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Novel membranes and surface modification able to activate specific cellular responses.

The design of new polymeric biomaterials together with new strategies to modify membrane surface are crucial to optimise cell-biomaterial interactions in vivo and in vitro biohybrid systems. In this study we report on the novel semipermeable membranes synthesised from a polymeric blend of modified polyetheretherketone and polyurethane able to support the long-term maintenance and differentiation of human liver cells and on the surface modification of polyethersulfone membranes by plasma polymerisation of acrylic acid monomers and by immobilization of arginine-glycine-aspartic acid (RGD) peptide through a hydrophilic "spacer arm" molecule. The performance of the modified and unmodified membranes was tested by evaluation of the liver function expression of primary human hepatocytes in terms of albumin production, protein secretion and drug biotransformation.

Benzophenones↗

Effect of glow discharge surface modification of plasma TFE vascular graft material on fibronectin and laminin retention and endothelial cell adhesion.

The effects of glow discharge surface modification of plasma TFE vascular graft material (plasma TFE, Atrium Medical Corp., Hollis, NH) on the binding and retention of fibronectin and laminin as well as endothelial adherence were examined. The binding of both fibronectin and laminin to plasma TFE increased as a function of protein concentration in the range of 0.02 to 200 micrograms/ml. Binding to plasma TFE was not saturable in this range of protein concentrations. Fibronectin and laminin binding to plasma TFE was time-dependent, reaching a maximal level (1.8 and 3.2 micrograms/cm2 of bound fibronectin and laminin, respectively) after 30 min (fibronectin) and 4 hr (laminin). Binding was not the result of an accumulation of unbound protein in graft interstices since graft prewetting did not alter the amount of either fibronectin or laminin associated with plasma TFE. In addition, binding was not the result of protein modification during radiolabeling, since unlabeled fibronectin and laminin could compete effectively with their iodinated counterparts for binding to plasma TFE. Dissociation of bound fibronectin and laminin from plasma TFE was rapid, and less than 12% remained bound 60 min after washing. Plasma TFE subjected to glow discharge in O2 and carrying negatively charged functional groups on graft surfaces, exhibited a fivefold increase in fibronectin and laminin binding. In addition, more than 85% of the bound fibronectin and laminin was retained 24 hr after washing. The enhanced retention of fibronectin or laminin by these grafts was associated with an increase in endothelial cell adhesion.(ABSTRACT TRUNCATED AT 250 WORDS)

Ammonia↗

Bonding of prosthetic composite material to Ti-6Al-7Nb alloy with eight metal conditioners and a surface modification technique.

PURPOSE: The purpose of the current study was to evaluate the adhesive performance of metal conditioners and a surface modification system when used for bonding between a prosthetic composite material and a titanium alloy. MATERIALS AND METHODS: Eight metal conditioners (Acryl Bond, All-Bond 2 Primer B, Alloy Primer, Ces II Opaque Primer, Eye Sight Opaque Primer, Metafast Bonding Liner, Metal Primer II, and MR Bond) and a bonding system (Siloc) were assessed. Cast disk specimens made of a titanium alloy (Ti-6Al-7Nb, T-Alloy Tough) were either primed with one of the eight primers or treated with the Siloc system and bonded with a light-activated prosthetic composite material (Artglass). Shear bond strengths were determined both before and after thermocycling (4 C-60 C, 60 s each, 20,000 cycles) for evaluation of the durability of the bonds. RESULTS: The results showed that the Siloc-treated group recorded the greatest post-thermocycling bond strength, followed by the two groups conditioned with the Cesead II Opaque Primer and Alloy Primer agents, both of which contain an identical hydrophobic phosphate-methacrylate functional monomer.

Alkanes↗

Solution-phase surface modification in intact poly(dimethylsiloxane) microfluidic channels.

