Surface modification with both phosphorylcholine and stearyl groups to adjust hydrophilicity and hydrophobicity

A new monolayer film with tunable hydrophilicity and hydrophobicity was constructed on glass coverslips by stepwise grafting with both phosphorylcholine (PC) and stearyl groups. The glass coverslips were firstly hydroxylized to provide reactive sites on the surfaces. Subsequently, chlorodimethyl-n-octadecylsilane was chemically adsorbed onto the surface to impart the required hydrophobicity. The remaining hydroxyl groups were grafted with 1,6-diisocyanatohexane. Finally, 2-hydroxy-2-ethylphosphorylcholine was grafted onto the attached isocyanate groups. Dynamic contact angle (DCA) measurement and X-ray photoelectron spectroscopy (XPS) analysis confirmed that the step-by-step modification process was successful. The adsorption of bovine serum albumin and bovine plasma fibrinogen, as well as the adhesion and aggregation of platelets were suppressed with the introduction of phospholipid moieties on the surfaces. This tunable surface may have potential applications in the fields of separation science, tissue engineering, cytobiology, drug delivery and gene therapy.     

Cellular reactions of osteoblast-like cells to a novel nanocomposite membrane for guided bone regeneration

This study investigated the bioactivity and biocompatibility of hydroxyapatite nanoparticles (n-HA)/Polyamide-66 (PA66) nanocomposite membrane and expanded-polytetrafluoroethylene (e-PTFE) membrane (as control) to MG63 osteoblast-like cells. The attachment and proliferation of the cells on the porous surface of nHA/PA66 membrane and the surface of e-PTFE membrane were evaluated by scanning electron microscope (SEM) observation and the MTT assay. The bioactivity of the cells on the surface of the two membranes was evaluated by testing cell viability and alkaline phosphatase (ALP) activities. The results suggested that the bioresponse of MG63 osteoblast-like cells on the porous surface of nHA/PA66 membrane was better than the bioresponse on the opposite surface of e-PTFE membrane. Because of a better cell attachment manner, there is a potential utilization of the guided bone regeneration (GBR) membrane to substitute nHA/PA66 membrane for e-PTFE membrane.     

Microstructure and osteoblast response of gradient bioceramic coating on titanium alloy fabricated by laser cladding

To construct a bioactive interface between metal implant and the surrounding bone tissue, the gradient calcium phosphate bioceramic coating on titanium alloy (Ti-6Al-4V) was designed and fabricated by laser cladding. The results demonstrated that the gradient bioceramic coating was metallurgically bonded to the titanium alloy substrate. The appearance of hydroxyapatite and β-tricalcium phosphate indicated that the bioactive phases were synthesized on the surface of coating. The microhardness gradually decreased from the coating to substrate, which could help stress relaxation between coating and bone tissue. Furthermore, the methyl thiazolyl tetrazolium (MTT) assay of cell proliferation revealed that the laser-cladded bioceramic coating had more favorable osteoblast response compared with the surface of untreated titanium alloy substrate.     

Synthesis and bioactivity of highly ordered TiO2 nanotube arrays

The highly ordered TiO₂ nanotube arrays were fabricated by potentiostatic anodization of Ti foils in fluorinated dimethyl sulfoxide (DMSO). TiO₂ nanotube arrays are formed using a 40 V anodization potential for 24 h, with a length of 12 μm, diameter of 170 nm and aspect ration of about 70. The as-prepared nanotubes are amorphous, but can be crystallized as the heat treatment temperature increases. Anatase phase appears at a temperature of about 300 °C, then transforms to rutile phase at about 600 °C. After heat treatment at 500 °C and soaking in SBF for 14d, a thick apatite layer of about 13 μm covers the whole surface of TiO₂ nanotube arrays, indicating their excellent in vitro bioactivity, which is mainly attributed to their high specific surface area and the anatase phase.     

Characterization and human gingival fibroblasts biocompatibility of hydroxyapatite/PMMA nanocomposites for provisional dental implant restoration

The aim of this study was to determine nHA/PMMA composites (H/P) in an optimal ratio with improved cytocompatibility as well as valid physical properties for provisional dental implant restoration. 20 wt.%, 30 wt.%, 40 wt.% and 50 wt.% H/P were developed and characterized using XPS, bending strength test and SEM. Human gingival fibroblasts cultured in extracts or directly on sample discs were investigated by fluorescent staining and MTT assay. Chemical integration in nHA/PMMA interface was indicated by XPS. Typical fusiform cells with adhesion spots were detected on H/P discs. MTT results also indicated higher cell viability in 30 wt.% and 40 wt.% H/P discs (P < 0.05). We conclude that nHA addition to PMMA enhances cytocompatibility and the optimal nHA/PMMA ratio for provisional fixed crowns (PFC) is 0.4:1.     

