Heparin-containing block copolymers

Newly synthesized heparin-containing block copolymers, consisting of a hydrophobic block of polystyrene (PS), a hydrophilic spacer-block of poly (ethylene oxide) (PEO) and covalently bonded heparin (Hep) as bioactive block, were coated either onto glass, poly (dimethylsiloxane), polyurethane or PS substrates. Coated surfaces were characterized by determination of the surface-bound heparin activity, adsorption of AT III, plasma recalcification time assays, adhesion of platelets and by an ex vivo rabbit A-A shunt model.It was demonstrated that heparin was available at the surface of all heparin-bound surfaces to interact with AT III and thrombin and to prevent the formation of clots. The maximum immobilized heparin activity was found to be 5.5×10^-3 U cm^-2. Coated surfaces showed a significant prolongation of the plasma reclacification times as compared to control surfaces, due to surface-immobilized heparin. The platelet adhesion demonstrated that platelets reacted only minimally with the heparin-containing block copolymers in the test system and that the heparin-containing block copolymers seemed to passify the surface as compared to control surfaces. In the ex vivo A-A shunt experiments, which were carried out under low flow and low shear conditions, the heparin-containing block copolymers exhibited prolonged occlusion times, indicating the ability of the heparin-containing block copolymers to reduce thrombus formation at the surface.     

Polystyrene/wood composites and hydrophobic wood coatings from water-based hydrophilic-hydrophobic block copolymers

 The combination of synthetic thermoplastic polymers and wood is normally problematic because wood surfaces are hydrophilic while typical thermoplastic polymers are hydrophobic. A possible solution is to use block copolymer coupling agents. In this work we show the use of a potentially useful synthetic method of producing hydrophilic-hydrophobic block copolymers as hydrophobic coatings and coupling agents in polystyrene/wood flour composites. In particular, wood veneers are coated with water-based emulsions of hydrophilic-hydrophobic block copolymers from styrene and methacrylic acid. Dried coated surfaces are shown to become hydrophobic through dynamic contact angle measurements. When wood flour is coated with the hydrophilic-hydrophobic block copolymer based on styrene and acrylic acid, significant improvement in the ultimate tensile properties of composites formed from coated wood flour/polystyrene mixtures is realized. Since no volatile organic compounds (VOCs) are used in coating wood surfaces and subsequent composite production, improvement in mechanical properties of thermoplastic/wood flour composites are shown to occur in environmentally responsible formulations. Received: 13 May 1999 / Accepted: 5 February 2000     

Glow discharge plasma-induced immobilization of heparin and insulin on polyethylene terephthalate film surfaces enhances anti-thrombogenic properties

Polyethylene terephthalate (PET) films were treated with DC glow discharge plasma followed by graft copolymerization with acrylic acid (AA) and polyethylene glycol (PEG). The obtained PET–PEG was coupled to heparin or insulin molecules. The surfaces were then characterized by contact angle measurements, atomic force microscopy (AFM) and X-ray photoelectron spectroscopy (XPS). The surface energies of the modified PET films were estimated using contact angle measurements, and the changes in crystallinity of the plasma-modified PET film surfaces were investigated by X-ray diffraction (XRD) analysis. The blood compatibilities of the surface-modified PETs were examined by in vitro thrombus formation, whole blood clotting time, platelet contact and protein adsorption experiments. The results revealed that the contact angle value decreased and that the interfacial tension between the modified PET films and blood protein was drastically diminished compared to unmodified PET film. The XPS results showed that the PET–AA surface containing carboxylic acid and the immobilized PET surface containing both carboxylic acid and amino groups exhibited a hydrophilic character, and AFM results showed marked morphological changes after grafting of AA, PEG and biomolecule immobilization. Heparin and insulin-coupled PET surfaces exhibited much less platelet adhesion and protein adsorption than the other surface-modified PET film surfaces.     

嵌段共聚物PEO-b-PS薄膜的微相分离形貌

为实现对PEO-b-PS薄膜微相分离形貌和纳米结构的调控,通过原子转移自由基聚合制备了不同嵌段结构的PEO-b-PS,使用原子力显微镜研究了嵌段结构及热处理条件对溶液旋涂制备的PEO-b-PS薄膜微相分离形貌的影响.结果表明:PEO-b-PS薄膜发生微相分离后呈现PS锥状突起的分散形貌;提高热处理温度使微相分离加快,相分离程度提高,PS微区尺寸增大;延长热处理时间使PS锥状突起更加明显;PEO链长一定时,PS链长增加导致PS锥状微区数量和尺寸增加;PS链长一定时,PEO链长增加使PS锥状微区数量减少;嵌段比一定时,嵌段共聚物分子量增加使PS微区尺寸增大.通过调节PEO-b-PS嵌段结构和薄膜的热处理条件,可以实现对PEO-b-PS薄膜微相分离结构的控制.     