An improved approach composed of an oxidation reaction in acidic H2O2 solution and a sequential silanization reaction using neat silane reagents for surface modification of poly(dimethylsiloxane) (PDMS) substrates was developed. This solution-phase approach is simple and convenient for some routine analytical applications in chemistry and biology laboratories and is designed for intact PDMS-based microfluidic devices, with no device postassembly required. Using this improved approach, two different functional groups, poly(ethylene glycol) (PEG) and amine (NH2), were introduced onto PDMS surfaces for passivation of nonspecific protein absorption and attachment of biomolecules, respectively. X-ray electron spectroscopy and temporal contact angle experiments were employed to monitor functional group transformation and dynamic characteristics of the PEG-grafted PDMS substrates; fluorescent protein solutions were introduced into the PEG-grafted PDMS microchannels to test their protein repelling characteristics. These analytical data indicate that the PEG-grafted PDMS surfaces exhibit improved short-term surface dynamics and robust long-term stability. The amino-grafted PDMS microchannels are also relatively stable and can be further activated for modifications with peptide, DNA, and protein on the surfaces of microfluidic channels. The resulting biomolecule-grafted PDMS microchannels can be utilized for cell immobilization and incubation, semiquantitative DNA hybridization, and immunoassay.

Amines↗

Surface modification of poly(glycolic acid) (PGA) for biomedical applications.

The immobilization of biological ligands (such as biotin and peptides) onto biodegradable polymer surfaces, including poly(glycolic acid) (PGA) sutures, is complicated by the absence of functional groups on the polymer backbone. We demonstrate a method for overcoming this problem, by attaching (+)-biotinyl-3,6,9-trioxaundecanediamine to the surface of PGA sutures, which immobilizes the ligand through an amide bond between amine (ligands) and carboxylic acid groups (surface-hydrolyzed PGA sutures). Fluorescence microscopy was used to verify the attachment of the biotin ligand to the surface of the PGA suture after a complexation with fluorescein-conjugated streptavidin. The strategy can be generalized to surface modifications of other biodegradable aliphatic polyesters, which would improve the properties of the polymers in biomedical applications such as active targeting of drugs based on ligand-attached, polymeric drug delivery systems.

Biodegradation, Environmental↗

Surface modification of corneal contact lens with phosphoryl choline by glow discharge.

Polymers like poly(methylmethacrylate) (PMMA) and poly(2-hydroxyethylmethacrylate) (PHEMA) are widely used in the development of hard and soft contact lenses. Cell adhesion and deposition of chemicals such as calcium, lipoproteins and mucin on the lens surface cause visual acuity which is the main problem in extended uses of contact ocular lenses. In order to minimise the cell adhesion and other type of depositions, a method of surface modification of lens involving the use of phosphoryl choline, a phospholipid and the glow discharge technique has been described. The power variation of the lenses after modification has been checked using Topcon lensometer. The possible power changes of the modified samples due to the exposure to the normal light in the laboratory, darkness, ultraviolet (U.V.) light or saline have been investigated by taking the visible and ultra violet spectra using Beckman spectrophotometer. Surface energy variations after modifications of the samples have been checked by sessile drop water contact angle measurements. Glow discharge treatment increases the hydrophilicity of the samples. It seems, the modifications do not affect the power of hard contact lens significantly. It is also observed that the exposure of samples to the normal light in the laboratory, darkness, U.V. light or saline make no significant change in the visible and ultraviolet spectra of the samples before and after modification.

Air↗

Probing rhodopsin-transducin interactions by surface modification and mass spectrometry.

The interactions of rhodopsin and the alpha-subunit of transducin (G(t)) have been mapped using a surface modification "footprinting" approach in conjunction with mass spectrometric analysis employing a synthetic peptide corresponding to C-terminal residues 340-350 of the alpha-subunit of G(t), G(t)alpha(340-350). Membrane preparations of unactivated (Rh) and light-activated rhodopsin (Rh*), each in the presence or absence of G(t)alpha(340-350), were acetylated with the water-soluble reagent sulfosuccinimidyl acetate, and the extent of the acetylation was determined by mass spectrometry. By comparing the differences in acetylation among Rh, Rh*, and the Rh-G(t)alpha(340-350) and Rh*-G(t)alpha(340-350) complexes, we demonstrate that the surface exposure of the acetylation sites was reduced by the conformational change associated with light activation, and that binding of G(t)alpha(340-350) blocks acetylation sites on cytoplasmic loops 1, 2, and 4 of Rh*. In addition, we show evidence of interaction between the end of the C-terminal tail of rhodopsin and G(t)alpha in the unactivated state of rhodopsin.

