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Although rhBMP-2 has excellent ability to accelerate the repair of normal bone defects, limitations of its application exist in the high cost and potential side effects. This study aimed to develop a composite photopolymerisable hydrogel incorporating rhBMP-2 loaded 2-N, 6-O-sulfated chitosan nanoparticles (PH/rhBMP-2/NPs) as the bone substitute to realize segmental bone defect repair at a low growth factor dose. Firstly rhBMP-2 loaded 2-N, 6-O-sulfated chitosan nanoparticles (rhBMP-2/NPs) were prepared and characterized by DLS and TEM. Composite materials, PH/rhBMP-2/NPs were developed and investigated by SEM-EDS as well as a series of physical characterizations. Using hMSCs as an in vitro cell model, composite photopolymerisable hydrogels incorporating NPs (PH/NPs) showed good cell viability, cell adhesion and time dependent cell ingrowth. In vitro release kinetics of rhBMP-2 showed a significantly lower initial burst release from the composite system compared with the growth factor-loaded particles alone or encapsulated directly within the hydrogel, followed by a slow release over time. The bioactivity of released rhBMP-2 was validated by alkaline phosphatase (ALP) activity as well as a mineralization assay. In in vivo studies, the PH/rhBMP-2/NPs induced ectopic bone formation in the mouse thigh. In addition, we further investigated the in vivo effects of rhBMP-2-loaded scaffolds in a rabbit radius critical defect by three dimensional micro-computed tomographic (μCT) imaging, histological analysis, and biomechanical measurements. Animals implanted with the composite hydrogel containing rhBMP-2-loaded nanoparticles underwent gradual resorption with more pronounced replacement by new bone and induced reunion of the bone marrow cavity at 12 weeks, compared with animals implanted with hydrogel encapsulated growth factors alone. These data provided strong evidence that the composite PH/rhBMP-2/NPs are a promising substitute for bone tissue engineering.

A biomimetic material that can assist bone tissue regeneration was proposed. A bone scaffold based on a hybrid hydrogel self-assembled from N-(2-hydroxypropyl)methacrylamide (HPMA) copolymers grafted with complementary β-sheet peptides was designed. Investigation of self-assembly by circular dichroism spectroscopy suggested that hydrogel formation was triggered through association of the complementary β-sheet motifs. Congo Red and thioflavin T binding, as well as transmission electron microscopy confirmed the formation of a fibril network. Besides mimicking the natural bone extracellular matrix and maintaining preosteoblast cells viability, this hydrogel, as shown by scanning electron microscopy and Fourier transform infrared spectroscopy, provided surfaces characterized by epitaxy that favored hydroxyapatite-like crystal nucleation and growth potentially beneficial for biointegration.

Chitosan and collagen type I are naturally-derived materials used as cell carriers because of their ability to mimic the extracellular environment and direct cell function. In this study beta-glycerophosphate (beta-GP), an osteogenic medium supplement and a weak base, was used to simultaneously initiate gelation of pure chitosan, pure collagen, and chitosan-collagen composite materials at physiological pH and temperature. Adult human bone marrow-derived stem cells (hBMSC) encapsulated in such hydrogels at chitosan/collagen ratios of 100/0, 65/35, 25/75, and 0/100 wt% exhibited high viability at day 1 after encapsulation, but DNA content dropped by about half over 12 days in pure chitosan materials while it increased two-fold in materials containing collagen. Collagen-containing materials compacted more strongly and were significantly stiffer than pure chitosan gels. In monolayer culture, exposure of hBMSC to beta-GP resulted in decreased cell metabolic activity that varied with concentration and exposure time, but washing effectively removed excess beta-GP from hydrogels. The presence of chitosan in materials resulted in higher expression of osterix and bone sialoprotein genes in medium with and without osteogenic supplements. Chitosan also increased alkaline phosphatase activity and calcium deposition in osteogenic medium. Chitosan-collagen composite materials have potential as matrices for cell encapsulation and delivery, or as in situ gel-forming materials for tissue repair.

Protein adsorption and cell adhesion on cationic, neutral, and anionic water-soluble 2-methacryloyloxyethyl phosphorylcholine (MPC) copolymer surfaces were compared. These model MPC copolymers coated SiO(2) surfaces exhibited comparable surface zeta-potentials of 26.1 mV, near 0 mV, and -24.2 mV, respectively. X-ray photoelectron spectroscopy analyses indicated the similarities and the differences in the surface composition between the sample surfaces. Atomic force microscopy analyses revealed that the type of the charged moiety did not affect the surface roughness. Static contact angle measurements and dynamic contact angle analyses not only indicated that the surfaces were very hydrophilic in general, but also provided information on the surface mobility and the dominant role of MPC at the surface in aqueous conditions. Comparing with the SiO(2) substrates on which protein seriously adsorbed and cell heavily adhered, three MPC copolymers coated surfaces, despite their different charge properties, exhibited significantly low adsorbed amounts of different proteins having various electrical natures and totally no cell adhesion. This suggested that the incorporation of charged moieties in the MPC copolymers did not significantly inspire both the protein adsorption and cell adhesion. The MPC moieties were predominant at the surface when in contact with aqueous conditions and thereby dominated the bio-adsorptions, while the possible effect from electrostatic interactions would be too small and too limited to influence the overall situation. Therefore, these MPC copolymer surfaces can satisfy those biological applications requiring not only electrical but also non-biofouling properties.

In this study, we report a new type of oxygen-generating scaffold, composed of human keratin, silk, gelatin and calcium peroxide (CPO). After mixing the silk/keratin (60:40) with 2% gelatin and 20% CPO, the film demonstrated excellent mechanical properties, non-cytotoxicity and oxygen-generative ability. The detailed structure of scaffold was revealed by confocal laser and electronic scanning microscopy. The gelatin formed the network structure, which mixed with silk fibroin and keratin. The CPOs were embedded into scaffold. A shell–core structure was formed in the CPO particles, in which the CPO was located in the core and the gelatin was mainly wrapped around the CPO. Furthermore, the oxygen-release test showed that scaffold was able to steadily release high level of oxygen over two weeks in vitro. In addition, the anti-bacterial function was also proved in the scaffold. Films with CPO enhanced the repair in dog urethral defect models, resulting in patent urethra. Improved organized muscle bundles and epithelial layer were observed in animals treated with CPO films compared with those treated with non-CPO films. This study suggests that this biomaterial could be suitable for tissue engineered urinary tract reconstruction.

Polyetheretherketone (PEEK) is desirable in orthopedic and dental applications because its mechanical properties are similar to those of natural bones but the bioinertness and inferior osteoconduction of PEEK have hampered many clinical applications. In this work, PEEK is sulfonated by concentrated sulfuric acid to fabricate a three-dimensional (3D) network. A hydrothermal treatment is subsequently conducted to remove the residues and the temperature is adjusted to obtain different sulfur concentrations. In vitro cell proliferation and real-time PCR analyses disclose enhanced proliferation and osteogenic differentiation of rat bone mesenchymal stem cells (rBMSCs) on the samples with small sulfur concentrations. The in vitro antibacterial evaluation reveals that all the sulfonated samples possess excellent resistance against Staphylococcus aureus and Escherichia coli. The in vivo rat femur implantation model is adopted and X-ray, micro-CT, and histological analyses indicate that not only the premeditated injected bacteria cells are sterilized, but also new bone forms around the samples with small sulfur concentrations. The in vitro and in vivo results reveal that the samples subjected to the hydrothermal treatment to remove excess sulfur have better osseointegration and antibacterial ability and PEEK modified by sulfonation and hydrothermal treatment is promising in orthopedic and dental applications.