Preparation and performance of a novel multifunctional plasma electrolytic oxidation composite coating formed on magnesium alloy

Plasma electrolytic oxidation (PEO) in an alkaline phosphate electrolyte was used to produce a novel multifunctional polytetrafluoroethylene (PTFE)-containing oxide composite coatings on AM60B magnesium alloys. The composition and microstructure of the PTFE-containing PEO coatings were analyzed by X-ray photoelectron spectroscope (XPS), X-ray diffraction (XRD), and scanning electron microscope (SEM). The electrochemical corrosion behavior, tribological properties, and wetting properties of the PTFE-containing PEO composite coatings were evaluated using potentiodynamic polarization measurements, a reciprocating ball-on-disk tribometer, and a contact angle meter, respectively. Results show that the PTFE-containing PEO composite coatings exhibited superior corrosion resistance, excellent self-lubricating property, and better hydrophobic property when compared with pure PEO coatings, and will be the attractive advanced materials for a wide range of functional applications.     

Functionalized surfaces of polylactide modified by Langmuir–Blodgett films of amphiphilic block copolymers

To modify the surface of poly(L-lactide) (PLA) supports, we have investigated the feasibility to deposit on the PLA surface Langmuir–Blodgett films of amphiphilic block copolymers based on poly(L-lactide). AB and ABA block copolymers were prepared with PLA as the A block and either poly(ethylene oxide), -methoxy--hydroxy poly(ethylene oxide), -carboxy--hydroxy poly(ethylene oxide) or poly(L-aspartic acid) as the B blocks. Films with phase-separated hydrophilic and hydrophobic blocks in a bilayer brush structure were prepared by compression of the copolymer Langmuir films on the water/air interface. The interfacial behavior of the monolayers and the effect of the copolymer composition on the phase separation was followed by measurements of the surface-pressure/area isotherms using a Langmuir trough and by contact angle measurement of deposited Langmuir–Blodgett (LB) films. The phase separation of the hydrophilic and PLA blocks is more effective in diblock AB copolymers compared with triblock ABA copolymers. The presence of ionic groups in the hydrophilic chains facilitates penetration of hydrophilic segments into the water subphase. Dynamic contact angle measurements were used to study the stability of the LB-films transferred on the PLA support and the changes in the surface properties upon incubation of surfaces in water.     

Investigation into the mechanism of bacterial adhesion to hydrogel-coated surfaces

As a model for hydrogel-coated biomaterials, self-assembled monolayers of polyoxyethylene (POE) derivatives on sheets of polymeric biomaterials were prepared. The POE derivatives consisted of hydrophilic chains with different lengths and a long-chain alkyl group that served as an anchor function. The coatings obtained were analyzed with XPS and contact angle measurements showing hydrophilic chains of different lengths extending away from the surface. Bacterial adhesion was measured with a clinically relevant Klebsiella pneumoniae type strain and measurements reproduced 12 times. Bacterial adhesion decreased markedly with increasing hydrophilic chain length. Based upon these findings a new model for bacterial adhesion to hydrogel-coated surfaces is suggested: steric repulsion effects that increase with increasing chain length of grafted hydrophilic chains play an important role in bacterial adhesion to hydrogel-coated surfaces. © 1999 Kluwer Academic Publishers     

The influence of surface chemistry and topography on the contact guidance of MG63 osteoblast cells

The purpose of the present study was to determine in vitro the effects of different surface topographies and chemistries of commercially pure titanium (cpTi) and diamond-like carbon (DLC) surfaces on osteoblast growth and attachment. Microgrooves (widths of 2, 4, 8 and 10 μm and a depth of 1.5–2 μm) were patterned onto silicon (Si) substrates using microlithography and reactive ion etching. The Si substrates were subsequently vapor coated with either cpTi or DLC coatings. All surfaces were characterized using atomic force microscopy (AFM), scanning electron microscopy (SEM), X-ray photoelectron spectroscopy (XPS) and contact angle measurements. Using the MG63 Osteoblast-Like cell line, we determined cell viability, adhesion, and morphology on different substrates over a 3 day culture period. The results showed cpTi surfaces to be significantly more hydrophilic than DLC for groove sizes larger than 2 μm. Cell contact guidance was observed for all grooved samples in comparison to the unpatterned controls. The cell viability tests indicated a significantly greater cell number for 8 and 10 μm grooves on cpTi surfaces compared to other groove sizes. The cell adhesion study showed that the smaller groove sizes, as well as the unpatterned control groups, displayed better cell adhesion to the substrate.     