Acetylation↗

Surface modification of silicone rubber membrane by plasma induced graft copolymerization as artificial cornea.

In this study a highly biocompatible polymer membrane was prepared by surface modification. An artificial cornea was also developed for clinical applications. Silicone rubber (SR) membrane was grafted with hydrophilic monomers such as 2-hydroxyethyl methacrylate (HEMA) and acrylic acid by plasma induced grafted polymerization. Surface properties of the SR were characterized using secondary ions mass spectra, Fourier transform infrared/attenuated total reflection, and element spectra for chemical analysis. The corneal epithelial (CE) cell was cultured in vitro, and penetrating keratoplasty of albino rabbit cornea (in vivo) was performed to evaluate biological properties of modified SR membranes. The ability of the CE cell to attach onto various SR membranes was observed by inverted microscopy. The proliferation of CE cell was conducted in approximately 96 h. Experimental results indicated that the attachment and growth of CE onto SR-g-pHEMA (75 micrograms/ cm2) is enhanced. The morphologies of an attached CE cell are similar to those of a primary CE cell. In the in vivo study, the depth of anterior chamber was maintained 2 weeks after penetrating keratoplasty was performed with a SR grafted with pHEMA (210 micrograms/cm2). This phenomenon displayed a high biocompatibility of modified SR membrane with the CE cell. Furthermore, results in this study provide a valuable reference for application of the modified SR for an artificial cornea.

Animals↗

XPS study on the weakest zone in the adhesion structure between resin containing 4-META and precious metal alloys treated with different surface modification methods.

Three precious metal alloys, Type IV gold alloy, 14 K gold alloy, and silver-based alloy, were treated with different surface modifications including a metal primer (VBATDT) application, a SiOx coating method, high-temperature oxidation, modification method with a liquid Ga-Sn alloy, and tin electroplating. Then thin PMMA films were bonded with a resin containing 4-META. Water durability at the adhesion interface was evaluated after water immersion, followed by thermal cycling used liquid nitrogen. The weakest zone at the interface was investigated using XPS only for the Ag-Pd alloy specimens that had been surface-treated with as-polishing, adhesive primer, and the SiOx coating method, since peeling of the PMMA film on the surface of specimens surface-treated by other methods was not observed. Metal elements were detected from the resin side at the adhesion interface. The chemical states of Cu in the resin before argon ion etching were characterized as metal oxides and/or states of chemical interaction with 4-META, VBATDT, or SiOx.

Acrylic Resins↗

Surface modification of liposomes by saccharides: vesicle size and stability of lactosyl liposomes studied by photon correlation spectroscopy.

The cell glycocalyx is an attractive model for surface modification of liposomes, because its hydrated oligosaccharide layer inhibits nonspecific protein adsorption and can provide specificity towards desired sites. Here, we report on the use of lactose as a model saccharide to modify the liposome surface and examine the vesicle size and stability. Two kinds of lactosyl lipids, including lactosyl ether-lipid (6a) and lactosyl ester-lipid (6b), which contain octadecyl and octadecanoyl as the lipid tails, respectively, were synthesized and their liposomes were prepared by the extrusion method. The effects of glycolipid structure, concentration, and the pore size of the extrusion membrane on vesicle size and stability were investigated at room temperature by photon correlation spectroscopy (PCS). All liposomes with 5 or 10 mol% of lactosyl lipids had a narrow size distribution and remained stable at room temperature for at least one month, which is comparable to 1,2-distearoyl-sn-glycero-3-phosphocholine (DSPC)- and poly(ethylene glycol) (PEG)-liposomes. The maximum incorporation of lactosyl ester-lipid into liposomes was 15 mol%, compared with only 10 mol% for the lactosyl ether-lipid. The lactosyl ester-liposomes had better stability and exhibited less size change than the lactosyl ether-liposomes at 15 or 20 mol% of lactosyl lipids incorporated. This may be attributed to the better structural compatibility of lactosyl ester-lipid with DSPC. The PCS results show that the glycolipid structure and concentrations are major factors that affect vesicle stability, while the pore size of extrusion membranes has no influence.