Commercial polypropylene pelvic mesh products were characterized in terms of their chemical compositions and molecular weight characteristics before and after implantation. These isotactic polypropylene mesh materials showed clear signs of oxidation by both Fourier-transform infrared spectroscopy and scanning electron microscopy with energy dispersive X-ray spectroscopy (SEM/EDS). The oxidation was accompanied by a decrease in both weight-average and z-average molecular weights and narrowing of the polydispersity index relative to that of the non-implanted material. SEM revealed the formation of transverse cracking of the fibers which generally, but with some exceptions, increased with implantation time. Collectively these results, as well as the loss of flexibility and embrittlement of polypropylene upon implantation as reported by other workers, may only be explained by in vivo oxidative degradation of polypropylene.

The purpose of this study was to produce a well-characterised electrospun polystyrene scaffold which could be used routinely for three-dimensional (3D) cell culture experimentation. A linear relationship ( p 0.01 ) between three principal process variables (applied voltage, working distance and polymer concentration) and fibre diameter was reliably established enabling a mathematical model to be developed to standardise the electrospinning process. Surface chemistry and bulk architecture were manipulated to increase wetting and handling characteristics, respectively. X-ray photoelectron spectroscopy (XPS) confirmed the presence of oxygen-containing groups after argon plasma treatment, resulting in a similar surface chemistry to treated tissue culture plastic. The bulk architecture of the scaffolds was characterised by scanning electron microscopy (SEM) to assess the alignment of both random and aligned electrospun fibres, which were calculated to be 0.15 and 0.66, respectively. This compared to 0.51 for collagen fibres associated with native tissue. Tensile strength and strain of approximately of 0.15 MPa and 2.5%, respectively, allowed the scaffolds to be routinely handled for tissue culture purposes. The efficiency of attachment of smooth muscle cells to electrospun scaffolds was assessed using a modified 3-[4,5-dimethyl(thiazol-2yl)-3,5-diphery] tetrazolium bromide assay and cell morphology was assessed by phalloidin-FITC staining of F-actin. Argon plasma treatment of electrospun polystyrene scaffold resulted in significantly increased cell attachment ( p 0.05 ). The alignment factors of the actin filaments were 0.19 and 0.74 for the random and aligned scaffold respectively, compared to 0.51 for the native tissue. The data suggests that electrospinning of polystyrene generates 3D scaffolds which complement polystyrene used in 2D cell culture systems.

A photo-immobilisation procedure was utilised to create two different rnicro-patterned surfaces (tracks 25 and 5 mu m wide) of hyaluronan (Hyal) on polyethylene-terephthalate (PET) previously plasma activated. Aim of the study was to investigate the proliferation and re-clifferentiation capacity of articular chondrocytes Cultured on micro-patterned Hyal, compared to homogeneous Hyal and plain plasma-treated (pt-)PET substrates. Cytotoxicity, cell proliferation, activation and differentiation of articular knee cartilage chondrocytes (Mongrel sheep) were evaluated after 14 days of culture. It was found that micro-patterned Hyal surfaces induced the adhesion, migration and alignment of chondrocytes, as shown by light and scanning electron microscopy. Furthermore, the same surfaces induced chondrocyte differentiation, with a significant increase of aggrecan and collagen type II production, while homogeneous Hyal and pt-PET surfaces did not. (c) 2005 Elsevier Ltd. All rights reserved.

Alginate–poly- l -lysine–alginate (APA) microcapsules are currently being investigated as a means to immuno-isolate transplanted cells, but their biocompatibility is limited. In this study, we verified the hypothesis that poly- l -lysine (PLL), which is immunogenic when unbound, is exposed at the APA microcapsule surface. To do so, we analysed the microcapsule membrane at the micrometric/nanometric scale using attenuated total reflectance Fourier transform infrared spectroscopy, X-ray photoelectron spectroscopy, and time-of-flight secondary ion mass spectrometry. The results indicate that PLL and alginate molecules interact within the membrane. PLL exists in considerable amounts near the surface, contributing to the majority of the carbon within the outermost 100 A of the membrane. PLL was also detected at the true surface (the outermost monolayer) of the microcapsules. The exposure of PLL does not appear to result from defects in the outer alginate coating. This physicochemical model of APA microcapsules could explain their immunogenicity and will play an important role in the optimization of the microcapsule design.

To improve the surface biocompatibility of titanium films, a layer-by-layer (LBL) self-assembly technique, based on the polyelectrolyte-mediated electrostatic adsorption of chitosan (Chi) and gelatin (Gel), was used leading to the formation of multilayers on the titanium thin film surfaces. The film growth was initialized by deposition of one layer of positively charged poly(ethylene imine) (PEI). Then the thin film was formed by the alternate deposition of negatively charged Gel and positively charged Chi utilizing electrostatic interactions. The LBL film growth was monitored by several techniques. The chemical composition, surface topography as well as wettability were investigated by using X-ray photoelectron spectroscopy (XPS), atomic force microscopy (AFM), confocal laser scanning microscopy (CLSM) and water contact angle measurement, respectively. Quantitative XPS analysis showed the alternative change of C/N ratio after four sequential cycles coating of Ti/PEI/Gel/Chi/Gel, which indicated the discrete layer structure of coatings. Uncoated titanium (control sample) displayed a smooth surface morphology (root mean square (RMS) roughness was around 2.5 nm). A full coverage of coating with Gel/Chi layers was achieved on the titanium surface only after the deposition layers of PEI/(Gel/Chi)2. The PEI/Gel/(Chi/Gel)3 layer displayed a rough surface morphology with a tree-like structure (RMS roughness is around 82 nm). These results showed that titanium films could be modified with Chi/Gel which may affect the biocompatibility of the modified titanium films. To confirm this hypothesis, cell proliferation and cell viability of osteoblasts on LBL-modified titanium films as well as control samples were investigated in vitro. The proliferation of osteoblasts on modified titanium films was found to be greater than that on control (p

Titanium has been a successful implant material owing to its excellent strength to weight ratio, toughness, and bioinert oxide surface. Significant progress has been made on the improvement of titanium's bioactivity by coating its oxide surface with calcium phosphates and bioactive molecules. Here, we report on the coating of titanium with a poly( l -lysine)-calcium phosphate hybrid material with a nanoscale texture. This hybrid coating was grown by first nucleating seed crystals of calcium phosphate, directly on the Ti surface and then exposing this surface to solutions containing Ca2+, PO43−, and poly( l -lysine). The resultant hybrid coating was characterized by electron microscopy, X-ray diffraction, Fourier transform infrared spectroscopy, thermogravimetric analysis, X-ray photoelectron spectroscopy, and elemental analysis. This material contained 14% by weight poly( l -lysine), and this organic component decreased greatly the dimensions of the surface features, thus enhancing surface area relative to the inorganic control. The highly textured hybrid material was more susceptible than the control to acidic and enzymatic degradation. The amino acid cysteine was covalently linked to the hybrid material, demonstrating the potential of this coating for further functionalization. These hybrid coatings may prove useful in enhancing the bioactivity of titanium.

