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1.
Hydroxyapatite (HA) and fluoridated hydroxyapatite (FHA) coatings were deposited on titanium substrates using an electrochemical technique. Different concentrations of F? ions were incorporated into the apatite structure by adding NaF into the electrolyte. Typical apatite structures were obtained for all the coatings after electrodeposition and subsequent post-treatment, including alkaline immersion and vacuum calcination. The coatings were uniform and dense, with a thickness of ~5 μm. When the F-concentration was higher than 0.012 M in the electrolyte, a saturation of F in the coating occurred and the F/Ca ratio in the coatings became almost constant (F/Ca ratio = 0.125). The FHA coatings showed higher bonding strength and lower dissolution rate than HA coating, particularly for those with a fluoridation level of 0.5–0.625. Compared with pure Ti, FHA and HA coatings exhibited higher biological affinity like cell proliferation and alkaline phosphatase activity. Regarding clinical application, it is suggested that a moderate content of F, such as Ca5(PO4)3(OH)0.375?0.5F0.5?0.625, be most suitable as a compromise among cell attachment, cell proliferation, apatite deposition and dissolution resistance.  相似文献   

2.
Transmission electron microscopy and supporting film analyses are used to investigate the changes in composition, morphology and structure of coatings formed on titanium during DC plasma electrolytic oxidation in a calcium- and phosphorus-containing electrolyte. The coatings are of potential interest as bioactive surfaces. The initial barrier film, of mixed amorphous and nanocrystalline structure, formed below the sparking voltage of 180 V, incorporates small amounts of phosphorus and calcium species, with phosphorus confined to the outer ~63% of the coating thickness. On commencement of sparking, calcium- and phosphorus-rich amorphous material forms at the coating surface, with local heating promoting crystallization in underlying and adjacent anodic titania. The amorphous material thickens with increased treatment time, comprising almost the whole of the ~5.7-μm-thick coating formed at 340 V. At this stage, the coating is ~4.4 times thicker than the oxidized titanium, with a near-surface composition of about 12 at.% Ti, 58 at.% O, 19 at.% P and 11 at.% Ca. Further, the amount of titanium consumed in forming the coating is similar to that calculated from the anodizing charge, although there may be non-Faradaic contributions to the coating growth.  相似文献   

3.
Titanium alloy, Ti6Al4V, is widely used in dental and orthopedic implants. Despite its excellent biocompatibility, Ti6Al4V releases toxic Al and V ions into the surrounding tissue after implantation. In addition, the elastic modulus of Ti6Al4V (~110 GPa) is significantly higher than that of bone (10–40 GPa), leading to a modulus mismatch and consequently implant loosening and deosteointegration. Zeolite coatings are proposed to prevent the release of the toxic ions into human tissue and enhance osteointegration by matching the mechanical properties of bone. Zeolite MFI coatings are successfully synthesized on commercially pure titanium and Ti6Al4V for the first time. The coating shows excellent adhesion by incorporating titanium from the substrate within the zeolite framework. Higher corrosion resistance than the bare titanium alloy is observed in 0.856 M NaCl solution at pHs of 7.0 and 1.0. Zeolite coatings eliminate the release of cytotoxic Al and V ions over a 7 day period. Pluripotent mouse embryonic stem cells show higher adhesion and cell proliferation on the three-dimensional zeolite microstructure surface compared with a two-dimensional glass surface, indicating that the zeolite coatings are highly biocompatible.  相似文献   

4.
Ulvan, extracted from the green algae Ulva lactuca, and chitosan, extracted from Loligo forbesis squid-pen, were carboxymethylated, yielding polysaccharides with an average degree of substitution of ~98% (carboxymethyl ulvan, CMU) and ~87% (carboxymethyl chitosan, N,O-CMC). The carboxymethylation was confirmed by Fourier transform infrared spectroscopy and quantified by conductimetric titration and 1H nuclear magnetic resonance. The average molecular weight increased with the carboxymethylation (chitosan, Mn 145→296 kDa and Mw 227→416 kDa; ulvan, Mn 139→261 kDa and Mw 368→640 kDa), indicating successful chemical modifications. Mixtures of the modified polysaccharides were tested in the formulation of polyacrylic acid-free glass-ionomer bone cements. Mechanical and in vitro bioactivity tests indicate that the inclusion of CMU in the cement formulation, i.e. 0.50:0.50 N,O-CMC:CMU, enhances its mechanical performance (compressive strength 52.4 ± 8.0 MPa and modulus 2.3 ± 0.3 GPa), generates non-cytotoxic cements and induces the diffusion of Ca and/or P-based moieties from the surface to the bulk of the cements.  相似文献   