Carbohydrate Conformation↗

Simple surface modification of poly(epsilon-caprolactone) to induce its apatite-forming ability.

A biodegradable polymer coated with a bone-like apatite layer on its surface is useful as a scaffold for bone tissue regeneration. In this work, a poly(epsilon-caprolactone) (PCL) surface was modified by an O2 plasma surface treatment to form oxygen-containing functional groups. The plasma-treated samples were subsequently dipped alternately in an alcoholic solution containing calcium ions and one containing phosphate ions to deposit apatite precursors on the surface. The surface-modified PCL samples formed a dense and uniform surface bone-like apatite layer after immersion for 24 h in a simulated body fluid with ion concentrations approximately equal to those of human blood plasma. This surface-modification process is applicable to two-dimensional PCL plates and three-dimensional PCL meshes. In the resulting apatite-PCL composite, the apatite layer strongly adhered to the PCL surface and remained intact after a tape-detachment test. Therefore, this type of composite material will be a useful scaffold for bone tissue engineering.

Absorbable Implants↗

Patterned polyelectrolyte multilayer: surface modification for enhancing selective adsorption.

This paper describes the use of surface chemical modification to enhance the difference of the surface charge on a patterned polyelectrolyte multilayer, which can be used for selectively adsorbing functional materials. We fabricated a patterned multilayer by combining the layer-by-layer self-assembly technique and photolithography and taking advantage of the different solubility of polyelectrolyte multilayers of diazo resins (DAR)/poly(acrylic acid) before and after UV irradiation. This patterned surface can be used as a matrix for selective adsorption of small molecular dyes, such as Methylene Blue. However the difference in surface charge on the patterned surface was not enough when we used it to selectively adsorb polystyrene (PS) nanoparticles using electrostatic force as the driving force. Therefore, we modified the patterned surface by interfacial chemistry. After modification, the patterned polyelectrolyte multilayer can be used as a good matrix for selective adsorption of PS nanoparticles with both positive and negative charges.

Journal Article↗

Surface modification of silicon and gold-patterned silicon surfaces for improved biocompatibility and cell patterning selectivity.

Clean silicon and gold-patterned silicon platforms were modified with methoxy-polyethylene glycol (M-PEG silane) via a self-assembly technique, which significantly improved their plasma protein resistance capability and cell patterning selectivity. Fibrinogen and IgG were used as model plasma proteins to study the efficacy of PEG layers in resisting protein adsorption. Selective cell patterning on the gold regions of a gold-patterned silicon substrate and tissue compatibility were studied with macrophage and fibroblast cells. The research also revealed how the presence of gold electrodes on a silicon substrate would influence the cell patterning selectivity. Our experimental results showed that the PEG-modified silicon surfaces had a high resistivity to protein and cell attachment and that the PEG-modified gold-patterned silicon surfaces nearly completely eliminated the protein adsorption and cell attachment on silicon. This study provides a new approach to developing biocompatible surfaces for silicon-based BioMEMS devices, particularly for biosensors where a metal-insulator format must be enforced.

Adsorption↗

A facile photochemical surface modification technique for the generation of microstructured fluorinated surfaces.

We describe a simple photochemical process which allows fluoropolymers to be chemically bound at room temperature onto SiO2 surfaces. To achieve this, at first a benzophenone silane is used to form a self-assembled monolayer on the surface of the substrate, which is subsequently coated with the fluoropolymer and irradiated with UV light of wavelength 365 nm. Using this very simple approach, we have been able to create ultrahydrophobic surfaces with very low surface free energies together with a good degree of control in thickness and composition as well as strong adhesion to the monolayer. The use of a UV-based process to attach the films on SiO2 surfaces opens the door for photopatterning of surfaces with fluorinated and nonfluorinated compounds to yield well-defined microstructures with spatial control of the wetting properties of the substrates.