A self-transformable sulfonated poly(ethylene glycol) acrylate diblock copolymer (PEG-SO3A/OA) entrapped into polysulfone membrane was studied. The asymmetric membrane structure was prepared by a phase inversion process. The induced hydrophilicity by reorientation of diblock copolymer at the interface was evaluated by contact angle measurement, platelet adhesion test, and electron spectroscopy for chemical analysis (ESCA) depth profiling with ion sputtering. Molecular dynamic (MD) simulations as a function of copolymer density were also performed to obtain optimum interfacial structure information. The dependency of water clustering behavior as a hydrophilicity parameter was described in terms of an atom-atom radial distribution function (RDF). The results showed that the sulfonated diblock copolymer enhanced the hydrophilicity and long-term stability more than the copolymer having no hydrophobic block. Also, according to the ESCA, oxygen composition significantly began to decrease along the membrane depth, indicating the reorientation of diblock chains. The copolymer-entrapped surfaces significantly induced the degree of water clustering, and the resulting equilibrium rearrangement of interfacial structure was distinctly dependent upon the density of the copolymer.

The aim of the present study is to investigate bone tissue reactions to various surface oxide properties, in particular to different surface oxide chemistry of oxidized titanium implants (grade 1). One control and three test screw-shaped implant groups were prepared. Controls were turned implants. Test implants, i.e. S implants, P implants and Ca implants were by the micro-arc oxidation (MAO) method. The surface characterizations were performed with X-ray photoelectron spectroscopy, Auger electron spectroscopy, scanning electron microscopy, X-ray diffractometry and TopScan 3D. Eighty implants were inserted in the femora and tibiae of ten mature New Zealand white rabbits for 6 weeks. The removal torque values (RTQ) showed significant differences between S implants and controls (p=0.022), Ca implants and controls (p=0.0001), Ca implants and P implants (p=0.005) but did not show significant differences between the others (p>0.05). In addition, the bone to metal contact (BMC) around the entire implants demonstrated 186% increase in S implants, 232% increase in P implants and 272% increase in Ca implants when compared to the paired control groups. Based on the comparative analysis of the surface characteristics resulting different bone responses between all groups, it was concluded that surface chemistry and topography separately or together play important roles in the bone response to the oxidized implants.

Allylamine was plasma polymerised onto a polyester (PET) membrane to obtain a surface with good cell adhesive properties. Samples were coated using a microwave plasma source operating at different process parameters. The effect of process parameters on the physical, and chemical properties of plasma-polymerised-allylamine (PPAa) was evaluated by studying elemental composition, amine concentration, wettability, and surface morphology. A relatively high amine concentration was measured (up to 50 nmol/cm2). In parallel, nitrogen enrichment was observed after exposure to high-energetic plasma. Irrespective of the treatment conditions, oxygen was incorporated into the polymer structure. PPAa surfaces were found to be more hydrophilic than PET. The wettability of the samples increased with increasing amine concentration. Pictures from scanning electron microscopy indicated that homogeneous pinhole-free PPAa layers were deposited on PET membranes, without a significant change of permeability. In vitro evaluation of biocompatibility was carried out by studying human skin fibroblast interaction with surfaces. Cell attachment and viability on PPAa layers were found to be more intensive than on the control PET, based on the higher metabolic activity of adhering cells, but also on morphological criteria including overall cell morphology.

Previously, we have demonstrated the suitability of bacterial adhesin-related peptides, directly immobilized on polystyrene surfaces, to bind and orient fibronectin (FN). For these studies a method to bind the large protein FN in a desired orientation on a solid substratum was developed which utilizes a bacterial adhesin-related peptide (designated BRP-A), which is known to bind specifically to the NH3-terminus end of FN. Glass substrata was first coated with an amine-terminated silane, followed by streptavidin (SA), which was used as an intermediate tether to bind the biotinylated bacterial adhesin-related peptide. The BRP-A peptide, used for these studies was synthesized with a terminal biotin to assure irreversible coupling of the BRP-A to the streptavidin. The biotinylated BRP-A was next immobilized on the SA-silanated glass surfaces. 125I-FN was used to quantify the amount of FN binding to the (BRP-A):SA-silanated glass surface. Monoclonal antibodies, which react with specific epitopes at either the NH3- or -COOH-termini of FN, were used to quantify the binding and orientation of FN. The results of these studies indicated: (1) FN bound to the BRP-A:SA-silanated glass surface; and (2) the bound FN was oriented such that NH2-terminal region of FN was bound towards the glass surface and the COOH-terminus was oriented away from the glass surface. These studies demonstrate that small peptides can be used to specifically bind and orient large proteins such as FN on the surfaces.

Nacre, also known as mother-of-pearl, constitutes the inner layer of mollusc shells. Nacre is a natural composite material consisting mostly of calcium carbonate in the aragonite crystal form and some organic matter. Previous studies have shown that geological aragonite, coral and nacre can convert hydrothermally to hydroxyapatite (HAP) in phosphate solution by a solid-state topotactic ion-exchange reaction. This conversion typically occurs within the range of 140-260 degrees C, although higher temperatures are possible. In this work, we have found that nacre can transform to HAP in a phosphate buffer solution at room temperature via a surface reaction. The morphology of the nacre-transformed HAP surface was investigated by scanning electron microscopy (SEM). The HAP surfaces were characterized by X-ray photoelectron spectroscopy (XPS) and secondary ion mass spectroscopy (SIMS). A layer covered with packed particles was found in contrast to the tablet structure typical of nacre surfaces. XPS and SIMS indicated that the mineral phase of the nacre surface had converted from an aragonite phase to an HAP phase. Fourier transform infrared spectroscopy (FTIR) showed that phosphate (PO(4)) bands appeared after nacre was soaked in a phosphate buffer and the intensity of the PO(4) bands increased with exposure time. The FTIR was consistent with XPS and SIMS results. We suggest that this surface reaction occurs by a dissolution-precipitation mechanism. Calcium ions are released from the nacre surface, react with phosphate ions in the buffer solution, and then precipitate as HAP on the nacre surface.

A series of gases were used for plasma treatment of poly-( l -lactide) (PLLA) under various conditions such as atmosphere, electric power, pressure and time. The NH 3 was preferably selected for modifying the surface of PLLA because it can obtain appropriate hydrophilicity and surface energy with high polar component compared to other gases. Subsequently, cells were seeded onto NH 3 modified surface and exposed to 29.5 N/m 2 of shear stress field by means of a parallel plate flow chamber in order to get good insight into the influence of N-containing incorporation on cell retention, cell morphology, and cell shape factor. The results showed that cell retention on the modified PLLA was much higher than that on the unmodified one. The NH 3 plasma modified PLLA with high cell affinity and resistance to shear stress was gained. Surface hydrophilicity, surface energy with high polar component and N-containing groups may play an important role in enhancing cell resistance to shear stress. It revealed that the parallel plate flow chamber is an effective device for evaluating the effects of surface modification on the cell affinity of a material.