5.
《Acta biomaterialia》2014,10(5):2282-2289
A nanostructured sodium hydrogen titanate layer ∼1 μm in thickness was initially produced on the surface of titanium metal (Ti) by soaking in NaOH solution. When the metal was subsequently soaked in a mixed solution of CaCl2 and SrCl2, its Na ions were replaced with Ca and Sr ions in an Sr/Ca ratio in the range 0.18–1.62. The metal was then heat-treated at 600 °C to form strontium-containing calcium titanate (SrCT) and rutile on its surface. The treated metal did not form apatite in a simulated body fluid (SBF) even after 7 days. When the metal formed with SrCT was subsequently soaked in water at 80 °C, the treated metal formed bone-like apatite on its surface within 1 day in SBF since the Ca ions were partially replaced with H3O+ ions. However, it released only 0.06 ppm of Sr ions even after 7 days in phosphate-buffered saline. When the metal was soaked after the heat treatment in 1 M SrCl2 solution instead of water, the treated metal released 0.92 ppm of Sr ions within 7 days while maintaining its apatite-forming ability. The Ti formed with this kind of bioactive SrCT layer on its surface is expected to be highly useful for orthopedic and dental implants, since it should be able to promote bone growth by releasing Sr ions and tightly bond to the bone through the apatite formed on its surface.  相似文献   

6.
Magnesium has shown potential application as a bio-absorbable biomaterial, such as for bone screws and plates. In order to improve the surface bioactivity, a calcium phosphate was coated on a magnesium alloy by a phosphating process (Ca–P coating). The surface characterization showed that a porous and netlike CaHPO4·2H2O layer with small amounts of Mg2+ and Zn2+ was formed on the surface of the Mg alloy. Cells L929 showed significantly good adherence and significantly high growth rate and proliferation characteristics on the Ca–P coated magnesium alloy (p < 0.05) in in-vitro cell experiments, demonstrating that the surface cytocompatibility of magnesium was significantly improved by the Ca–P coating. In vivo implantations of the Ca–P coated and the naked alloy rods were carried out to investigate the bone response at the early stage. Both routine pathological examination and immunohistochemical analysis demonstrated that the Ca–P coating provided magnesium with a significantly good surface bioactivity (p < 0.05) and promoted early bone growth at the implant/bone interface. It was suggested that the Ca–P coating might be an effective method to improve the surface bioactivity of magnesium alloy.  相似文献   

7.
Despite the excellent bioactivity of hydroxyapatite (HA) ceramics, poor mechanical strength has limited the applications of these materials primarily to coatings and other non-load-bearing areas as bone grafts. Using synthesized HA nanopowder, dense compacts with grain sizes in the nanometer to micrometer range were processed via microwave sintering between 1000 and 1150 °C for 20 min. Here we demonstrate that the mechanical properties, such as compressive strength, hardness and indentation fracture toughness, of HA compacts increased with a decrease in grain size. HA with 168 ± 86 nm grain size showed the highest compressive strength of 395 ± 42 MPa, hardness of 8.4 ± 0.4 GPa and indentation fracture toughness of 1.9 ± 0.2 MPa m1/2. To study the in vitro biological properties, HA compacts with grain size between 168 nm and 1.16 μm were assessed for in vitro bone cell–material interactions with human osteoblast cell line. Vinculin protein expression for cell attachment and bone cell proliferation using MTT assay showed that surfaces with finer grains provided better bone cell–material interactions than coarse-grained samples. Our results indicate simultaneous improvements in mechanical and biological properties in microwave sintered HA compacts with nanoscale grain size.  相似文献   

