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Surface hydroxylation of styrene-butadiene-styrene block copolymers for biomaterials.

This work pertains to the development of high strength elastomers potentially useful as nonthrombogenic cardiovascular prostheses. Triblock copolymers of the styrene-butadiene-styrene type have been subjected to surface hydroxylation which provide reactive sites at the surface for the subsequent coupling of heparin while retaining the unique mechanical properties of the SBS copolymers. Curves of hydroxyl content versus the copolymer film thickness demonstrate the effect of swelling in the surface region on the product distribution and on the time dependence of the hydroxylation process. In addition, the effect of time, temperature, and the composition of the reaction bath on the diffusion/reaction process is shown. Finally, the general applicability of this surface modification scheme to the development of biomaterials is discussed.

Adsorption↗

Evaluating interface strength of calcium phosphate sol-gel-derived thin films to Ti6Al4V substrate.

The interface shear strength of Ca-P thin films applied to Ti6Al4V substrates have been evaluated in this study using a substrate straining method--a shear lag model. The Ca-P films were synthesized using sol-gel methods from either an inorganic or organic precursor solution. Strong interface bonding was demonstrated for both film types. The films were identified as non-stoichiometric hydroxyapatite but with different Ca/P ratios. The Ca-P films were 1-1.5 microm thick and testing and analysis using the shear lag approach revealed a shear strength of approximately 347 and 280 MPa for Inorganic and Organic Route-formed films, respectively. Overall, the exceptional mechanical properties of Ca-P/Ti6Al4V system along with the inherent advantages of sol-gel processing support continued studies to utilize this technology for bone-interfacing implant surface modification.

Adhesiveness↗

Organic surfaces excited by low-energy ions: atomic collisions, molecular desorption and buckminsterfullerenes.

This article reviews the recent progress in the understanding of kiloelectronvolt particle interactions with organic solids, including atomic displacements in a light organic medium, vibrational excitation and desorption of fragments and entire molecules. This new insight is the result of a combination of theoretical and experimental approaches, essentially molecular dynamics (MD) simulations and secondary ion mass spectrometry (SIMS). Classical MD simulations provide us with a detailed microscopic view of the processes occurring in the bombarded target, from the collision cascade specifics to the scenarios of molecular emission. Time-of-flight SIMS measures the mass and energy distributions of sputtered ionized fragments and molecular species, a precious source of information concerning their formation, desorption, ionization and delayed unimolecular dissociation in the gas phase. The mechanisms of energy transfer and sputtering are compared for bulk molecular solids, organic overlayers on metal and large molecules embedded in a low-molecular weight matrix. These comparisons help understand some of the beneficial effects of metal substrates and matrices for the analysis of molecules by SIMS. In parallel, I briefly describe the distinct ionization channels of molecules sputtered from organic solids and overlayers. The specific processes induced by polyatomic projectile bombardment, especially fullerenes, are discussed on the basis of new measurements and calculations. Finally, the perspective addresses the state-of-the-art and potential developments in the fields of surface modification and analysis of organic materials by kiloelectronvolt ion beams.

Fullerenes↗

Direct bone formation on sand-blasted titanium implants: an experimental study.

Surface modifications of an implant have been demonstrated to be important in influencing the tissue reactions around the implant. Recently, osteoblasts have been shown to be capable of laying down a mineralized matrix in direct contact with the titanium surface. The aim of the present study was to analyse the early bone responses to titanium implants with an aluminium dioxide sand-blasted surface. Microscopical analysis showed that in the first week it was possible to observe the presence of mineralized bone in direct contact with the metal surface, while in other portions of the interface, osteoblasts were seen at the implant surface. These results were confirmed in the 2 and 4 wk observations. Our results could help to explain the increased removal torque forces reported in the literature concerning sand-blasted implants.

Animals↗

Surface characterization of biomedical materials by measurement of electroosmosis.

This paper reviews recent studies by the authors on the surface characterization of biomedically significant materials through electroosmosis determination. The surfaces studied include transparent and nontransparent materials such as quartz, ceramics, paper, and cast polymer capillaries, slides, and particles, in both native and surface modified form. The method is nondestructive, relatively fast, mechanistically simple, automatable to varying degrees, and can be used to analyze samples under physiologically compatible conditions. New experimental and mathematical modeling approaches allow estimates to be obtained with regard to the surface density and pK of various chemical groups, as well as the thickness of polymer or other surface coatings. Surface modifications which may be characterized include, covalent alteration via radiofrequency plasma discharge or organosilane grafting, noncovalent alteration via polymer adsorption, and covalent grafting of neutral polymers, such as poly(ethylene glycol) or dextran. Results complement those from other surface analysis techniques, and correlate with physiologically significant phenomena such as protein adsorption.