Ti and Ti-based alloys have been widely used for the biomedical applications due to their superiorities of biocompatibility, mechanical properties and corrosion resistance. However, there has been the limiting factor for these metals to show the low affinity to the living bone. Most of commercially used Ti alloys have harmful alloying elements such as Al, V, etc. The purposes of this study are design of new Ti alloy having the good mechanical properties and corrosion resistivity without harmful alloying elements and to improve the bone-bonding ability between Ti-based alloy and living bone through the chemically activated process (alkali treatment) and thermally activated one (heat treatment). Mechanical properties of the Ti-In-Nb-Ta alloy were observed by tensile test (Instron model 8511). Corrosion potential and corrosion rate were investigated using a Potentiostate machine (EG&G, Princeton Applied Model 273, Boston, USA) with saline solution (9% NaCl) without dissolved oxygen at 37 degrees C. After alkali and heat treatments, the effects of the pre-treatments on the bonding property were evaluated by in vitro test. In this study, the surface changing behavior, which is apatite formation, of newly designed Ti-In-Nb-Ta alloy without harmful alloying elements was investigated through analyzing its surface by using X-ray photoelectron spectroscopy after surface activation treatments (alkali and heat treatments) and after subsequent soaking in the simulated body fluid.

Materials that adsorb specific proteins may find a variety of applications in the biomedical field. The aim of this study was the preparation of a hydrophilic surface, with low protein adsorption, to be used in the future as a support for the immobilisation of several species, e.g. Cibacron Blue F3G-A, which has been described to induce specific albumin adsorption. Poly(hydroxyethylmethacrylate) (PHEMA) and poly(hydroxyethylacrylate) (PHEA) were chosen as the hydrophilic surface because they can be easily polymerised and possess hydroxyl groups that can be used for the immobilisation of different compounds. Thin films of PHEMA and PHEA were successfully graft polymerised onto the surface of a commercial poly(etherurethane) (PU) using ceric ion as initiator. Grafting polymerisations were followed by mass gain and attenuated total reflection Fourier transform infrared spectroscopy (ATR-FTIR). Since stability tests demonstrated that only PU–PHEMA was stable in alkaline solutions, a necessary condition to future immobilisations, the investigation was focused on the coating of PU with PHEMA. PU–PHEMA films were characterised in detail using several techniques as mass gain, ATR-FTIR, contact angle measurements, X-ray photoelectron spectroscopy (XPS) and scanning electron microscopy (SEM). Protein adsorption was evaluated using radiolabelled albumin and fibrinogen from pure solutions and from mixtures of both proteins. PU surfaces modified with PHEMA have demonstrated low protein adsorption, showing their potential use as substrates. This opens the possibly of exploring the advantages of selective adsorption by appropriate immobilisation of specific molecules.

The effects of phosphorylated chitin (P-chitin) on the tissue responses to two kinds of calcium phosphate cements (CPCs) were investigated using experimental rabbits. One of them consisting of monocalcium phosphate monohydrate, calcium oxide, 1 m phosphate buffer (pH: 7.4) and different amounts of P-chitin (CPC-I or P-CPC-I) with relatively neutral initial pH was filled as paste into tibial defects of the rabbits for 1, 4, 12 and 22 weeks. The other kind of cement made from dicacium phosphate dihydrate/ calcium hydroxide/1 m Na2HPO4/different amounts of P-chitin (CPC-II or P-CPC-II) with relatively higher initial pH was implanted as prehardened cylinders into the radial defects of the rabbits for the same periods. Pure CPC-I and CPC-II were used as controls. Histological and histomorphological studies were performed on thin un-decalcified and decalcified sections. Three different bone formation types in the resorption lacuna of the P-CPCs were found during this study. The biodegradation rate of the P-CPCs had a negative relationship with the P-chitin content. Most of the low P-chitin-containing samples were bioabsorbed in 16 weeks, while the high P-chitin-containing samples disappeared in 22 weeks. The newly formed bone was identified with back scattered scanning electron microscopy and X-ray energy-dispersive spectrometry. The results show that with P-chitin component in a certain range, the P-CPCs are biocompatible, bioabsorbable and osteoinductive and could be used as promising candidates of bone repair materials. r 2002 Elsevier Science Ltd. All rights reserved.

Immobilization of biomolecules on surfaces enables both localization and retention of molecules at the cell-biomaterial interface. Since metallic biomaterials used for orthopedic and dental implants possess a paucity of reactive functional groups, biomolecular modification of these materials is challenging. In the present work, we investigated the use of a plasma surface modification strategy to enable immobilization of bioactive molecules on a "bioinert" metal. Conditions during plasma polymerization of allyl amine on Ti-6Al-4V were varied to yield 5 ("low")- and 12 ("high")-NH2/nm2. One- and two-step carbodiimide schemes were used to immobilize lysozyme, a model biomolecule, and bone morphogenetic protein-4 (BMP-4) on the aminated surfaces. Both schemes could be varied to control the amount of protein bound, but the one-step method destroyed the activity of immobilized lysozyme because of crosslinking. BMP-4 was then immobilized using the two-step scheme. Although BMP bound to both low- and high-NH2 surfaces was initially able to induce alkaline phosphatase activity in pluripotent C3H10T1/2 cells, only high amino group surfaces were effective following removal of weakly bound protein by incubation in cell culture medium.

In this study we report semimetal nanomaterials of antimony (Sb) as highly efficient agent for photoacoustic imaging (PAI) and photothermal therapy (PTT). The Sb nanorod bundles have been synthesized through a facile route by mixing 1-octadecane (ODE) and oleyl amine (OAm) as the solvent. The aqueous dispersion of PEGylated Sb NPs, due to its broad and strong photoabsorption ranging from ultraviolet (UV) to near-infrared (NIR) wavelengths, is applicable as a photothermal agent driven by 808 nm laser with photothermal conversion efficiency up to 41%, noticeably higher than most of the PTT agents reported before. Our in vitro experiments also showed that cancer cell ablation effect of PEGylated Sb NPs was dependent on laser power. By intratumoral administration of PEGylated Sb NPs, 100% tumor ablation can be realized by using NIR laser irradiation with a lower power of 1 W/cm(2) for 5 min (or 0.5 W/cm(2) for 10 min) and no obvious toxic side effect is identified after photothermal treatment. Moreover, intense PA signal was also observed after intratumoral injection of PEGylated Sb NPs and NIR laser irradiation due to their strong NIR photoabsorption, suggesting PEGylated Sb NPs as a potential NIR PA agent. Based on the findings of this work, further development of using other semimetal nanocrystals as highly efficient NIR agents can be achieved for vivo tumor imaging and PTT.

