFE were studied under in vitro conditions. The plasma treatment and the subsequent biphenyldithiol and Au nanoparticles grafting led to changes in the polymer surface chemistry, morphology, roughness and wettability. The polymer grafting with biphenyl-4,4′-dithiol (BFD) and subsequently with Au nanoparticles led to a decrease in the surface polarity. XPS measurements proved the presence of S and Au on the PTFE surface. Grafting with BFD and Au nanoparticles led to the decrease in surface roughness. In comparison with the pristine polymer, the plasma treatment and Au nanoparticles grafting increased the adhesion and proliferation of vascular smooth muscle cell.     

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.     

Improving the Adhesion of Polyethylene by UV Grafting

This article briefly reviews the progress in ultraviolet (UV) or photoinitiated grafting for improving the adhesion property of polyethylene (PE). The first part involves the progress in the fundamental study of UV grafting, including the grafting methods, the photoinitiators, and the self-initiated grafting; the second part focuses on the progress in adhesion improvements of PE by UV grafting, including the auto-adhesion or adhesive free adhesion, the photolamination, and the grafting of reactive functional monomers. The factors affecting the adhesion of grafted PE are also discussed.     

Improving the Adhesion of Polyethylene by UV Grafting

This article briefly reviews the progress in ultraviolet (UV) or photoinitiated grafting for improving the adhesion property of polyethylene (PE). The first part involves the progress in the fundamental study of UV grafting, including the grafting methods, the photoinitiators, and the self-initiated grafting; the second part focuses on the progress in adhesion improvements of PE by UV grafting, including the auto-adhesion or adhesive free adhesion, the photolamination, and the grafting of reactive functional monomers. The factors affecting the adhesion of grafted PE are also discussed.     

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.     

Grafting of branched polymers onto nano-sized silica surface: Postgrafting of polymers with pendant isocyanate groups of polymer chain grafted onto nano-sized silica surface

To control the surface wettability of nano-sized silica surface, the postgrafting of hydrophilic and hydrophobic polymers to grafted polymer chains on the surface was investigated. Polymers having blocked isocyanate groups were successfully grafted onto nano-sized silica surface by the graft copolymerization of methyl methacrylate (MMA) with 2-(O-[1′-methylpropylideneamino]caboxyamino)ethyl methacrylate (MOIB) initiated by azo groups previously introduced onto the surface. The blocked isocyanate groups of poly(MMA-co-MOIB)-grafted silica were stable in a desiccator, but isocyanate groups were readily regenerated by heating at 150 °C. The hydrophilic polymers, such as poly(ethylene glycol) (PEG) and poly(ethyleneimine) (PEI), were postgrafted onto the poly(MMA-co-MOIB)-grafted silica by the reaction of functional groups of PEG and PEI with pendant isocyanate groups of poly(MMA-co-MOI)-grafted silica to give branched polymer-grafted silica. The percentage of grafting increased with increasing molecular weight of PEG, but the number of postgrafted chain decreased, because of steric hindrance. The hydrophobic polymers, such as poly(dimethylsiloxane) were also postgrafted onto poly(MMA-co-MOI)-grafted silica. It was found that the grafting of hydrophobic polymer and the postgrafting of hydrophilic polymer branches readily controls the wettability of silica surface to water.     

Electrochemical properties of polyethylene membrane modified with sulfonic and phosphonic acid groups

Ion-exchange membranes modified with sulfonic (-SO₃H) and phosphonic acid (-PO₃H) groups were prepared by radiation-induced grafting of glycidyl methacrylate (GMA) onto polyethylene (PE) films and sub-sequent sulfonation and phosphonation of poly(GMA) graft chains. The surface area, thickness and volume of grafted PE film increased with increasing grafting yield. The specific electrical resistance of PE membrane modified with the -PO₃H and -SO₃H groups decreased with increasing the ion-exchange capacity. The PE membrane modified with -PO₃H group had a lower specific electrical resistance than that of PE membrane modified with -SO₃H group.     