Biocompatible Materials↗

Bone formation at titanium implants prepared with iso- and anisotropic surfaces of similar roughness: an in vivo study.

BACKGROUND: Implant surface topography influences the bone response after implantation. However, the importance of surface orientation is not known. PURPOSE: The aim of this study was to investigate the bone tissue response and the stability of titanium implants prepared with isotropic and anisotropic surfaces of similar roughness. MATERIALS AND METHODS: A total of 18 implants were divided into two groups and were inserted into the femurs of nine rabbits for 12 weeks. Confocal laser scanning microscopy was used for the topographic description to verify that the two different surfaces were modified as intended. The stability of the implants was recorded by resonance frequency (RF) measurements at insertion and at time of removal, after which the implants were evaluated histomorphometrically. RESULTS: RF measurements showed that implant stability increased with time. However, there was no significant difference between the two different surface modifications at insertion and after 12 weeks. The histomorphometric comparison revealed no statistically significant differences in regard to either bone-to-metal contact or bone area inside the threads. CONCLUSION: Titanium implants prepared with isotropic and anisotropic surfaces of similar roughness integrate similarly to bone during the 3 months after implantation.

Animals↗

Chromate sorption and reduction kinetics onto an aminated biosorbent.

A novel biosorbent was prepared by chemically grafting of polyethylenimine (PEI) onto the fungal biomass of Penicillium chrysogenum through a two-step reaction. The modified biosorbent is favorable for the removal of anionic Cr(VI) species from aqueous solution due to the protonation of amine groups on the biomass surface. The sorption capacity for Cr(VI) increased by 7.2-fold after surface modification. Sorption kinetics results show that the pseudo-second-order kinetic model described the experimental data well. During the sorption process, X-ray photoelectron spectroscopy (XPS) was used to analyze the chromium species on the biosorbent surface and the results indicate that part of the Cr(VI) ions were reduced to Cr(III) ions which can be chelated with the amine groups on the biomass surface. The reduced Cr(III) ions formed some aggregates on the surface at higher solution pHs.

Adsorption↗

Low fluorescence background electroblotting membrane for DNA sequencing.

A low fluorescence background polypropylene (PP) membrane has been developed for ultimate use as an electroblotting membrane in DNA sequencing based on fluorescence detection. The DNA binding capacity of this membrane is improved by a surface modification using radio frequency plasma discharge (RFPD) in ammonia gas. The RFPD operational parameters are evaluated both in terms of membrane nitrogen content and in terms of the product's capacity for binding radioisotope-labeled DNA fragments. The surface morphologies of the derivatized membranes are examined by scanning electron microscopy; their mechanical and electrical properties, which are important for the subsequent sequencing procedures, are likewise established. Due to the goal of developing a membrane suitable for multiplex processing, in which the electroblotted DNA must withstand dozens of hybridization/stripping cycles, special attention is given the covalent attachment of DNA to the membrane. The modified PP membrane is evaluated in a multiplex sequencing application using radioisotope-labeled DNA probes, and found to yield somewhat better binding of a given amount of electroblotted DNA than the commonly used GeneScreen membrane. A tenfold repetition of the probing indicates little loss of signal; the membrane-bound DNA is stable upon storage and shows no detectable loss in probing efficiency after one month.

Base Sequence↗

Bovine serum albumin conformation on methyl and amine functionalized surfaces compared by scanning force microscopy.

We investigated the adsorption of albumin on chemically modified gold surfaces by scanning force microscopy operating both in contact and noncontact mode. The surface modification was performed with thiol-based self-assembling molecules carrying amine or methyl groups. The albumin on the aminoethanethiol-coated gold formed a uniform layer and single molecules could be distinguished. On the dodecanethiol-coated surface the protein adsorbed in aggregates or single isolated molecules depending on the incubation time. The width of the albumin molecule on both surface was similar, but the height was much lower on the amine than on the methyl surface. This was interpreted as a difference in the conformation of albumin depending on the substrate, and could explain the promotion of cell adhesion on amine-treated polymers coated with albumin.

Adsorption↗

Highly effective and slow-biodegradable network-type cationic gene delivery polymer: small library-like approach synthesis and characterization.