cited By 32; International audience; In order to fulfill the clinical requirements for strong, tough and stable ceramics used in dental applications, we designed and developed innovative zirconia-based composites, in which equiaxial α-Al2O3 and elongated SrAl12O19 phases are dispersed in a ceria-stabilized zirconia matrix. The composite powders were prepared by an innovative surface coating route, in which commercial zirconia powders were coated by inorganic precursors of the second phases, which crystallize on the zirconia particles surface under proper thermal treatment. Samples containing four different ceria contents (in the range 10.0-11.5mol%) were prepared by carefully tailoring the amount of the cerium precursor during the elaboration process. Slip cast green bodies were sintered at 1450°C for 1h, leading to fully dense materials. Characterization of composites by SEM and TEM analyses showed highly homogeneous microstructures with an even distribution of both equiaxial and elongated-shape grains inside a very fine zirconia matrix.Ce content plays a major role on aging kinetics, and should be carefully controlled: sample with 10mol% of ceria were transformable, whereas above 10.5mol% there is negligible or no transformation during autoclave treatment.Thus, in this paper we show the potential of the innovative surface coating route, which allows a perfect tailoring of the microstructural, morphological and compositional features of the composites; moreover, its processing costs and environmental impacts are limited, which is beneficial for further scale-up and real use in the biomedical field. © 2015 Elsevier Ltd.

Surface-grafted poly(ethylene glycol) (PEG) molecules are known to prevent protein adsorption to the surface. The protein-repulsive property of PEG molecules are maximized by covalent grafting. We have synthesized silanated monomethoxy-PEG (m-PEG) for covalent grafting of PEG to surfaces with oxide layers. Two different trialkoxysilylated PEGs were synthesized and characterized. The first trialkoxysilylated PEG was prepared by direct coupling of m-PEG with 3-isocyanatopropyltriethoxysilane through a urethane bond (silanated PEG I). The other silanated PEG (silanated PEG II) containing a long hydrophobic domain between PEG and a silane domain was prepared by reacting m-PEG with 1,6-diisocyanatohexane and 10-undecen-1-ol in sequence before silylation with 3-mercaptopropyl trimethoxysilane. Silanated PEGs I and II were grafted onto glass, a model surface used in our study. The PEG-grafted glass surfaces were characterized by contact angle, X-ray photoelectron spectroscopy (XPS), and atomic force microscopy (AFM). Although contact angle did not change much as the bulk concentration of silanated PEG used for grafting increased from 0.1 to 20 mg/ml for both PEGs I and II, the surface atomic concentrations from XPS measurements showed successful PEG grafting. Surface PEG grafting increased concentration of surface carbon but decreased silicone concentration. The high resolution C1s spectra showed higher ether carbon with lower hydrocarbon compositions for the PEG-grafted surfaces compared to the control surface. AFM images showed that more PEG molecules were grafted onto the surface as the bulk concentration used for grafting was increased. AFM images of the dried surfaces showed that the surfaces were not completely covered by PEG molecules. After hydration, however, the surface appears to be covered completely probably due to the hydration of the grafted PEG chains. Glass surfaces modified with silanated PEGs reduced fibrinogen adsorption by more than 95% as compared with the control surface. Silanated PEGs provides a simple method for PEG grafting to the surface containing oxide layers.

Preliminary results on the modifications induced by the growth of a Chinese Hamster Ovary (CHO) cell line on the surface of a CORD 1014 ceramic cordierite are reported. Results proved that cells strongly modify the crystallography and the chemical composition of the surface and near surface regions of the cordierite.

Poly(ethylene glycol)-dextran (PEG-DEX) conjugates have been used as a combined stabilizer and surface modifier to produce resorbable poly( DL -lactide-co-glycolide) (PLG) microparticles by, an emulsification/solvent evaporation technique. The use of PEG or dextran polymers alone was incapable of producing microparticles. Particle size measurements revealed smaller mean particle sizes (480 nm) and improved polydispersity when using a 1.2% PEG substituted conjugate relative to a 9% substituted material (680 nm). PLG microparticles modified by post-adsorbed PEG-DEX conjugates flocculated in 0.01 M salt solutions, whereas PLG microparticles prepared using PEG-DEX as a surfactant were stable in at least 0.5 M NaCl solutions. Surface modification of PLG microparticles was confirmed by zeta potential measurements and surface analysis using X-ray photoelectron spectroscopy. The presence of surface exposed dextran was confirmed by an immunological detection method using a dextran-specific antiserum in an enzyme-linked immunosorbent assay. The findings support a model in which the PEG component of the PEG-DEX conjugate provides an anchor to the microparticle surface while the dextran component extends from the particle surface to contribute a steric stabilization function. This approach offers opportunities for attaching hydrophilic species such as targeting moieties to biodegradable microparticles to improve the interaction of drug carriers and vaccines with specific tissue sites.

The functionalization of polytetrafluoroethylene (PTFE) for human thrombomodulin (hTM) binding has been achieved by CO2 plasma activation and subsequent vapour phase graft polymerization of acrylic acid (AA). The PTFE surfaces after CO2 plasma treatment, AA grafting and hTM immobilization were characterized by attenuated total reflection Fourier transform infrared (ATR-FTIR) spectroscopy, X-ray photoelectron spectroscopy (XPS) and electron spin resonance (ESR) spectroscopy, as well as by zeta potential and wetting measurements to quantitatively control each step of modification. The activity of immobilized hTM was estimated by the protein C activation test.

Titanium implant surfaces are known to spontaneously nucleate apatite layers when in contact with simulated body fluids. However, adsorption of proteins may influence the process of apatite layer formation. In this study the role of bovine serum albumin (BSA) adsorption in the process of apatite deposition on titanium substrates is investigated. Deposition of calcium phosphate was induced by immersing titanium substrates in a Hank's balanced salt solution (HBSS) for times ranging from 1 to 23 days. The resulting substrates were studied by scanning electron microscopy (SEM), energy dispersive spectroscopy (EDS), X-ray photoelectron spectroscopy (XPS), wettability measurements and electrochemical impedance determinations. All these methods indicate the presence of a calcium phosphate layer. The same procedure was repeated substituting HBSS with a solution of BSA in HBSS. Although SEM, EDS and electrochemical impedance spectra do not reveal the presence of an apatite layer, XPS analysis strongly indicates that the inhibition of apatite formation by BSA is only partial. The competition between BSA adsorption and apatite deposition seems to lead to a mixed film where the protein co-exists with calcium phosphate. Wettability studies suggest that this surface film is heterogeneous and porous, similar to the thicker films formed in albumin-free HBSS.

