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Viscosity and yield stress reduction in non-colloidal concentrated suspensions by surface modification with polymers and surfactants and/or nanoparticle addition.

A custom-designed apparatus termed the yield stress adaptor (YSA) has been used to evaluate the effect of polymer-surfactant coatings, and the addition of nanoparticles of different size, shape and surface chemistry, on the rheological properties of large hydrophilic particulates, sand, with the aim of reducing interparticle friction forces. Experimental results show that the flow properties of sand slurries at high volume fractions of sand (>50%) can be significantly enhanced by adding nanoparticles, and by surface modification with polymer/surfactant mixtures. A lesser effect is observed for polymer-only and surfactant-only coated samples. X-ray photoelectron spectroscopy was used to determine the concentration of organic species at the surface. The effect of polymer/surfactant concentration, adsorption time, polymer molecular weight, as well as surfactant charge and chemical structure were also addressed.

Adsorption↗

Safety of plasma-based sterilization: surface modifications of polymeric medical devices induced by Sterrad and Plazlyte processes.

Plasma-based sterilization is a promising alternative to the use of pure ethylene oxide (EO), for low-temperature clinical sterilization of medical instruments and devices. However, few studies have been published that evaluate its safety in terms of possible damage to materials, particularly polymers. The objective of this work was to evaluate polymer surface modifications induced by commercial plasma-based sterilizers, in comparison with pure EO: Samples from 5 polymer-based devices were subjected to 1, 5, and 10 sterilization cycles by Sterrad-100, Plazlyte, and pure EO. Surface analysis was carried out by X-ray photoelectron spectroscopy (XPS), dynamic contact angle measurements (DCA), and scanning electron microscopy (SEM). Surface oxidation and wettability changes were observed on all samples sterilized by plasma-based techniques, the degree of modifications depending on the sterilizer (Sterrad, Plazlyte) and the type of polymer. Drastic changes of surface appearance were also observed by SEM on PVC samples sterilized by Plazlyte and by pure EO. Possible repercussions on safety are discussed.

Adsorption↗

Surface modification of polyethylene terephthalate using PEO-polybutadiene-PEO triblock copolymers.

The initial step of thrombus formation on blood-contacting biomaterials is known to be adsorption of blood proteins followed by platelet adhesion. It is generally accepted that surface modification of the biomaterials with poly(ethylene oxide) (PEO) substantially reduces protein adsorption and cell adhesion. Dacron(R) (polyethylene terephthalate) fabric, which is one of the biomaterials commonly used in blood-contacting devices, was grafted with PEO. A simple two-step procedure for covalent grafting of PEO onto the surface of Dacron(R) fabric was used. The surface was first treated with PEO-polybutadiene-PEO (PEO-PB-PEO) triblock copolymer, to introduce a layer of double bonds onto the surface. The Dacron(R) surface was then exposed to a solution of Pluronic(R) F108 (PF108), a commercially available PEO-poly(propylene oxide)-PEO (PEO-PPO-PEO) triblock copolymer. The surface with two adsorbed layers of PEO-PB-PEO and PF108 was gamma-irradiated in the presence of PF108 in the bulk solution for a total radiation dose of 0.8 Mrad. The bulk concentrations of PEO-PB-PEO and PF108 were varied to maximize the efficiency of PEO grafting. Fibrinogen adsorption on PEO-grafted surfaces was reduced more than 90%, compared with that on control surfaces, irrespective of the bulk concentrations of polymers used for grafting. Platelet adhesion was also reduced substantially by PEO grafting. Only a few round platelets were able to adhere to the PEO-grafted surface, while the control surface was fully covered with aggregates of activated platelets. PEO grafting on polyethylene terephthalate using PEO-PB-PEO and PEO-PPO-PEO block copolymers is a simple approach that can be used for various other biomaterials.

Journal Article↗

Design of a photocatalyst for bromate decomposition: surface modification of TiO2 by pseudo-boehmite.