Over the past years, macromolecular biodegradable polymers have been attracting considerable attention as gene delivery vehicles due to their safety and many potential applications. In the process of developing such biopolymers, we synthesized a biodegradable, network-type poly(amino ester) polymer (nt-PAE), which showed desirable chemical properties and a mechanical durability with high transfection efficiency. A small library-like approach to polymer synthesis using melt polycondensation followed by surface modification with aminohexanoic acid resulted in the final polymer, nt-PAE. The network-type structure of nt-PAE consists of biodegradable ester linkages and tertiary amines embedded in the backbone, and primary amines positioned at the surface. Unlike other rapidly degrading ester polymers, the nt-PAE exhibited fairly slow degradation, as the polymer sustained its DNA complexing ability for 10 days under physiological buffer conditions. In addition, the transfection efficiency of the nt-PAE could be increased to the same level comparable with that of PEI even in the presence of serum. Low toxicity and high transfection efficiency with a slow degradation profile implies that the nt-PAE can be used as a valuable nonviral gene delivery system.

Biocompatible Materials↗

Micropatterning of proteins on nanospheres.

Currently micropatterning of proteins is mainly carried out on a planar substrate, which involves multi-step surface modifications directly on the substrate. Efficiency of chemical reactions is usually low, resulting in low signal-to-noise (S/N) ratio and poor repeatability of results. Here we presented a micropatterning method using polystyrene nanospheres with non-planar surface as a solid support for attaching proteins, which introduces many advantages. The patterning of proteins was carried out in two approaches: one was to dispense polystyrene nanospheres into an array of microwells and then attach proteins onto the nanospheres, and another was to coat polystyrene nanospheres with proteins first and then deposit the spheres into the microwells. For both approaches, a uniform pattern of proteins was generated. The amount of proteins attached via nanospheres was much higher than that on planar surface.

Fluorescein-5-isothiocyanate↗

Thin film of low-crystalline calcium phosphate apatite formed at low temperature.

Surface modification of biomaterials to improve biocompatibility without changing their bulk properties is desired for many clinical applications and has become an emerging technology in biomaterial research and industry. In the present study, a simple method of coating the solid surfaces of metals, organic tissue matrices, glasses, inorganic ceramics as well as organic polymers with a thin film of low-crystalline apatite crystals (LCA) was developed. Acidic solution containing calcium and phosphate ions was neutralized with alkaline solution to form calcium phosphate precipitates at low temperature. Precipitates of solid calcium phosphate particles were, then, removed by filtration. Concentration of free ions in the filtered ion solution which were not involved in the formation of calcium phosphate precipitate was high enough to induce the heterogeneous nucleation on the solid surfaces at low temperature. Thin layers of calcium phosphate crystals were formed on the surfaces of metals, glasses, inorganic ceramics, organic polymers including hydrophobic ones, and biological tissue matrices with this solution. The thin layer of crystals consisted of poorly crystalline calcium phosphate apatite crystals which contain high amount of labile ions like bone crystals and did not dissolve in the physiologic solutions. Various cells attached to this crystal layer and proliferated well.

Biocompatible Materials↗

Neutral postgrafted colloidal particles for gene delivery.

Surface modification of cationic lipoplexes has been carried out by means of a postgrafting reaction. The original lipoplexes described comprise a cationic lipid, a neutral lipid, poly(ethylene glycol)-cholesterol (with or without a targeting ligand) and DNA. Modifying their surface via a chemical, postgrafting reaction did not alter their size (approximately 100 nm) nor their ability to compact DNA, but did give a reduced zeta potential (approximately 0 mV) to afford surface neutral particles. With the modified lipoplexes nonspecific NIH3T3 cell surface binding in vitro was inhibited. Intravenous injection of the neutralized lipoplexes in mice showed decreased accumulation of the particles in the lung as compared to PEGylated cationic lipoplexes. Tumor targeting was also achieved in vivo by the addition of an RGD-PEG-Cholesterol as a lipid-ligand in the postgrafted lipoplex formulation.

Acetates↗

Factors affecting microbial adhesion to stainless steel and other materials used in medical devices.

The role of biofilm in medical device associated infections is well documented. Biofilms are more resistant to antibiotics than planktonic cells, these are extremely difficult to treat. Prevention strategies include efforts to insert implants under stringent aseptic conditions, and also encompass the development of novel materials which interfere with the initial attachment of microorganisms to the surface of the device. Microbial cells also attach onto hygienic surfaces in the hospital setting, and thereby pose a cross-infection problem. In this case, vigorous cleaning and sanitizing regimes may be employed in addition to any surface modifications. Many factors affect the initial attachment of organisms to inert substrata, and their subsequent retention or removal/detachment, including the physical and chemical nature and location of the substratum, the type of organic material and microorganisms potentially fouling the surface, and the nature of the interface (solid-liquid in the body; solid-air on environmental surfaces). Focusing on one factor, surface topography, it is apparent that many further variables need to be defined in order to fully understand the interactions occurring between the cell and surface. It is therefore important when modifying one substratum surface property in order to reduce adhesion, to also consider other potentially confounding factors.