MMA/MPEOMA/VSA copolymer as a novel blood-compatible material: ex vivo platelet adhesion study

MMA/MPEOMA/VSA copolymers with both pendant polyethylene oxide (PEO) side chains and negatively chargeable side groups were synthesized by random copolymerization of methyl methacrylate (MMA), methoxy PEO monomethacrylate (MPEOMA; PEO mol. wt, 1000), and vinyl sulfonic acid sodium salt (VSA) monomers with different monomer composition to evaluate their blood compatibility. MMA/MPEOMA copolymer (with PEO side chains) and MMA/VSA copolymer (with negatively chargeable side groups) were also synthesized for the comparison purpose. The synthesized copolymers were coated onto polyurethane (PU) tubes (inner diameter, 4.6 mm) by a spin coating. The platelet adhesion of the MMA/MPEOMA/VSA copolymer-coated tube surfaces was compared with that of tube surface coated with MMA/MPEOMA or MMA/VSA copolymer with similar MPEOMA or VSA composition, using an ex vivo canine arterio-artery shunt method. The platelet adhesion was evaluated by radioactivity counting of technetium (99mTc)-labeled platelets adhered on the surfaces after 30 and 120 min of blood circulation. The MMA/MPEOMA/VSA copolymer (monomer molar ratio 9/0.5/0.5 or 8/1/1) was better in preventing platelet adhesion on the surface than the MMA/MPEOMA or MMA/VSA copolymer with similar MPEOMA or VSA composition, probably owing to the combined effects of highly mobile, hydrophilic PEO side chains and negatively charged VSA side groups.     

聚氨酯-聚丙烯酸酯共聚乳液的成膜和性能

通过XPS和接触角测试研究了聚氨酯-聚丙烯酸酯共聚乳液在不同基材上的成膜情况，并对共聚胶膜的耐水性和附着力进行了考察．由于该共聚乳液同时存在着亲水组分和疏水组分，所以它在不同的基材上成膜可导致其膜表面的组成成分不同，因而导致其耐水性和附着力也随基材而异。结果表明，亲水性的聚氨酯组分均富集于胶膜内部，但胶膜底层聚氨酯组分的含量却随基材的不同而不同。在憎水且表面张力较高的基材上，共聚胶膜的耐水性良好；共聚胶膜的附着力在表面张力较高的基材上也良好。     

Wetting behavior of polymer coated nanoporous anodic alumina films: transition from super-hydrophilicity to super-hydrophobicity

We show that nanoporous anodic alumina films, with pore diameters in the range 10-80 nm, can be transformed from being very hydrophilic (or super-hydrophilic) to very hydrophobic (or super-hydrophobic) by coating the surface with a thin (2-3 nm) layer of a hydrophobic polymer. This dramatic transformation happens as a result of the interplay between surface morphology and surface chemistry. The coated surfaces exhibit 'sticky' hydrophobicity as a result of ingress of water into the pores by capillary action. The wetting parameters (contact angle and contact angle hysteresis) exhibit qualitatively different dependences on pore diameters in coated and uncoated films, which are explained by invoking appropriate models for wetting.     

Molecular Design of the Solid Copolymer Electrolyte- Poly(styrene-b-ethylene oxide) for Lithium Ion Batteries

Poly(ethylene oxide) (PEO) is a commonly used electrolytic polymer in lithium ion batteries because of its high viscosity which allows fabricating thin layers. However, its inherent low ionic conductivity must be enhanced by the addition of highly conductive salt additives. Also its weak mechanical strength needs a complementary block, such as poly(styrene) (PS), to strengthen the electrolytic membrane during charging/discharging processes. PS is a strong material to complement the PEO and to create a reinforced copolymer electrolyte termed as the poly(styrene-b-ethylene oxide) (PS-PEO). In this work, molecular dynamics simulations are employed to study the effects of doping the PS constituents into the PEO based copolymer electrolyte. The results reveal that strengthening the mechanical strength increases the intra conjugation forces which penalize the ionic conductivity. Hence both ionic conductivity and mechanical strength of the copolymer have to be compromised. This paper designs the optimized molecular structure through the atomistic analysis instead of try-and-error experiments.     