The rate of BrO3- reduction by a commercial TiO2 photocatalyst under UV illumination in an aqueous solution was increased by lowering the pH from 7 to 5. The effect is attributable to an enhancement of the electrical interaction between BrO3- and the positively charged surfaces of the TiO2 photocatalyst. The surface charge can be controlled by a surface modification of the TiO2 photocatalyst without controlling the pH of the water. In fact, the isoelectric point of surface-modified TiO2 was higher than that of the unloaded TiO2 photocatalyst, resulting in an increase in the rate of the photocatalytic reduction of BrO3- at a neutral pH. This increase is explained by an increase in the amount of adsorbed BrO3- on the photocatalyst surface.

Bromates↗

Corrosion degradation and prevention by surface modification of biometallic materials.

Metals, in addition to ceramics and polymers, are important class of materials considered for replacement of non-functional parts in the body. Stainless steel 316, titanium and titanium alloys, Co-Cr, and nitinol shape memory alloys are the most frequently used metallic materials. These alloys are prone to corrosion in various extents. This review briefly discusses the important biomaterials, their properties, and the physiological environment to which these materials are exposed. Corrosion performance of currently used metallic materials has been assessed and threat to the biocompatibility from corrosion products/metal ions is discussed. The possible preventive measures to improve corrosion resistance by surface modification and to increase the bioactivity of the metallic surfaces have also been discussed. Importance of the formation of oxide layers on the metal surface, another aspect of corrosion process, has been correlated with the host response. The gap areas and future direction of research are also outlined in the paper.

Alloys↗

Biomimetic surface modification of poly(L-lactic acid) with chitosan and its effects on articular chondrocytes in vitro.

The objective of this study was to investigate the efficiency of two treatments for poly(L-lactic acid) (PLLA) surface modification with chitosan, via entrapment and coupling by using 1-ethyl-3-(3-dimethylaminopropyl)carbodiimide and N-hydroxysuccinimide. The properties of original PLLA films, chitosan-entrapped and coupled PLLA films were investigated by water contact angle measurement and electron spectroscopy for chemical analysis (ESCA). The contact angle indicated the change in hydrophilicity and the ESCA data suggested that the modified PLLA films became enriched with nitrogen atoms. The cytocompatibility of modified PLLA films might be improved. Therefore, the attachment and proliferation of bovine articular chondrocyte seeded on modified PLLA films and control one were examined. A whole cell enzyme-linked immunosorbent assay (Cell ELISA) that detects the BrdU incorporation during DNA synthesis and collagen type II secretion was applied to evaluate the chondrocytes on different PLLA films and tissue culture plates. Cell viability was estimated by the MTT assay and cell function were assessed by measuring sulfated glycosaminoglycan secreted by chondrocytes. These results implied that chitosan used to modify PLLA surface through entrapment and coupling could enhance the chondrocyte adhesion, proliferation and function.

Animals↗

Biomimetic surface modification of poly (L-lactic acid) with gelatin and its effects on articular chondrocytes in vitro.

Our objective in this study was to investigate the efficiency of two treatments for poly (L-lactic acid) (PLLA) surface modification with gelatin, via entrapment and coupling, using 1-ethyl-3-(3-dimethylaminopropyl)carbodiimide (EDC) and N-hydroxysuccinimide (NHS). The properties of original PLLA, gelatin-entrapped, and coupled PLLA films were investigated by water contact angle measurement and electron spectroscopy for chemical analysis (ESCA). The water contact angle indicated that the incorporation of gelatin resulted in a change in hydrophilicity, and the ESCA data suggested that the modified PLLA films became enriched with nitrogen atoms. The cytocompatibility of modified PLLA films might be improved. Therefore, we examined the attachment and proliferation of bovine articular chondrocyte seeded on modified PLLA films and virgin films. A whole-cell enzyme-linked immunosorbent assay (cell ELISA) that detects 5-bromo-2'-deoxyuridine (BrdU) incorporation during DNA synthesis and collagen type II secretion was applied to evaluate the chondrocytes on different PLLA films and tissue culture plates (TCPS). Cell viability was estimated by the MTT [3-(4,5-dimethylthiazol-2-yl)-2,5-diphenyl tetrazolium bromide] assay, and cell function was assessed by measuring glycosaminoglycan (GAG) secreted by chondrocytes. These results implied that gelatin used to modify the PLLA surface through entrapment and coupling could enhance chondrocyte adhesion, proliferation, and function.