A synthetic peptide, Gly-Arg-Gly-Asp-Ser-Pro-Lys (GRGDSPK), which includes the cell-adhesive region of fibronectin, Arg-Gly-Asp (RGD), was covalently bound to a dialdehyde starch (DAS) coating on a polymer surface by reductive amination. The GRGDSPK/DAS-coated surface was characterized by atomic force microscopy (AFM), X-ray photoelectron spectroscopy (XPS) and scanning electron microscopy (SEM). AFM and SEM revealed a uniform, roughened, textured surface, much more so than standard polymer or adhesive protein-coated polymer surfaces. XPS showed that GRGDSPK binding to DAS occurred in dose-dependent fashion in the 0-200 micrograms ml-1 GRGDSPK concentration range, with a plateau happening in the 200-400 micrograms ml-1 range. AFM revealed a uniform peptide layer on the DAS surface with a maximum separation distance of 50 nm between peptides. Angle-dependent XPS showed that the peptide is present in nearly constant amounts to at least 10 nm depth of the DAS coating. The attachment, spreading and growth properties of anchorage-dependent human umbilical vein endothelial cells (EC) on the GRGDSPK/DAS-coated polystyrene surface were compared with a standard fibronectin-coated polystyrene surface. EC adhesion, spreading and growth properties were similar for cells plated on polystyrene surfaces coated with fibronectin (5 micrograms cm-2) and GRGDSPK (25-50 micrograms ml-1)/DAS. In contrast, EC adhesion, spreading and growth performance significantly increased for cells plated on GRGDSPK (100-200 micrograms ml-1)/DAS compared with the fibronectin-coated surface. These findings support the conclusion that the GRGDSPK/DAS-coated surface can be substituted for an adhesive protein-coated surface in the culture of anchorage-dependent cells.

Three polymeric materials (silicone, PVC and nylon) were compared in an in vitro perfusion model, whereby 5 ml whole blood were perfused along 1 m lengths of polymeric tubing of 1 mm internal diameter at wall shear rates of up to 1000 s −1 . Perfusion took place at 37 °C for 30 min. The polymers were investigated for platelet activation, granulocyte secretion, complement activation and contact phase activation. These parameters were also analysed in static contact for comparison. All the parameters measured displayed a dependence on wall shear rate. In all the materials studied, platelet adhesion and platelet activation increased with increasing flow rate. Granulocyte elastase release increased slightly with increasing flow rate up to 300 s −1 . Complement activation was greatest for PVC at 1000 s −1 , greatest for nylon at 100 s −1 , but there was no measurable difference at either rate for silicone. All samples caused an increase in clotting time with increasing wall shear rate. PVC was the most platelet compatible material, nylon the worst. Silicone caused least contact phase activation, PVC and nylon the most.

The photothermal effect of Fe3O4 magnetic nanoparticles is investigated for cancer therapy both in vitro and in vivo experiments. Heat is found to be rapidly generated by red and near-infrared (NIR) range laser irradiation of Fe3O4 nanoparticles with spherical, hexagonal and wire-like shapes. These Fe3O4 nanoparticles are coated with carboxyl-terminated poly (ethylene glycol)-phospholipid for enhanced dispersion in water. The surface-functionalized Fe3O4 nanoparticles can be taken up by esophageal cancer cells and do not obviously affect the cell structure and viability. Upon irradiation at 808 nm however, the esophageal cancer cell viability is effectively suppressed, and the cellular organelles are obviously damaged when incubated with the NIR laser activated Fe3O4 nanoparticles. Mouse esophageal tumor growth was found to be significantly inhibited by the photothermal effect of Fe3O4 nanoparticles, resulting in effective tumor reduction. A morphological examination revealed that after a photothermal therapy, the tumor tissue structure exhibited discontinuation, the cells were significantly shriveled and some cells have finally disintegrated. (c) 2013 Elsevier Ltd. All rights reserved.Z

Wear debris associated with the polyethylene components of total joint replacements has been shown to induce bone resorption which contributes to implant loosening. In an effort to promote lubrication and reduce wear in artificial hip joints, the use of the cushion bearing concept has been proposed previously; however, an elastomeric material tested as a cushion bearing has been shown to have poor tribological properties during initiation of motion from rest. The goal of this project was to fabricate and characterize an elastomer that has the ability to attract to its surface naturally occurring boundary lubricants from an aqueous solution. The test elastomer and appropriate controls were characterized using fluorescence, electron spin resonance and X-ray photoelectron spectroscopy. The test elastomer was found to have an enhanced ability to attract dipalmitoylphosphatidylcholine, a known physiological boundary lubricant. A cushion bearing that also encourages boundary lubrication represents a potential improvement over currently existing orthopaedic implant-bearing materials.

Surface modifications of glass-reinforced hydroxyapatite composites immersed in a simulated physiological solution were studied using X-ray photoelectron spectroscopy, scanning electron microscopy and energy dispersive X-ray spectroscopy. In the first stages of the apatite formation process, calcium and silicon ions were leached out from the surface of the composites. After 12 days of immersion, apatite crystals were detected on the surface indicating bioactive behaviour. Sodium ions attributed to sodium sulphate were also found in the apatite layer. Bound water on the surface also increased with immersion time.

The surface characteristics of A-B-A type triblock copolymer (GIG) membranes consisting of α-helical poly(γ-benzyl- l -glutamate) (PBLG) as the A component and polyisoprene (PI) as the B component were investigated by X-ray photoelectron spectroscopy (XPS) and contact angle measurements. The XPS measurements showed the copolymer composition of the outermost surface to be quite different from the bulk composition. Results of contact angle measurements indicated the existence of an interfacial region between the α-helical A component and the B component at the surfaces of the block copolymer membranes. Finally, the results of in vivo tests on tissue compatibility indicate that the GIG block copolymer membranes have good biocompatibility.

Bioceramic coatings, created by the high velocity oxy-fuel combustion spraying of hydroxyapatite (HA) powders onto commercially pure titanium, were characterized in order to determine whether this relatively new coating process can be successfully applied to bioceramic coatings of orthopaedic and dental implants. Fourier transform infrared spectroscopy, X-ray diffraction and scanning electron microscopy were used to characterize both the HA starting powders and coatings. A 12 wk immersion test was conducted and the resulting changes in the coatings were also characterized. Calcium ion release during dissolution was measured with flame atomic absorption during the first 6 weeks of the immersion study. A comparison of powder and coating X-ray diffraction patterns and lattice parameters revealed an HA-type coating with some loss in crystallinity. Fourier transform infrared results showed a partial loss of the OH- group during spraying, however the phosphate groups were still present. Scanning electron microscopy analysis showed a lamellar structure with very close coating-to-substrate apposition. The coatings experienced a loss of calcium during the immersion study, with the greatest release in calcium occurring during the first 6 days of the study. No significant structural or chemical changes were observed during the 12 wk immersion study. These results indicate that the high velocity oxy-fuel process can produce an HA-type coating; however, the process needs further optimization, specifically in the areas of coating-to-substrate bond strength and minimization of phases present other than HA, before it would be recommended for commercial use.

Recent advances in material science and chemistry have led to the development of nanoparticles with diverse physicochemical properties, e.g. size, charge, shape, and surface chemistry. Evaluating which physicochemical properties are best for imaging and therapeutic studies is challenging not only because of the multitude of samples to evaluate, but also because of the large experimental variability associated with in vivo studies (e.g. differences in tumor size, injected dose, subject weight, etc.). To address this issue, we have developed a lanthanide-doped nanoparticle system and analytical method that allows for the quantitative comparison of multiple nanoparticle compositions simultaneously. Specifically, superparamagnetic iron oxide (SPIO) with a range of different sizes and charges were synthesized, each with a unique lanthanide dopant. Following the simultaneous injection of the various SPIO compositions into tumor-bearing mice, inductively coupled plasma mass spectroscopy (ICP-MS) was used to quantitatively and orthogonally assess the concentration of each SPIO composition in serial blood samples and the resected tumor and organs. The method proved generalizable to other nanoparticle platforms, including dendrimers, liposomes, and polymersomes. This approach provides a simple, cost-effective, and non-radiative method to quantitatively compare tumor localization, biodistribution, and blood clearance of more than 10 nanoparticle compositions simultaneously, removing subject-to-subject variability.