Controlling cell-material interactions with polymer nanocomposites by use of surface modifying additives

Polymer nanocomposites (NC) are fabricated by incorporating well dispersed nanoscale particles within a polymer matrix. This study focuses on elastomeric polyurethane (PU) based nanocomposites, containing organically modified silicates (OMS), as bioactive materials. Nanocomposites incorporating chlorhexidine diacetate as an organic modifier (OM) were demonstrated to be antibacterial with a dose dependence related to both the silicate loading and the loading of OM. When the non-antibacterial OM dodecylamine was used, both cell and platelet adhesion were decreased on the nanocomposite surface. These results suggest that OM is released from the polymer and can impact on cell behaviour at the interface. Nanocomposites have potential use as bioactive materials in a range of biomedical applications.     

Enhanced corrosion resistance of Zr coating on biomedical TiNi alloy prepared by plasma immersion ion implantation and deposition

Zirconium film was prepared on TiNi alloy by plasma immersion ion implantation and deposition (PIIID) technique to enhance its corrosion resistance and prolong its working lifetime. The atomic force microscopy (AFM) results show that the film was relatively smooth with the root mean square roughness being 9.166 nm. The X-ray photoelectron spectroscopy (XPS) and X-ray diffraction (XRD) results indicate that the implant element of Zr was oxidation partialness. The potentiodynamic polarization measurements in the Hank's solution at 37 °C show that the corrosion resistance of the alloy was improved by the Zr coating film and the atomic absorption spectrometry (AAS) tests also indicate that Ni ion concentration released from the substrate in the Hank's solution after the polarization test was reduced greatly, in comparison to the unmodified TiNi alloy sample.     

Surface modification of biphasic calcium phosphate bioceramic powders

Biphasic calcium phosphate (BCP)/poly l-lactide (PLLA) biocomposite is proven to be a promising bone graft material or scaffold for bone tissue engineering. To improve the interfacial compatibility of BCP bioceramic with biopolymer-PLLA, BCP powders were surface-modified in different condition to graft polymer groups onto the surface of the BCP powders. l-lactide and l-lactic acid (LA) oligomer were used to modify the BCP surface with stannous octanoate (Sn(Oct)₂) and stannous chloride (SnCl₂) as catalyst, respectively. Results show that the surface modification effect is obvious and the amount of grafted organic group is above 6.5 wt.%. Sn(Oct)₂ and SnCl₂ are the optimal catalysts for the surface grafting reaction of l-lactide and l-LA oligomer, respectively. The surface grafting slightly increase the particle size of BCP powders and reduce the tendency for their agglomeration.     

Modification of medical metals by ion implantation of copper

The effect of copper ion implantation on the antibacterial activity, wear performance and corrosion resistance of medical metals including 317 L of stainless steels, pure titanium, and Ti-Al-Nb alloy was studied in this work. The specimens were implanted with copper ions using a MEVVA source ion implanter with ion doses ranging from 0.5 × 10¹⁷ to 4 × 10¹⁷ ions/cm² at an energy of 80 keV. The antibacterial effect, wear rate, and inflexion potential were measured as a function of ion dose. The results obtained indicate that copper ion implantation improves the antibacterial effect and wear behaviour for all the three medical materials studied. However, corrosion resistance decreases after ion implantation of copper. Experimental results indicate that the antibacterial property and corrosion resistance should be balanced for medical titanium materials. The marked deteriorated corrosion resistance of 317 L suggests that copper implantation may not be an effective method of improving its antibacterial activity.     

Preparation and characterization of the sol-gel nano-bioactive glasses modified by the coupling agent gamma-aminopropyltriethoxysilane

The sol-gel derived bioactive glasses (SBG) have been used in bone-tissue engineering because of their excellent biocompatibility and osteoconductivity. In this study, nano-SBG was successfully achieved through a wet mechanical grinding technique, and to further improve its dispersibility and cells proliferation, a silane coupling agent was coupled onto the surface of nano-SBG. Gamma-aminopropyltriethoxysilane (APTES) was used to the surface modification of the nano-SBG (60 mol%SiO₂, 36 mol%CaO, 4 mol%P₂O₅) by a wet-chemical method in a dynamic inert nitrogen atmosphere. The surface properties of the biomaterials before and after modification were characterized and compared using FTIR and XPS. The characteristic peaks in FTIR spectra indicated that -CH₂CH₃ and -NH₂ groups appeared on the surface of modified nano-SBG, and also, XPS spectra analysis revealed that nitrogen element was detected and carbon concentration increased on the surface of nano-SBG after modification. The above analysis proved that the desired groups of APTES had been covalently bonded onto the surface of nano-SBG.     