Bacterial Adhesion↗

Decellularized umbilical artery treated with thin polyelectrolyte multilayer films: potential use in vascular engineering.

Decellularized allograft tissues have been identified as a potential extracellular matrix scaffold for tissue-engineered vascular substitutes. In order to improve the thromboresistance, it is necessary to pre-coat the intra-luminal vessel surface. Recently a new surface modification technique appeared, based on the alternate adsorption of positive and negative charged polyelectrolytes. Our objective was to develop an alternative vascular scaffold made of decellularized human umbilical arteries treated with a PAH/PSS polyelectrolyte multilayered film. The vessels luminal surfaces covered with the multilayer film were observed by electronic scanning microscopy. Our observations showed that the luminal surface is completely devoid of ECs following treatment with trypsin. A top view of the coated artery indicated that the multilayer uniformly covered internal surface of the vessels. The successful of the multilayer correct deposition and retention on the arterial wall were controlled by confocal microscopy using a fluorescent polyelectrolyte (rhodamine-PAH). The data suggest that decellularized cryopreserved arteries represent a potential scaffold for further vascular tissue engineering efforts. Moreover, the multilayer films can be used to coat biological surfaces and following the terminated layer (PAH or PSS), favour the cell adhesion or cell resistance.

Arteries↗

The cell surface of Mycobacterium avium-intracellulare and M. scrofulaceum: effect of specific chemical modifications on cell surface charge.

Cells of representative strains of the Mycobacterium avium-intracellulare and Mycobacterium scrofulaceum (MAIS) group had mixed cationic/anionic surfaces, unlike the surfaces of other mycobacteria. The pH electrophoretic mobility curves demonstrated that all MAIS strains examined had a net negative mobility above pH 3.5-4.5 and a positive mobility below that pH range. Based upon the pH electrophoretic mobility of cells following chemical or enzymatic treatment, it appears that the surface molecules contributing to charge are amino groups (primarily contributed by proteins), carboxyl and phosphate (and phosphodiester-linked) groups.

Cell Membrane↗

Surface-modified nanocrystalline ceramics for drug delivery applications.

Drug delivery systems comprised of various types of carriers have long been the object of pharmacological investigation. The search has been stimulated by the belief that carriers will lead to reduced drug toxicity, dosage requirements, enhanced cellular targeting and improved shelf-life. Among the carriers investigated are complex polymeric carbohydrates, synthetic proteins and liposomal structures. For the past four years, we have been experimenting with a radically new class of carriers comprised of surface-modified nanocrystalline ceramics. While the ceramics provide the structural stability of a largely immutable solid, the surface modification creates a glassy molecular stabilization film to which pharmacological agents may be bound non-covalently from an aqueous phase with minimal structural denaturation. As a consequence of maintained structural integrity and owing to concentration effects afforded by the surfaces of the nanocrystalline materials, drug activity following surface immobilization is preserved. We have used successfully surface-modified nanocrystalline ceramics to deliver viral antigens for the purpose of evoking an immune response, oxygenated haemoglobin for cell respiration and insulin for carbohydrate metabolism. The theoretical principles, technical details and experimental results are reviewed. Surface-modified nanocrystalline materials offer an exciting new approach to the well-recognized challenges of drug delivery.

Animals↗

EGF-grafted PDMS surfaces in artificial cornea applications.

Lack of epithelial cell coverage has remained a persistent problem in the design of an artificial cornea. In this work, polydimethylsiloxane (PDMS) surfaces were modified with epidermal growth factor (EGF) to improve the growth of corneal epithelial cells. The EGF was covalently tethered to PDMS substrates aminated by plasma polymerization of allylamine via a homobifunctional polyethylene glycol (PEG) spacer. Surface modification was confirmed by contact angle and X-ray photoelectron spectroscopy measurements. By varying the ratio of EGF to PEG from 1:50 to 1:5, EGF amounts from 40 to 90 ng/cm2 could be bound, as determined by surface plasmon resonance (SPR) and 125I radiolabelling. Human corneal epithelial cells on the various modified surfaces were cultured both in the presence and absence of EGF in the culture medium to determine the effect of covalently bound EGF on the cells. The results demonstrated that covalently bound EGF on the surfaces is active with respect to promoting epithelial cell coverage. This was significant when compared to unmodified controls.

Adsorption↗