Behaviors of keratinocytes and fibroblasts on films of PLA50–PEO–PLA50 triblock copolymers with various PLA segment lengths

The growth of human primary keratinocytes and fibroblasts on PLA–PEO–PLA copolymer films was investigated as an intermediate stage of a strategy aimed at making implantable dermo-epidermal substitutes. Four PLA–PEO–PLA triblock copolymers with the same PEO block and different dl-lactic acid/ethylene oxide molar ratios (LA/EO) (0.8, 1.4, 1.8 and 2), were synthesized and characterized by ¹H-nuclear magnetic resonance and infrared spectroscopy. The films made of these copolymers were more hydrophilic than PLA₅₀ and than tissue culture polystyrene controls according to contact angles with water. Proliferation and adhesion of human skin cells were evaluated by MTT assay and by scanning electron microscopy. The presence of PEO in the triblock copolymers influenced cell adhesion and proliferation of fibroblasts, whereas keratinocyte adhesion and proliferation were not affected. These features emphasize the interest of PLA–PEO–PLA triblock copolymers to serve as better compounds than the racemic PLA previously investigated to make supports for human skin primary cells and scaffolds for skin engineering.     

Stable permanently hydrophilic protein-resistant thin-film coatings on poly(dimethylsiloxane) substrates by electrostatic self-assembly and chemical cross-linking

Poly(dimethylsiloxane) (PDMS) is a biomaterial that presents serious surface instability characterized by hydrophobicity recovery. Permanently hydrophilic PDMS surfaces were created using electrostatic self-assembly of polyethyleneimine and poly(acrylic acid) on top of a hydrolyzed poly(styrene-alt-maleic anhydride) base layer adsorbed on PDMS. Cross-linking of the polyelectrolyte multilayers (PEMS) by carbodiimide coupling and covalent attachment of poly(ethylene glycol) (PEG) chains to the PEMS produced stable, hydrophilic, protein-resistant coatings, which resisted hydrophobicity recovery in air. Attenuated total reflection Fourier transform infrared spectroscopy and X-ray photoelectron spectroscopy revealed that the thin films had excellent chemical stability and resisted hydrophobicity recovery in air over 77 days of measurement. The spectra also showed a dense coverage for PEG dialdehyde and excellent resistance to protein adsorption from undiluted rat serum. Atomic force microscopy revealed dense coverage with PEG dialdehyde and PEG diamine. Contact angle measurements showed that all films were hydrophilic and that the PEG dialdehyde-topped thin film had a virtually constant contact angle (approximately 20 degrees ) over the five months of the study. Electrokinetic analysis of the coatings in microchannels always exposed to air also gave good protein separation and constant electroosmotic flow during the five months that the measurements were done. We expect that the stable, hydrophilic, protein-resistant thin-film coatings will be useful for many applications that require long-term surface stability.     

Fabrication and biocompatibility of polyethyleneimine/heparin self-assembly coating on NiTi alloy

NiTi alloy has been used widely as biomaterials. But because of toxic effects possibly caused by excess Ni ions released during the corrosion process in the physiological environment, it is still a controversial material. Fabricating medicine-loaded coating, which is expected to decrease the release of Ni ions and improve the biocompatibility of the materials, is a potential way to solve the problem. In this paper, NiTi alloy is coated by polyethyleneimine/heparin films via layer-by-layer (LBL) self-assembly method. UV-Vis, FT-IR, atomic force microscopy (AFM) and contact angle measurements are used to characterize the microstructure of coatings and select the best fabrication conditions. Potentiodynamic polarization researches in sodium chloride and dynamic clotting time experiment are utilized to study its corrosion resistance capability and biocompatibility of coatings, respectively. The results indicate that PEI/heparin multilayer coating can improve the biocompatibility of NiTi alloy surface.     