Animals↗

The effect of surface modification of a porous TiO2/perlite composite on the ingrowth of bone tissue in vivo.

The porous TiO2/perlite composite Ecopore is a synthetic biomaterial with possible clinical application in bone substitution. In our previous work, we demonstrated that surface modification of Ecopore with fibronectin (FN) enhanced spreading and growth of human osteoblasts in vitro. In the present study, we implanted untreated, alkaline-etched and FN-coated Ecopore cylinders into critical size defects of rabbit femora and applied pulsed polychrome sequence staining. After 6 weeks, sections of the implants were investigated via conventional and fluorescence microscopy. A partial ingrowth of bone matrix into the pore system of the Ecopore implants was observed. At the contact zones, the bone appeared to be directly connected to the implant without detectable gaps. Defect healing was complete within 6 weeks, while fibrous tissue generation or inflammation were absent in the implant modification groups, demonstrating basic Ecopore biocompatibility. The mean bone apposition rates within the implant cross-section were 4.1+/-0.6 microm/day (p<0.001) in the FN-coated group and 3.3+/-0.5 microm/day (p<0.05) in the NaOH-etched group. In both treated Ecopore modification groups, the apposition rates were significantly higher than in the non-modified control (2.9+/-0.6 microm/day), indicating bone growth stimulation by pre-treatment. Energy-dispersive X-ray analysis confirmed that significantly more bone tissue was formed inside the pores of the FN-coated implants compared to the unmodified control. The cross-sectional areas identified as ingrown bone amounted to 18.5+/-6.1% (p<0.05) in the FN group, 13.4+/-5.1% (p>0.05) in the NaOH-etched group and 10.2+/-5.5% in the unmodified group. In summary, we conclude that bone tissue tolerates Ecopore well and that tissue ingrowth can be enhanced by etching and coating with FN.

Animals↗

[Researches on surface modification for prevention of bacterial adhesion to implanting biomaterials].

The failure of operation caused by biomaterials centered infections (BCI) has seriously restricted the clinical application of biomaterials. Two mechanisms of bacterial adhesion and the relationship between surface free energy of bimaterials and bacterial adhesion are introduced and discussed in this paper. Increasing the surface free energy can improve (decrease) the adhesion of some kinds of bacteria. At last, some methods of the surface modification are reviewed.

Bacterial Adhesion↗

Surface Modification of Conventional Polymers by Depositing Plasma Polymers of Trimethylsilane and of Trimethylsilane + O2.

The static wetting properties of TMS (trimethylsilane) and TMS + O2 plasma deposited films on eleven low energy conventional polymers were investigated using the sessile droplet method. The static advancing contact angle is an excellent indication of the change in surface state properties from plasma surface modification. However, traditional contact angle measuring techniques possess a methodological limitation, which can leave a water droplet on the substrate surface for up to 3 min before a measurement is obtained. The static "advancing" contact angles of different size water droplets on teflon and nylon surfaces were observed to change significantly in 2 min while equilibrating with the surface and surroundings. A new quick image-capturing device enables static contact angle measurement 2 to 4 s after contact with the substrate. This technique virtually eliminates the time dependent effects of evaporation and surface state change, which are believed to be responsible for the change in static advancing contact angles. Furthermore, static contact angles independent of droplet volume and contact time may be taken as a surface characteristic property, which is denoted as the intrinsic static contact angle, &theta;S. The static "advancing" contact angle, measured in this fashion, indicated that the wetting properties of TMS and TMS + O2 plasma polymer deposition on 10 conventional polymers were modified virtually independent of the underlying substrate. The average advancing contact angles on TMS and TMS + O2 modified polymers are &theta;S = 94 +/- 2.2 (cos &theta;S = -0.0645) and &theta;S = 32 +/- 6.9 (cos &theta;S = 0.8452), respectively. Copyright 1999 Academic Press.

Journal Article↗

Surface modification of poly(ethylene terephthalate) angioplasty balloons with a hydrophilic poly(acrylamide-co-ethylene glycol) interpenetrating polymer network coating.