Improving the bioactivity of NiTi shape memory alloy by heat and alkali treatment

TiO₂ films were formed on an NiTi alloy surface by heat treatment in air at 600 °C. Heat treated NiTi shape memory alloys were subsequently alkali treated with 1 M, 3 M and 5 M NaOH solutions respectively, to improve their bioactivity. Then treated NiTi samples were soaked in 1.5SBF to evaluate their in vitro performance. The results showed that the 3 M NaOH treatment is the most appropriate method. A large amount of apatite formed within 1 day's soaking in 1.5SBF, after 7 day's soaking TiO₂/HA composite layer formed on the NiTi surface. SEM, XRD, FT-IR and TEM results showed that the morphology and microstructure are similar to the human bone apatite.     

The application with protocatechualdehyde to improve anticoagulant activity and cell affinity of silk fibroin

Protocatechualdehyde (PCA) is one of the effective ingredients extracted from Danshen (Radix Salviae Miltiorrhizae) and was employed to modify the silk fibroin (SF) by graft polymerization and surface adsorption. The surface composition of modified SF was characterized by attenuated total reflectance Fourier-transform infrared (ATR-FTIR), X-ray photoelectron spectroscopy (XPS), and UV spectrophotometer. The anticoagulant activity of modified SF was assessed by in vitro coagulation test and platelet adhesion measurement. The endothelial cell affinity was evaluated by a parallel plate flow chamber. The test results indicated that with the introduction of PCA into SF, the anticoagulant activity has been improved obviously. And the SF surface composition altered by PCA, but did not disturb its β-sheet conformation. Moreover, the adsorbed PCA on SF surface can enhance the endothelial cell affinity.     

Interaction of endothelial cells with biodegradable strontium-doped calcium polyphosphate for bone tissue engineering

Angiogenesis is of great importance in bone tissue engineering, and has gained large attention in the recent 10 years. However, little research has been done on the effect of biodegradable materials, especially their degradation products on the angiogenesis process. Strontium-doped calcium polyphosphate (SCPP) has been proved to be able to promote osteoblasts growth in vitro before. In the present work, the interaction of endothelial cells (ECs) with the scaffold of SCPP was investigated to evaluate its potential influences on angiogenesis. The cell adhesion on SCPP scaffold as well as the angiogenic behaviors including proliferation, migration and tube-like structure (TLS) formation of ECs treated by its degradation products was tested. The results were compared with those of CPP group and physiological saline (negative control). As the results showed, the surface of SCPP could promote the adhesion and spreading of ECs. Ca²⁺ and Pi as well as Sr²⁺ were the main degradation products of SCPP. They did not inhibit but could promote the proliferation of ECs within 90 days. Moreover, they could induce the migration and TLS formation of ECs. Since SCPP bears the ability to improve the adhesion and angiogenic behaviors of endothelial cells, it might benefit angiogenesis and serve as a more promising scaffold for bone tissue engineering application. Besides, this work may provide a new method for in vitro evaluation of biodegradable materials’ potential effects on angiogenesis.     

Inhomogeneity of calcium phosphate coatings deposited by laser ablation at high deposition rate

Calcium phosphate coatings were deposited with a KrF excimer laser onto titanium alloy to study their homogeneity. Deposition was performed at a high deposition rate under a water vapour atmosphere of 45 Pa and at a substrate temperature of 575 °C. Samples were also submitted to annealing under the same conditions of deposition for different times just after deposition. The effects of the annealing were also investigated. The morphology of the coatings was studied by scanning electron microscopy. Their structure and phase distribution was analysed by X-ray diffractometry and infrared and micro-Raman spectroscopies. Besides the non-uniform thickness, the results reveal an inhomogeneity in the spatial distribution of calcium phosphate phases in the coatings. The phase distribution can be almost completely correlated with the deposition rate. High deposition rates (0.5 nm/pulse) occurring in the centre of deposition results in the formation of amorphous calcium phosphate, while lower deposition rates favour the presence of hydroxyapatite and alpha tricalcium phosphate. At intermediate deposition rates, beta tricalcium phosphate is found, probably because the superimposed effect of energetic particles bombardment. The annealing process promotes the crystallisation of the amorphous material. The importance of the deposition rate in the phases obtained is stated after comparing these results with a previous work where homogeneous hydroxyapatite coatings were obtained under the same conditions of laser fluence, temperature and pressure, but at lower deposition rates. Received: 22 November 2001 / Accepted: 12 March 2002 / Published online: 5 July 2002 RID="*" ID="*"Corresponding author. Fax: +34-93/402-1138, E-mail: jmfernandez@fao.ub.es     

In vitro evaluation of bioactivity of CaO-SiO2-P2O5-Na2O-Fe2O3 glasses

Glasses with compositions 41CaO(52 − x)SiO₂4P₂O₅·xFe₂O₃3Na₂O (2 ≤ x ≤ 10 mol.%) were prepared by melt quenching method. Bioactivity of the different glass compositions was studied in vitro by treating them with simulated body fluid (SBF). The glasses treated for various time periods in SBF were evaluated by examining apatite formation on their surface using grazing incidence X-ray diffraction, Fourier transform infrared reflection spectroscopy, scanning electron microscopy and energy dispersive spectroscopy techniques. Increase in bioactivity with increasing iron oxide content was observed. The results have been used to understand the evolution of the apatite surface layer as a function of immersion time in SBF and glass composition.     