8.
In this work, plasma-sprayed nanostructured zirconia coatings stabilized with 3 mol.% yttria (3Y-TZP) were deposited on Ti substrates. The microstructure and phase composition of coatings were characterized using scanning electron microscopy and X-ray diffraction. The in vitro bioactivity of coatings was evaluated by examining the formation of bone-like apatite on its surface in simulated body fluid. MG63 cell lines were cultured on the coating to investigate its cytocompatibility. The crystalline phase of the as-sprayed coating was tetragonal zirconia, and no monoclinic zirconia was detected. The size of the grains on the as-sprayed coating surface was less than 100 nm. The apatite could precipitate on the surface of the coating immersed in simulated body fluid for 28 days while no apatite was formed on the surface of 3Y-TZP ceramic control, indicating that the bioactivity of the coating is superior to the ceramic with the same composition. It also revealed that the polished coating whose nanostructural outmost layer was removed was bioinert, implying the significance of the nanosized grains for its bioactivity. MG63 cells could adhere, grow and proliferate well on the coating surface, indicating that the coating had good cytocompatibility. Phase stability of plasma-sprayed 3Y-TZP coating was evaluated under hydrothermal conditions at 134 °C. It revealed that the plasma-sprayed nanostructured zirconia coating was more sensitive to aging than that of zirconia ceramics.  相似文献   

9.
In the present study, the influence of calcium ion deposition on the apatite-inducing ability of porous titanium(Ti) was investigated in a modified simulated body fluid (m-SBF). Calcium hydroxide (Ca(OH)2) solutions with five degrees of saturation were used to hydrothermally deposit Ca ions on porous Ti with a porosity of 80%. Apatite-inducing ability of the Ca-ion-deposited porous Ti was evaluated by soaking them in m-SBF for up to 14 days. Scanning electron microscopy (SEM) and X-ray diffractometry (XRD) confirmed that a thin layer of calcium titanate (CaTiO3)/calcium oxide (CaO) mixture with a nanostructured porous network was produced on porous Ti substrates after hydrothermal treatment at 200 °C for 8 h. X-ray photoelectron spectroscopy results demonstrated that the content of the Ca ions deposited on Ti and the thickness of the CaTiO3/CaO layer increased with increasing saturation degree of the Ca(OH)2 solution. The thickest (over 10 nm) CaTiO3/CaO layer with the highest Ca content was achieved on the Ti treated in an oversaturated Ca(OH)2 solution (0.2 M). SEM, XRD, transmission electron microscopy and Fourier transformed infrared spectroscopy analysis indicated that the porous Ti samples deposited with the highest content of Ca ions exhibited the best apatite-inducing ability, producing a dense and complete carbonated apatite coating after a 14 day soaking in m-SBF. The present study illustrated the validity of using Ca ion deposition as a pre-treatment to endow desirable apatite-inducing ability of porous Ti for bone tissue engineering applications.  相似文献   

10.
In this study, we report a hybrid organic–inorganic TEOS–MTES (tetraethylorthosilicate–methyltriethoxysilane) sol–gel-made coating as a potential solution to improve the in vivo performance of AISI 316L stainless steel, which is used as permanent bone implant material. These coatings act as barriers for ion migration, promoting the bioactivity of the implant surface. The addition of SiO2 colloidal particles to the TEOS–MTES sol (10 or 30 mol.%) leads to thicker films and also acts as a film reinforcement. Also, the addition of bioactive glass–ceramic particles is considered responsible for enhancing osseointegration. In vitro assays for bioactivity in simulated body fluid showed the presence of crystalline hydroxyapatite (HA) crystals on the surface of the double coating with 10 mol.% SiO2 samples on stainless steel after 30 days of immersion. The HA crystal lattice parameters are slightly different from stoichiometric HA. In vivo implantation experiments were carried out in a rat model to observe the osteointegration of the coated implants. The coatings promote the development of newly formed bone in the periphery of the implant, in both the remodellation zone and the marrow zone. The quality of the newly formed bone was assessed for mechanical and structural integrity by nanoindentation and small-angle X-ray scattering experiments. The different amount of colloidal silica present in the inner layer of the coating slightly affects the material quality of the newly formed bone but the nanoindentation results reveal that the lower amount of silica in the coating leads to mechanical properties similar to cortical bone.  相似文献   