Calcium phosphate and hydroxyapatite nanoparticles are extensively researched for medical applications, including bone implant materials, DNA and SiRNA delivery vectors and slow release vaccines. Elucidating the mechanisms by which cells internalize nanoparticles is fundamental for their long-term exploitation. In this study, we demonstrate that hydrophilic hydroxyapatite nanoparticles are sequestered within a specialized compartment called SCC (surface-connected compartment). This membrane-bound compartment is an elaborate labyrinth-like structure directly connected to the extracellular space. This continuity is demonstrated by in vivo 2-photon microscopy of ionic calcium using both cell-permeable and cell-impermeable dyes and by 3-D reconstructions from serial block-face SEM of fixed cells. Previously, this compartment was thought to be initiated specifically by exposure of macrophages to hydrophobic nanoparticles. However, we show that the SCC can be triggered by a much wider range of nanoparticles. Furthermore, we demonstrate its formation in A549 human lung epithelial cells, which are considerably less phagocytic than macrophages. EDX shows that extensive amounts of hydroxyapatite nanoparticles can be sequestered in this manner. We propose that SCC formation may be a means to remove large amounts of foreign material from the extracellular space, followed by slow degradation, may be to avoid excessive damage to surrounding cells or tissues.

Casted titanium for dental crowns has been investigated by means of X-ray Photoelectron Spectroscopy (XPS), X-Ray Diffraction (XRD) and Scanning Electron Microscopy (SEM). The samples were prepared according to the Ohara process. XRD analysis revealed that the investment consisted essentially of SiO2, Mg2P2O7, SiO2 · H2O and Mg2SiO4. SEM experiments combined with EDX analysis revealed the following atomic concentrations Si (62.6%), Mg (19.7%), P (17.1%), and Ca (0.6%). After casting, the titanium samples exhibit a rough and irregular surface, and XRD analysis indicated that titanium contains essentially the α phase and traces of the β phase. After demoulding titanium samples, the investment side which was in contact with titanium was black colored, proving the reaction between titanium and the investment. XPS analysis performed on this side of the investment indicated that the Si 2p peak presents a shoulder on the low binding energy side and thus suggest that SiO2 has been transformed into metallic Si.

The aim of this study is the grafting of photoreactive α-propylsulphate-poly(ethylene oxide) (PEO-SO 3 ), one end of which is capped with an azidophenyl group, on polyurethane (PU) surfaces via a photochemical technique. The anti-Factor Xa activity and the platelet adhesion characteristics of the modified PU surface were evaluated by a chromogenic assay method and by a flow-controlled chamber method, respectively. X-ray photoelectron spectroscopy analysis showed that PEO-SO 3 was covalently grafted on the PU surface. The grafted surface showed anti-Factor Xa activity in the presence of antithrombin III, and significantly reduced platelet adhesion characteristics as compared with those of the unmodified PU surface. These results suggest that the grafting of PEO-SO 3 improves the antithrombogenicity of PU surfaces.

This study aims to fabricate biodegradable polymeric particles by electrohydrodynamic atomization (EHDA) for applications in sustained delivery of anticancer drug—paclitaxel to treat C6 glioma in vitro. Controllable morphologies such as spheres, donut shapes and corrugated shapes with sizes from several tens of microns to hundred nanometers of particles were observed by scanning electron microscopy (SEM) and field emission electron microscope (FSEM). The differential scanning calorimetry (DSC) study indicated that paclitaxel could be either in an amorphous or disordered-crystalline phase of a molecular dispersion or a solid solution state in the polymer matrix after fabrication. The X-ray photoelectron spectroscopy (XPS) result suggested that some amount of paclitaxel could exist on the surface layer of the microparticles. The encapsulation efficiency was around 80% and more than 30 days in vitro sustained release profile could be achieved. Cell cycling results suggested that paclitaxel after encapsulation by EHDA could keep its biological function and inhibit C6 glioma cells in G2/M phase. The cytotoxicity of paclitaxel-loaded biodegradable microparticles to C6 glioma cells could be higher than Taxol ® in the long-term in vitro tests evaluated by MTS assay. The drug delivery devices developed by EHDA in this study could be promising for the local drug delivery to treat malignant glioma.

A series of segmented multiblock polyurethanes (MPUs) were synthesized by polyaddition reaction using hexamethylene diisocyanate (HDI)/poly(ethylene oxide) (PEO, as a hydrophilic component)/ poly(tetramethylene oxide) (PTMO)/ poly(butadiene diol)(PBD)/1,4-butanediol(BD)/{2-[bis(2-hydroxyethyl) methyl ammonio]ethyl stearyl phosphate}[BESP, as a phospholipids component: 0–42 mol% (0–9 wt%)]. To improve the blood compatibility of biomedical grade polyurethane (Pellethene ® ), the Pellethene ® was blended with MPUs and then crosslinked using dicumyl peroxide as a crosslinking agent. Effects of BESP content [0–42 mol% (0–9 wt%)] in MPUs on the properties of MPUs and blend (Pellethene ® /MPUs) films were investigated. The X-ray photoelectron spectra indicated that the BESP moieties were located at the surface of the crosslinked blend (Pellethene ® /MPUs) films. As the BESP content in MPUs increased, the water contact angle on the surfaces of corsslinked blend film was decreased but the water absorption and mechanical properties were markedly increased. By the test of platelet adhesion on the surfaces of corsslinked blend film, it was found that the platelet adhesion on the surface was significantly decreased from 70% to 6% by increasing BESP content from 0 to 42 mol% (0–9 wt%) in MPUs. These results suggest that crosslinked blend films may have more potential as a new material for biomedical applications, which are directly in contact with blood.

Leukocyte beta2 integrins Mac-1 and p150,95 are promiscuous cell-surface receptors that recognise and mediate cell adhesion to a variety of adsorbed and denatured proteins. We used albumin as a model protein to study whether leukocyte adhesion and activation depended on the nm-scale topography of a protein adlayer. Albumin adsorbed from the native conformation gave rise to different adlayer topographies and different amounts of adsorbed protein on hydrophobic and relatively hydrophilic polystyrene and silanised silicon-wafer surfaces, whereas adsorption of pre-denatured Alb resulted in similar adlayer topographies and similar amounts of adsorbed protein on these surfaces. All three distinct protein-adlayer topographies supported adhesion of in vitro differentiated, macrophage-like U937 and THP-1 cells, but did not support adhesion of their promonocytic precursors. Human monocytes freshly isolated from peripheral blood did not adhere to adsorbed albumin, not even in the presence of monocyte chemoattractant protein-1 and macrophage inflammatory protein-1alpha chemokines. Adhesion of the macrophage-like cells to albumin in any of the three topographies was inhibited by antibodies against beta2 integrins, but not by antibodies against beta1 integrins, and did not induce secretion of the proinflammatory cytokine tumour necrosis factor-alpha.