An interpenetrating polymer network (IPN) of poly(acrylamide-co-ethylene glycol) (p(AAm-co-EG)) hydrogel was covalently grafted to polyethylene terephthalate (PET) angioplasty balloons to increase surface hydrophilicity and improve lubricity. A 2-step graft polymerization protocol was followed to first polymerize and cross-link acrylamide onto the substrate with a photosensitizer and/or oxygen plasma pretreatment. The effects of varying photo-initiation and plasma exposure times were investigated separately and conjunctively using water contact angles to obtain optimal coating deposition parameters. A poly(ethylene glycol) network was then grafted by swelling the preexisting polyacrylamide network to allow inter-diffusion of the monomer and cross-linker, which were then polymerized by photo-initiation. When the photo-initiation time was long enough to reach near gelation, pretreatment of PET with oxygen plasma did not offer significant benefit. X-ray photoelectron spectroscopy confirmed the presence of both polymer layers, and composition depth profiles supported the assessment that an interpenetrating network was formed. Tensile testing and application of Weibull statistics on unmodified and modified films indicated that the surface modification approach did not significantly alter the mechanical integrity of the material. These findings indicate that a p(AAm-co-EG) coating can be effectively deposited on PET surfaces without compromising the structural integrity of the substrate.

Acrylic Resins↗

Surface modification of ultra thin poly (epsilon-caprolactone) films using acrylic acid and collagen.

Poly (epsilon-caprolactone) (PCL) has been used as a bioresorbable polymer in numerous medical devices as well as for tissue engineering applications. Its main advantage is its biocompatibility and slow degradation rate. PCL surface, however, is hydrophobic and cell-biomaterial interaction is not the best. We attempt for the first time to modify an ultra thin PCL surface with collagen. The PCL film was prepared using solvent casting and biaxial stretching technique developed in our laboratory. This biaxial stretching produced an ultra thin PCL 3-7 microm thick, ideal for membrane tissue engineering applications. The PCL film was pretreated using Argon plasma, and then UV polymerized with acrylic acid (AAc). Collagen immobilization was then carried out. The modified film surface was characterized by Fourier Transform Infrared (FT-IR) and X-ray Photoelectron Spectroscopy (XPS). Water contact angles were also measured to evaluate the hydrophilicity of the modified surface. Results showed that the hydrophilicity of the surface has improved significantly after surface modification. The water contact angle dropped from 66 degrees to 32 degrees. Atomic Force Microscopy (AFM) showed an increase in roughness of the film. A change from 46 to 60 nm in the surface morphology was also observed. The effect of cells attachment on the PCL film was studied. Human dermal fibroblasts and myoblasts attachment and proliferation were improved remarkably on the modified surface. The films showed excellent cell attachment and proliferation rate.

Acrylates↗

Surface modifications of titanium in calcium-ion-containing solutions.

The surface of titanium was modified in calcium-ion-containing solutions to improve bone conductivity. Three kinds of aqueous solutions for the modification were prepared using calcium nitrate, calcium chloride, and calcium oxide. The pH values of the solutions were 3.9, 7.4, and 12.6, respectively. At first, anatase powder was immersed in the solutions of 7 days to confirm the effect of the solutions on the modification. As a result, calcium titanate was formed on the anatase powder, indicating that the titanium surface was possibly modified by the solutions. Titanium plates were then immersed in the solutions at ambient temperature for 7 days, washed by deionized water, and dried. X-ray photo-electron spectroscopy of surface-modified titanium revealed that the surface-modified layer contained calcium hydroxide and/or calcium titanate. The surface-modified layer in which titanium was modified was thickest in this order: calcium oxide, calcium chloride, and calcium nitrate solutions. Apatite was formed on the surface-modified titanium in Hanks' solution while apatite was undetected on unmodified titanium. Therefore, the surface modification of titanium may improve bone conductivity. The amount of apatite corresponded to the thickness of the surface-modified layer and the amount of calcium in the layer.

Apatites↗

Synthesis and characterization of a photocleavable cross-linker and its application on tunable surface modification and protein photodelivery.