11.
Titanate nanomesh layers were fabricated on Ti-based bulk metallic glass (BMG) to induce bioactivity in the form of apatite-forming ability. Titanate nanomesh layers were prepared by hydrothermal–electrochemical treatment at 90 °C for 2 h, with an aqueous solution of NaOH as an electrolyte. A constant electric current of 0.5 mA cm?2 was applied between the BMG substrate and a Pt electrode acting as the anode and cathode, respectively. A nanomesh layer, consisting of nanowires (~20 nm in diameter) formed on the BMG. An immersion test in simulated body fluid for 12 days revealed that the titanate nanomesh layer on the BMG promoted the growth of bone-like hydroxyapatite.  相似文献   

12.
Electrically polarized bulk sintered hydroxyapatite (HAp) compacts have been shown to accelerate mineralization and bone tissue ingrowth in vivo. In this work, a comprehensive study has been carried out to investigate the influence of surface charge and polarity on in vitro bone cell adhesion, proliferation and differentiation on electrically polarized HAp-coated Ti. Uniform and crack free sol–gel derived HAp coatings of 20 ± 1.38 μm thickness were polarized by application of an external d.c. field of 2.0 kV cm?1 at 400 °C for 1h. In vitro bioactivity of polarized HAp coatings was evaluated by soaking in simulated body fluid, and bone cell–material interactions were studied by culturing with human fetal osteoblast cells (hFOB) for a maximum period of 11 days. Scanning electron microscopic observation showed that accelerated mineralization on negatively charged surfaces favored rapid cell attachment and faster tissue ingrowth over non-polarized HAp coating surfaces, while positive charge on HAp coating surfaces restricted apatite nucleation with limited cellular response. Immunochemistry and confocal microscopy confirmed that the cell adhesion and early stage differentiation were more pronounced on negatively charged coating surfaces as hFOB cells expressed higher vinculin and alkaline phosphatase proteins on negatively charged surface compared to cells grown on all other surfaces. Our results in this study are process independent and potentially applicable to any other commercially available coating techniques.  相似文献   

13.
Zinc-containing apatite layers were successfully formed on commercially available anodically oxidized Ti external fixation rods using ZnCl2-containing supersaturated calcium phosphate solutions. With an increase in concentration of ZnCl2 in the supersaturated calcium phosphate solutions, the amounts of zinc that precipitated on the Ti external fixation rods increased (from 0 to 0.195 ± 0.020 μg cm?2); meanwhile, the amounts of calcium and phosphorus that precipitated on the Ti external fixation rods decreased (from 11.2 ± 1.5 and 4.8 ± 0.5 μg cm?2 to 2.9 ± 1.6 and 1.3 ± 0.9 μg cm?2, respectively). The zinc-containing apatite layers precipitated on the Ti external fixation rods caused a significant increase in fibroblastic proliferation, osteoblastic proliferation and differentiation in vitro. The Ti external fixation rods coated with zinc-containing apatite layers are expected to be more effective in accelerating the tissue regeneration around the surgical site than those coated with an apatite layer.  相似文献   

14.
The mechanical properties and biocompatibility of an Ni-free Zr-based bulk metallic glass (BMG) Zr60.14Cu22.31Fe4.85Al9.7Ag3 were investigated in detail to evaluate its potential as a biomaterial. The BMG was found to have a low Young’s modulus of 82 ± 1.9 GPa, a high strength of 1720 ± 28 MPa and a high fracture toughness of 94 ± 19 MPa m1/2, as well as good fatigue strength over 400 MPa. The corrosion behavior of the alloy was investigated in simulated body fluid (SBF) by electrochemical measurements, which indicates that the Zr-based BMG has a better corrosion resistance than pure Zr and Ti6Al4V. X-ray photoelectron spectroscopy analysis revealed that the passive film formed on the BMG surface is enriched in Al- and Zr-oxides, which could account for the good corrosion resistance of the BMG. On the other hand, metal ion release of the BMG in SBF was determined by inductively coupled plasma mass spectrometry after the BMG was immersed in SBF at 37 °C for 30 days, showing a ppb (ng ml?1) level of metal ion release. The in vitro test via cell culture indicates that the BMG exhibits a cytotoxicity of Grade 0–1, which is as good as Ti6Al4V alloy. Cell adhesion morphological analysis shows that the cells were flattened and well spread out on the surfaces of the BMG, showing that the BMG had good biocompatibility. The combination of good mechanical properties and biocompatibility demonstrates that the Ni-free Zr-based BMG studied in this work is a good candidate for a new type of load-bearing biomedical material.  相似文献   