Journal Article↗

Two-Step Surface Modification of Chemically Resistant Polymers: Blend Formation and Subsequent Chemistry1

Supercritical fluid (SCF) carbon dioxide processing has been studied as a new route to polymer surface modification. Three fluoropolymer substrates were studied: poly(tetrafluoroethylene) (PTFE), poly(chlorotrifluoroethylene) (PCTFE) and poly(tetrafluoroethylene-co-hexafluoropropylene) (FEP) using a two-step modification procedure. In the first step, blends or semiinterpenetrating networks were prepared by carrying out a free radical polymerization of styrene (or styrene with divinylbenzene or triallyl cyanurate) within the SCF-swollen polymer substrate. The second step involved sulfonating the polystyrene using heterogeneous (solution-solid) sulfonation conditions. Composition of the surfaces was determined by X-ray photoelectron spectroscopy, and wettability was assessed using water contact angle measurements. Depressed advancing and receding contact angles indicate increased wettability of all of the fluoropolymer samples.

Journal Article↗

Towards a methodology for the effective surface modification of porous polymer scaffolds.

A novel low-pressure radio-frequency plasma treatment protocol was developed to achieve the effective through-thickness surface modification of large porous poly (D,L-lactide) (PDLLA) polymer scaffolds using air or water: ammonia plasma treatments. Polymer films were modified as controls. Scanning electron micrographs and maximum bubble point measurements demonstrated that the PDLLA foams have the high porosity, void fraction and interconnected pores required for use as tissue engineering scaffolds. The polymer surface of the virgin polymer does contain acidic functional groups but is hydrophobic. Following exposure to air or water: ammonia plasma, an increased number of polar functional groups and improved wetting behaviour, i.e. hydrophilicity, of wet surfaces was detected. The number of polar surface functional groups increased (hence the decrease in water contact angles) with increasing exposure time to plasma. The change in surface composition and wettablility of wet polymer constructs was characterised by zeta potential and contact angle measurements. The hydrophobic recovery of the treated PDLLA polymer surfaces was also studied. Storage of the treated polymer constructs in ambient air caused an appreciable hydrophobic recovery, whereas in water only partial hydrophobic recovery occurred. However, in both cases the initial surface characteristics decay as function of time.

Absorbable Implants↗

Surface modification of poly (L-lactide) by atmospheric pressure plasma treatment and cell response.

This study investigated the influence of atmospheric pressure plasma treatment on the surface properties and cell response of poly(L-lactide) (PLLA) samples. The samples were analyzed by means of X-ray photoelectron spectroscopy (XPS), atomic force microscopy (AFM), micro- and nanosurface roughness, water contact angle, and zeta potential. Furthermore, cell adhesion assay and cell proliferation assay on the samples were carried out using MC3T3-E1 cells. Plasma treatment significantly increased the oxygen content of the samples and decreased the contact angle and zeta potential of the samples, resulting in hydrophilic surfaces. Further, plasma treatment of the samples also enhanced the number and growth of adhering MC3T3-E1 cells. These results therefore indicate that plasma treatment is effective for surface modification and cell responses.

Animals↗

[Surface modification of poly methyl methacrylate intraocular lens by alpha-allyl glucoside].

A method for improving the biocompatibility of the intraocular lens (IOL) and reducing the cell attachment was adopted in this study. The alpha-Allyl glucoside was used for the surface modification of the poly methyl methacrylate (PMMA) IOL by way of plasma-induced in situ polymerization. The surfaces of the control and treatment IOLs were characterized by contact angle estimation and ESCA techniques. The resolution, diopter and anti-fatigue of loops were determined by physical and optical methods. Cell attachment on the surfaces was examined by light microscopy. The results indicated that all of the treatment groups had excellent physical and optical properties. The modification with the use of alpha-Allyl glucoside could improve the hydrophilicity of the anterior surface of the PMMA IOLs and reduce the cell attachment.

Allyl Compounds↗