Surface Modification of Nanoporous Poly(ϵ-caprolactone) Membrane with Poly(ethylene glycol) to Prevent Biofouling: Part I. Effects of Plasma Power and Treatment Time

Biofouling, a result of protein adsorption and cell adhesion on a surface, is detrimental to membrane performance. The objective of this study is to modify the polycaprolactone (PCL) membrane surface with poly(ethylene glycol) (PEG) to prevent fibroblast adhesion. To achieve this goal, oxygen plasma and PEG(400)-monoacrylate were used to graft the PEG onto the membrane surface through covalent bonding. Various plasma treatment conditions were investigated to optimize the PEG-grafting quality and to achieve minimum fibroblast adhesion. After the treatment, the water contact angle decreased significantly. Attenuated total reflectance-Fourier transform infrared spectroscopy (ATR-FTIR) spectra indicated that PEG was successfully grafted onto the PCL membrane with the appearance of the PEG characteristic peaks. X-ray photoelectron spectroscopy (XPS) revealed that different plasma powers and treatment times changed the surface composition of membranes. To evaluate the applicability of this new strategy for the prevention of biofouling, NIH 3T3 fibroblast was used as a model biofoulant. Cell adhesion and morphology studies indicate that either lower plasma power or shorter treatment time is able to improve resistance to the cell adhesion. This simple and efficient method can be applied to inhibit biofouling on the membrane surface.     

Comparison of two approaches to grafting hydrophilic polymer chains onto polysulfone films

To reduce the surface protein adsorption of polysulfone (PSf) film, we improved the hydrophilicity of this film by photochemical grafting of methoxypoly (ethylene glycol) (MPEG) derivatives on its surface. Grafting was achieved with both the simultaneous method and the sequential method. Surface analysis of the grafted film by X‐ray photoelectron spectroscopy (XPS) revealed that the PEG chains had successfully grafted onto the surface of the film. The grafting efficiencies by simultaneous and sequential methods were 20.8% and 10.2%, respectively. With an atomic force microscope (AFM), the surface topography of PEG‐grafted films by these two methods was compared. Static water contact angle measurement indicated that the surface hydrophilicity of the film had been improved. Protein adsorption measurement showed that the surface protein adsorption of the modified film was significantly reduced compared with that of the unmodified PSf film. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 103: 3818–3826, 2007     

Influence of polydopamine deposition conditions on pure water flux and foulant adhesion resistance of reverse osmosis, ultrafiltration, and microfiltration membranes

The influence of polydopamine (PDOPA) deposition and poly(ethylene glycol) (PEG) grafting on pure water flux and bovine serum albumin (BSA) adhesion of two polysulfone ultrafiltration (UF) membranes, a poly(vinylidene fluoride) microfiltration (MF) membrane, and a polyamide reverse osmosis (RO) membrane is reported. When modified with PDOPA, all membranes exhibited a systematic reduction in protein adhesion. For example, 90 min of PDOPA deposition led to at least 96% reduction in BSA adhesion to these membranes at neutral pH. BSA adhesion was further reduced by subsequent PEG grafting to PDOPA (PDOPA-g-PEG). The membranes’ pure water flux values (i.e., with no foulants present) were influenced to different extents by PDOPA and PDOPA-g-PEG modifications. In the porous membranes (i.e., the UF and MF membranes), the pure water flux reduction due to these modifications correlated with membrane pore size, with the smallest flux reductions observed in the MF membrane (e.g., <1% flux reduction for all PDOPA modification times considered), which have the largest pores, and the largest flux reductions occurring in UF membranes (e.g., a 40% flux reduction after 90 min of PDOPA deposition), which have pore sizes on the order of the PDOPA deposition thickness. The RO membranes, which are essentially non-porous, exhibited a flux reduction of 25% after 90 min of PDOPA deposition.