嵌段共聚物PEO-b-PS与聚苯乙烯共混薄膜的表面形貌及性能

通过原子转移自由基聚合(ATRP)制备了嵌段共聚物聚氧化乙烯(PEO-b-聚苯乙烯(PS)),将PEO-b-PS与PS溶液共混成膜,使用接触角测试仪(CA)和原子力显微镜(AFM)考察了PEO-b-PS含量与共混薄膜表面形貌及性能之间的关系。研究发现,嵌段共聚物在薄膜中发生微相分离并在薄膜表面形成PEO微相区,随PEO-b-PS含量增加,薄膜表面PEO相区尺寸增大,但分布密度下降。通过共混薄膜表面形貌的变化,解释了共混薄膜的亲水性和表面张力随PEO-b-PS含量增加的变化趋势。     

Plasma polymer coatings to aid retinal pigment epithelial growth for transplantation in the treatment of age related macular degeneration

Subretinal transplantation of functioning retinal pigment epithelial (RPE) cells grown on a synthetic substrate is a potential treatment for age-related macular degeneration (AMD), a common cause of irreversible vision loss in developed countries. Plasma polymers give the opportunity to tailor the surface chemistry of the artificial substrate whilst maintaining the bulk properties. In this study, plasma polymers with different functionalities were investigated in terms of their effect on RPE attachment and growth. Plasma polymers of acrylic acid (AC), allyl amine (AM) and allyl alcohol (AL) were fabricated and characterised using X-ray photoelectron spectroscopy (XPS) and water contact angle measurements. Octadiene (OD) hydrocarbon films and tissue culture polystyrene were used as controls. Wettability varied from hydrophobic OD to relatively hydrophilic AC. XPS demonstrated four very different surfaces with the expected functionalities. Attachment, proliferation and morphological examination of an RPE cell line and primary RPE cells were investigated. Both cell types grew on all surfaces, with the exception of OD, although the proliferation rate of primary cells was low. Good epithelial morphology was also demonstrated. Plasma polymerised films show potential as cell carrier surfaces for RPE cells in the treatment of AMD.     

Adhesive properties of polypropylene (PP) and polyethylene terephthalate (PET) film surfaces treated by DC glow discharge plasma

In this study, the adhesive properties of the plasma modified polypropylene (PP) and polyethylene terephthalate (PET) film surfaces have been investigated. Hydrophilicity of these polymer film surfaces was studied by contact angle measurements. The surface energy of the polymer films was calculated from contact angle data using Fowkes method. The chemical composition of the polymer films was analyzed by X-ray photoelectron spectroscopy (XPS). Atomic force microscopy (AFM) was used to study the changes in surface feature of the polymer surfaces due to plasma treatment. The adhesion strength of the plasma modified film was studied by T-peel strength test. The results showed a considerable improvement in surface wettability even for short exposure times. The AFM and XPS analyses showed changes in surface topography and formation of polar groups on the plasma modified PP and PET surfaces. These changes enhanced the adhesive properties of polymer film surfaces.     

A novel activation for electroless plating on preparing Ni/PS microspheres

A novel and facile surface activation for electroless nickel plating was proposed, avoiding complex surface functionalization or pretreatment. The samples were characterized by XPS, TEM, XRD and SEM. The results indicated that the coatings of Ni/PS microspheres were smooth, compact and uniform, and the Ni coatings thickness was about 0.15 µm. It can be concluded that the novel surface activation was effective for the uniform nickel deposition on the surfaces of PS microspheres, due to more palladium catalytic active sites generated on PS microspheres surfaces.     

MMA/MPEOMA copolymers as coating materials for improved blood compatibility: protein adsorption study

Surface-induced thrombosis remains one of the main problems in the development of blood-contacting devices. When a foreign surface comes in contact with blood, the initial blood response is adsorption of blood proteins, followed by platelet adhesion and activation, leading to thrombus formation. A particularly effective polymer for the prevention of protein adsorption and platelet adhesion appears to be polyethylene oxide (PEO). In this study, water-insoluble copolymers of methyl methacrylate (MMA) and methoxy PEO monomethacrylates (MPEOMA) with different PEO molecular weights (200, 400, and 1000) and monomer composition were synthesized and characterized by gel permeation chromatography and ¹H-nuclear magnetic resonance spectroscopy. The synthesized copolymers were coated on glass slides by a spin coating method to prepare PEO-rich surfaces as blood-compatible surfaces. The surface properties of the copolymers and their interaction with blood proteins (albumin, γ-globulin, fibrinogen, and plasma proteins) were investigated by the measurement of water contact angles and by electron spectroscopy for chemical analysis, respectively. It was observed that the protein adsorption on the copolymer surfaces decreased with increasing PEO molecular weight and MPEOMA content in the copolymers. The copolymers with long PEO chains in MPEOMA (MMA/MPEO₀₀₀MA copolymers) were effective in preventing protein adsorption, even though their MPEOMA content was less than the copolymers with shorter PEO chains. © 1999 Kluwer Academic Publishers