A heterobifunctional photocleavable cross-linker based on an o-nitrobenzyl ester moiety was synthesized. The cross-linker has N-hydroxysuccinimidyl and disulfide groups attached at each end and thus can anchor a protein to a gold-coated substrate surface. Steady-state spectroscopic studies suggest that the cross-linker undergoes a clean C-O fragmentation upon irradiation with a quantum yield of 0.1. Consequently, immobilized proteins (such as avidin or antibodies) on a substrate surface can be released efficiently (>95%) under UV irradiation (lambda > 300 nm) without degrading the protein functionality. We also demonstrated protein delivery via bioconjugation of protein molecules to a gold-coated atomic-force microscope (AFM) tip. When the proteins are photoreleased from the AFM tip, they are delivered to the substrate surface as protein clusters of uniform size. This has been confirmed using both AFM and fluorescence microscopy. The application of bioconjugation in this study opens a new avenue for tunable surface modification and controllable protein delivery in studies of biological systems on the nanometer scale.

Cross-Linking Reagents↗

Using a nitrilase for the surface modification of acrylic fibres.

The surface of an acrylic fibre was modified with a commercial nitrilase (EC 3.5.5.1). The effect of fibre solvents and polyols on nitrilase catalysis efficiency and stability was investigated. The nitrilase action on the acrylic fabric was improved by the combined addition of 1 M sorbitol and 4% N, N-dimethylacetamide. The colour levels for samples treated with nitrilase increased 156% comparing to the control samples. When the additives were introduced in the treatment media, the colour levels increased 199%. The enzymatic conversion of nitrile groups into the corresponding carboxylic groups, on the fibre surface, was followed by the release of ammonia and polyacrylic acid. A surface erosion phenomenon took place and determined the "oscillatory" behaviour of the amount of dye uptake with time of treatment. These results showed that the outcome of the application of the nitrilase for the acrylic treatment is intimately dependent on reaction media parameters, such as time, enzyme activity and formulation.

Acetamides↗

Plasma surface modification in biomedical applications.

New medical products, materials and surgical procedures keep improving current health-care practices. Many of these innovations involve polymeric devices that must meet certain clinical and cost requirements. Chief among these pressures is the need for biocompatibility between the physiological environment and the biomaterial surface. Plasma surface modification can improve biocompatibility and biofunctionality. This article reviews the capabilities and applications of the technology.

Biocompatible Materials↗

Surface modification of an experimental silicone rubber aimed at reducing initial candidal adhesion.

Silicone rubber, which is a widely used biomaterial, is often used to make soft liners for permanent denture. Colonization of denture soft lining materials by Candida albicans can result in clinical problems. The aim of this study was to chemically modify the surface of an experimental silicone rubber in order to produce a silicone that was less susceptible to candidal colonization. Surface modification was carried out with the use of argon-plasma bombardment followed by silane treatment, which caused the incorporation of either hydrophilic or hydrophobic functional groups onto the surface. Changes in water contact angles and chemical analysis of the materials with scanning ion mass spectroscopy confirmed surface changes. In vitro assays were carried out using C. albicans to measure levels of adherence to the surface-modified silicone after 1 h. C. albicans exhibited very low adherence to all silane-treated surfaces, whether hydrophobic or hydrophilic. This led to the conclusion that incorporated long-chain functional groups were inhibiting the adherence of the yeast, possibly by the formation of a barrier between the surface of the material and the yeast. In conclusion, silane surface treatment of an experimental silicone rubber has been successful in reducing candidal adherence.

Biocompatible Materials↗

Surface modifications of a glass and a glass-ceramic of the MgO-3CaO.P2O5-SiO2 system in a simulated body fluid.

A glass of nominal composition (wt%) 17.25 MgO-52.75 3CaO.P2O5-30 SiO2 and a glass-ceramic obtained from it showed surface modifications when immersed in an acellular medium having a composition similar to that of human blood plasma. A (Ca, P)-rich layer, with an approximate Ca/P atomic ratio of 1.7, identified as hydroxyapatite, developed on both samples. The precipitated film on the glassy sample was weakly bonded, whereas that formed on the glass-ceramic was strongly adherent. The apatite precipitated during the in vitro tests on both samples grew as a needle-like structure with crystals about 150-200 nm long and 50-70 nm thick, as measured on specimens soaked for 1 month in the simulated body fluid (SBF). The presence of calcium and phosphate ions in the SBF contributed to the precipitation of the (Ca, P)-rich layers on both specimens.

Binding Sites↗