15.
《Acta biomaterialia》2014,10(5):2187-2199
Thin ultrananocrystalline diamond (UNCD) films were evaluated for use as hermetic and bioinert encapsulating coatings for implantable microchips, where the reaction to UNCD in vitro and in vivo tissue was investigated. Leakage current tests showed that depositing UNCD coatings, which were conformally grown in (1% H2) Ar/CH4 plasma, on microchips rendered the surface electrochemically inactive, i.e. with a very low leakage current density (2.8 × 10−5 A cm−2 at −1 V and 1.9 × 10−3 A cm−2 at ± 5 V) ex vivo. The impact of UNCD with different surface modifications on the growth and activation of macrophages was compared to that of standard-grade polystyrene. Macrophages attached to oxygen-terminated UNCD films down-regulated their production of cytokines and chemokines. Moreover, with UNCD-coated microchips, which were implanted subcutaneously into BALB/c mice for up to 3 months, the tissue reaction and capsule formation was significantly decreased compared to the medical-grade titanium alloy Ti–6Al–4V and bare silicon. Additionally, the leakage current density, elicited by electrochemical activity, on silicon chips encapsulated in oxygen-terminated UNCD coatings remained at the low level of 2.5 × 10−3 A cm−2 at 5 V for up to 3 months in vivo, which is half the level of those encapsulated in hydrogen-terminated UNCD coatings. Thus, controlling the surface properties of UNCDs makes it possible to manipulate the in vivo functionality and stability of implantable devices so as to reduce the host inflammatory response following implantation. These observations suggest that oxygen-terminated UNCDs are promising candidates for use as encapsulating coatings for implantable microelectronic devices.  相似文献   

16.
Mg/Ca (1 wt.%, 5 wt.%, 10 wt.% Ca) composites were prepared from pure magnesium and calcium powders using the powder metallurgy method, aiming to enlarge the addition of Ca content without the formation of Mg2Ca. The microstructures, mechanical properties and cytotoxicities of Mg/Ca composite samples were investigated. The corrosion of Mg/Ca composites in Dulbecco’s modified Eagle’s medium (DMEM) for various immersion intervals was studied by electrochemical impedance spectroscopy measurements and environmental scanning electron microscope, with the concentrations of released Mg and Ca ions in DMEM for various immersion time intervals being measured. It was shown that the main constitutional phases were Mg and Ca, which were uniformly distributed in the Mg matrix. The ultimate tensile strength (UTS) and elongation of experimental composites decreased with increasing Ca content, and the UTS of Mg/1Ca composite was comparable with that of as-extruded Mg–1Ca alloy. The corrosion potential increased with increasing Ca content, whereas the current density and the impedance decreased. It was found that the protective surface film formed quickly at the initial immersion stage. With increasing immersion time, the surface film became compact, and the corrosion rate of Mg/Ca composites slowed down. The surface film consisted mainly of CaCO3, MgCO3·3H2O, HA and Mg(OH)2 after 72 h immersion in DMEM. Mg/1Ca and Mg/5Ca composite extracts had no significant toxicity (p > 0.05) to L-929 cells, whereas Mg/10Ca composite extract induced ~40% reduced cell viability.  相似文献   

17.
Long and uniform HA whiskers with high crystallinity, controlled morphology and high aspect ratio were successfully synthesized by hydrothermal homogeneous precipitation using acetamide. Compared with the additive urea, which is commonly used to raise the pH to drive nucleation and growth of HA crystals, acetamide has a low hydrolysis rate under the required hydrothermal conditions. This allows better and easier control, giving rise to rapid growth of whiskers at a low supersaturation. Whisker length and width were in turn determined by solution conditions, including the concentration of Ca and PO4. Whiskers had a mean length of 60–116 μm and an aspect ratio of 68–103 for starting solutions containing 42–84 mmol L?1 Ca and 25–50 mmol L?1 PO4 with a fixed Ca/P ratio of 1.67. Such whiskers are favourable for their improved bone bonding and bioactivity, as well as their mechanical properties. Whiskers were slightly Ca-deficient with Ca/P = 1.60–1.65, with the preferred direction of growth along the c-axis. Variation of acetamide concentration did not affect the constitution, the crystallinity or the crystal growth habit.  相似文献   