Surface morphology of laser tracks used for forming the non-smooth biomimetic unit of 3Cr2W8V steel under different processing parameters

Aiming to form the high quality of non-smooth biomimetic unit, the influence of laser processing parameters (pulse energy, pulse duration, frequency and scanning speed in the present work) on the surface morphology of scanned tracks was studied based on the 3Cr2W8V die steel. The evolution of the surface morphology was explained according to the degree of melting and vaporization of surface material, and the trend of mean surface roughness and maximum peak-to-valley height. Cross-section morphology revealed the significant microstructural characteristic of the laser-treated zone used for forming the functional zone on the biomimetic surface. Results showed that the combination of pulse energy and pulse duration plays a major role in determining the local height difference on the irradiated surface and the occurrence of melting or vaporization. While frequency and scanning speed have a minor effect on the change of the surface morphology, acting mainly by the different overlapping amount and overlapping mode. The mechanisms behind these influences were discussed, and schematic drawings were introduced to describe the mechanisms.     

Tensile property of H13 die steel with convex-shaped biomimetic surface

The H13 steel specimens with non-smooth surface were fabricated by biomimetic method and laser technique, and the effect of these biomimetic surfaces on the tensile properties was investigated. The results indicated that the biomimetic surface has an advantageous effect on improving the tensile properties of H13 steel. As the area ratio occupied by non-smooth units on the biomimetic surface grows to 26.7%, the ultimate tensile strength (UTS) and 0.2% yield strength (YS) of materials linearly increase by about 8.4% and 17.2%, respectively. The elongation to fracture of materials reaches to the peak value of about 41.3% at the point of 17.1% area ratio, and further heightening the area ratio can result in a reduced ductility relative to this peak value. This improvement of tensile properties can be attributed to the combined effects of the microstructure characteristics within the unit zone and the unit-distribution features on the surface. Meanwhile, the regressed relation equations of UTS, YS and elongation regarding the area ratio were obtained via statistical theory. The tests of regression significance showed that the confidence of these equations achieved 99% above.     

A combined finite element and modal decomposition method to study the interaction of Lamb modes with micro-defects

This paper presents a combined finite element and modal decomposition method to study the interaction of Lamb waves with damaged area. The finite element mesh is used to describe the region around the defects. On the contrary to other hybrid models already developed, the interaction between Lamb waves and defects is computed in the temporal domain. Then, the modal decomposition method permits to determine the wave reflected and transmitted by the damaged area. Modal analysis allows also identifying the mode conversions induced by the defects. These numerical results agree with previous finite element results concerning the interaction of Lamb modes with a notch. Experiments, carried out with gauged defects on an aluminum plate, are also compared to numerical predictions to validate the simulation. Compared to classical techniques of simulation, this new method allows us to investigate the interaction of Lamb modes generated at high frequency-thickness product with micro-defects as corrosion pitting.     

Electrochemical oxidation of La2CuO4 thin films grown by molecular beam epitaxy

Thin insulating and c-axis oriented films of La₂CuO₄ are grown using a molecular beam epitaxy technique. Subsequently, these films are oxidized electrochemically using a 1N KOH solution. This approach is used to induce superconductivity, leading to a maximum T_c0 of 31 K,, measured both resistively and inductively. The surface morphology, lattice constants and the resistivity before and after the electrochemical treatment are compared.     

Solar cells with porous silicon: modification of surface-recombination velocity

Laser-induced transient-grating measurements were performed to monitor the influence of porous silicon on the surface recombination of a highly doped n⁺-silicon emitter of solar cells. With this technique, photocarrier diffusion and recombination with a time resolution of some tens of picoseconds can be studied. Using pulses of the second- and third-harmonic radiation from an Nd³⁺:YAG laser (quantum energy 2.34 and 3.51 eV, respectively), two different-depth regions of the emitter were excited. Using a kinetic model, which includes carrier diffusion and recombination at the surface and in the bulk of the emitter, surface-recombination velocities in a series of samples typical for each successive operation of solar-cell technology with different surface-doping level and surface preparation were evaluated. From the analysis, we conclude that porous silicon formed on the emitter passivates the surface of the silicon layer, i.e. reduces the rate of surface recombination at the porous silicon–crystalline silicon interface. Ytterbium as a co-dopant of the emitter increases the surface-recombination velocity. Received: 26 June 2000 / Accepted: 4 December 2000 / Published online: 26 April 2001