Coating porous titanium with calcium phosphate (Ca-P) is an effective way to enhance titanium's osteoinduction capability. This study investigated the effectiveness of two coating methods: biomimetic deposition (BD) and electrochemical deposition (ED) in aqueous solutions. The titanium surfaces were treated by acidic etching and alkaline before coating. Effects of the pre-coating treatments on Ca-P coating were also investigated. Both deposition methods could produce Ca-P coatings on the inner pore surfaces of the titanium. The BD coatings were thicker and more uniform than were the ED coatings. On the other hand, ED was less sensitive to the condition of the titanium surface, and much faster in the coating deposition. However, ED produces less uniform and thinner coating layers on the inner pore surfaces of the titanium than does BD. The crystal structure of the coating is octacalcium phosphate (OCP) regardless of the deposition method. The morphology of flake-like OCP crystals in the deposition layers is similar for both deposition methods, except that the crystal flakes rupture after ED.

Electrostatic layer-by-layer film assembly is an attractive way to non-covalently incorporate proteins and bioactive moieties into the surface of conventional biomaterials. Selection of polycationic and polyanionic components and deposition conditions can be used to control the interfacial properties, and through them protein adsorption, cell adhesion, and tissue development. In this study the polycation was poly(allylamine hydrochloride) (PAH), which is a weak base and consequently adsorbs at interfaces in a pH-dependent manner, and the polyanion was heparin, which is capable of interacting with many adhesion ligands and growth factors. PAH/heparin multilayer films were formed using PAH solutions of pH 6.4, 7.4, 8.4, and 9.4. Film thickness increased both with the number of PAH/heparin bilayers and the pH of the PAH solution. Films consisting of 10 bilayers with heparin topmost exhibited similar bulk atomic compositions and penetration of PAH into the heparin top layer. Finally, fibronectin adsorption and cell adhesion were maximal at an intermediate pH (pH 8.4>pH 9.4>pH 7.4). These results demonstrate that heparin-containing electrostatic films support cell adhesion and protein adsorption in a manner sensitive to film deposition conditions.

Exoelectron spectroscopy and ultrasound velocity (USV) measurements have been applied to analyse both the electron and mechanical behaviour of compact bone tissue and its main components--collagen and hydroxyapatite (HAP)--in the temperature range 20-80 degrees C. The special exoelectron method with additional IR illumination has been pioneered for the above objective. Thermally induced variations of the electron structure of bone tissue and HAP were manifested at 55 degrees C, but in collagen they were near 75 degrees C. The greatest decrease in USV was at 35-65 degrees C in collagen and at 55-70 degrees C in bone. No changes of USV in HAP were revealed. The coincidence of temperatures of the exoemission maxima and of the USV most expressed gradient in fresh bone and collagen proves the correlation between electron and mechanical behaviour during heating, connected with the partial denaturation of collagen.

An asymmetric viologen, N -hexyl-N′-(4-vinylbenzyl)-4,4′-bipyridinium bromide chloride (HVV), was synthesized and graft copolymerized with commercial PET films. The surface graft concentration of HVV on the PET film is easily controlled by varying the monomer concentration used in the UV-induced graft copolymerization process. The HVV surface functionalized PET film functions as a smart window whose transmittance is reduced upon exposure to light. Concomitantly, the film possesses antibacterial activity, as shown by its bactericidal effect on Escherichia coli ( E. coli ). The antibacterial activity depends on the concentration of pyridinium groups on the surface and a surface concentration of 25 nmol/cm 2 on PET has been shown to be highly effective in killing the bacteria.

Hydrogen in silicon has been widely applied in semiconductor fields. In this paper, the application of hydrogen-implanted silicon wafer in biomedical fields was explored by investigating its bioactivity. Hydrogen implanted silicon wafers were prepared using plasma immersion ion implantation. The surface structures of the 1.4 x 10(17) cm(-2) hydrogen-implanted silicon wafers were investigated using atomic force microscopy and transmission electron microscopy (TEM). The hydrogen depth profiles were acquired by SIMS and the crystal quality of the as-implanted silicon was studied by channeling Rutherford backscattering spectrometry (RBS). The bioactivity of the implanted silicon was evaluated using the biomimetic growth of apatite on its surface after it was soaked in simulated body fluid for a period of time. The TEM, SIMS and RBS results indicate the formation of an amorphous hydrogenated silicon (a-Si:Hx) layer has been formed on the surface of the hydrogen-implanted silicon wafer. After immersion in SBF for 14 days, bone-like apatite is observed to nucleate and grow on the surface. With longer soaking time, more apatite appeared on the surface of the hydrogen implanted silicon but our control experiments did not reveal any apatite formation on the surface of the un-implanted silicon wafer, hydrogenated crystalline silicon wafer (with hydrogen, but no amorphous surface), or argon-implanted silicon wafer (amorphous surface but without hydrogen). Our results indicated that the bioactivity of silicon wafer can be improved after hydrogen implantation and the formation of the amorphous hydrogenated silicon (a-Si:Hx) surface also plays a synergistic role to improve the bioactivity.

Cell adhesion to biomaterials is mediated primarily by the interaction between surface bound proteins and corresponding receptors on the membrane of the cells. The attachment of fibronectin onto poly(vinylidenefluoride) (PVDF) surface and the application of PVDF as biomaterial in bone contact was the subject of our study. PVDF is a biomaterial established for soft tissue applications. Surface modifications of PVDF were performed by plasma induced graft copolymerisation of acrylic acid or CVD polymerisation of 4-amino[2.2]paracyclophane. The provided functionalised PVDF surface was used to immobilise fibronectin using different techniques. All modification steps were verified by means of X-ray photoelectron spectroscopy (XPS), attenuated total reflection infrared spectroscopy (IR-ATR) and contact angle measurements. Surface topology was studied by atomic force measurements (AFM). Protein adsorption was controlled by enzyme linked immunosorbent assay (ELISA). Cell attachment was enhanced if physically adsorbed fibronectin was used, while enhanced attachment and proliferation were induced by covalently binding fibronectin to the surface modified PVDF.

Hydrogen embrittlement of a beta titanium orthodontic wire has been examined by means of a delayed-fracture test in acid and neutral fluoride aqueous solutions and hydrogen thermal desorption analysis. The time to fracture increased with decreasing applied stress in 2.0% and 0.2% acidulated phosphate fluoride (APF) solutions. The fracture mode changed from ductile to brittle when the applied stress was lower than 500MPa in 2.0% APF solution. On the other hand, the delayed fracture did not occur within 1000h in neutral NaF solutions, although general corrosion was also observed similar to that in APF solutions. Hydrogen desorption of the delayed-fracture-tested specimens was observed with a peak at approximately 500 degrees C. The amount of absorbed hydrogen was 5000-6500 mass ppm under an applied stress in 2.0% APF solution for 24h. It is concluded that the immersion in fluoride solutions leads to the degradation of the mechanical properties and fracture of beta titanium alloy associated with hydrogen absorption.