18.
Hydroxyapatite containing levels of titanium (TiHA) of up to 1.6 wt.% has been produced via a chemical co-precipitation route. The distribution of Ti was seen by transmission electron microscopy/energy-dispersive X-ray analysis to be uniform throughout as-prepared nanosized TiHA particles (20 nm × 100 nm). The incorporation of Ti into the HA structure was found to influence the ceramic microstructure on sintering and the grain size was found to decrease from 0.89 μm with HA to 0.63 μm with 0.8 wt.% TiHA (0.8 TiHA) and 0.45 μm with 1.6 wt.% TiHA (1.6 TiHA). Rietveld refinement analysis showed that there was a proportional increase in both the a and c axis with incorporation of Ti into the HA lattice structure, leading to an increase in the cell volume with the addition of Ti. Fourier transform-Raman analysis showed a slight increase in the ratio of O–H/P–O peaks on TiHA, in comparison with HA. A bone-like apatite layer was formed on the surface of TiHA after immersion in simulated body fluid for 3 days, which demonstrated the high in vitro bioactivity of TiHA. In vitro culture with primary human osteoblast (HOB) cells revealed that TiHA was able to support the growth and proliferation of HOB cells in vitro, with a significantly higher cell activity being observed on 0.8 TiHA after 7 days of culture in comparison with that on HA. Well-organized actin cytoskeletal protein was developed after 1 day of culture, and an increase in cell filopodia (attachment) was observed on TiHA sample surfaces. The results indicate that TiHA has great potential for biomedical applications.  相似文献   

19.
We have demonstrated the successful production of titanium phosphate glass microspheres in the size range of ~10–200 μm using an inexpensive, efficient, easily scalable process and assessed their use in bone tissue engineering applications. Glasses of the following compositions were prepared by melt-quench techniques: 0.5P2O5–0.4CaO–(0.1 ? x)Na2O–xTiO2, where x = 0.03, 0.05 and 0.07 mol fraction (denoted as Ti3, Ti5 and Ti7 respectively). Several characterization studies such as differential thermal analysis, degradation (performed using a novel time lapse imaging technique) and pH and ion release measurements revealed significant densification of the glass structure with increased incorporation of TiO2 in the glass from 3 to 5 mol.%, although further TiO2 incorporation up to 7 mol.% did not affect the glass structure to the same extent. Cell culture studies performed using MG63 cells over a 7-day period clearly showed the ability of the microspheres to provide a stable surface for cell attachment, growth and proliferation. Taken together, the results confirm that 5 mol.% TiO2 glass microspheres, on account of their relative ease of preparation and favourable biocompatibility, are worthy candidates for use as substrate materials in bone tissue engineering applications.  相似文献   

20.
Silicon nitride (Si3N4) is an industrial ceramic used in spinal fusion and maxillofacial reconstruction. Maximizing bone formation and minimizing bacterial infection are desirable attributes in orthopedic implants designed to adhere to living bone. This study has compared these attributes of Si3N4 implants with implants made from two other orthopedic biomaterials, i.e. poly(ether ether ketone) (PEEK) and titanium (Ti). Dense implants made of Si3N4, PEEK, or Ti were surgically implanted into matching rat calvarial defects. Bacterial infection was induced with an injection of 1 × 104 Staphylococcus epidermidis. Control animals received saline only. On 3, 7, and 14 days, and 3 months post-surgery four rats per time period and material were killed, and calvariae were examined to quantify new bone formation and the presence or absence of bacteria. Quantitative evaluation of osteointegration to adjacent bone was done by measuring the resistance to implant push-out (n = 8 rats each for Ti and PEEK, and n = 16 rats for Si3N4). Three months after surgery in the absence of bacterial injection new bone formation around Si3N4 was ~69%, compared with 24% and 36% for PEEK and Ti, respectively. In the presence of bacteria new bone formation for Si3N4, Ti, and PEEK was 41%, 26%, and 21%, respectively. Live bacteria were identified around PEEK (88%) and Ti (21%) implants, whereas none were present adjacent to Si3N4. Push-out strength testing demonstrated statistically superior bone growth onto Si3N4 compared with Ti and PEEK. Si3N4 bioceramic implants demonstrated superior new bone formation and resistance to bacterial infection compared with Ti and PEEK.  相似文献   

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