含氟、鋅、銀的羥基磷灰石涂層的制備及其生物學(xué)效應(yīng)的研究
發(fā)布時間：2019-03-21 17:41
【摘要】：生物材料是最具發(fā)展?jié)摿Φ牟牧?其中羥基磷灰石(Ca10(PO4)6(OH)2HA)以其優(yōu)良的生物相容性和分子結(jié)構(gòu)與人體骨組織分子結(jié)構(gòu)高度相似性成為最具有代表性的骨修復(fù)和骨替代材料,常被用于醫(yī)用金屬材料的表面改性涂層[1]。而在眾多的金屬材料中,鈦合金以其優(yōu)良的抗腐蝕性能和力學(xué)性能,已經(jīng)得到了廣泛的臨床應(yīng)用,如Ti6A14V、Ti6A17Nb等常被應(yīng)用于人體硬組織植入物如人工關(guān)節(jié)、骨折固定器等領(lǐng)域[2、3]。因此目前研究最多的就是將HA以薄膜的形式涂到鈦合金表面,制備出兼具有生物活性,而且力學(xué)性能和抗腐蝕性能優(yōu)良的新型材料[4]。 但新型材料在實際的運用中出現(xiàn)了一系列新的問題。比如羥基磷灰石在人體內(nèi)的降解速率太快[5],導(dǎo)致其在體內(nèi)過早失效；部分植入材料和骨替代材料術(shù)后患者出現(xiàn)感染癥狀,而導(dǎo)致手術(shù)失敗。通過添加部分微量元素,可以在很大程度上改善上述缺陷。加入微量元素氟,以氟替代羥基磷灰石中的羥基,可以在很大程度上降低材料的溶解度,延長材料使用壽命；加入微量元素銀,以銀替代小部分羥基磷灰石的鈣,可以提高材料的抗菌性能,降低術(shù)后患者的感染風(fēng)險；另外鋅元素的加入對成骨細胞的增殖有直接刺激作用,同時對破骨細胞有一定的抑制作用,可以提高羥基磷灰石的生物活性。因此,同時將三種元素加入到羥基磷灰石中,制備出一種新型的生物材料,有著良好的應(yīng)用前景和實際意義。 通過查閱大量文獻和相關(guān)專業(yè)的資料的基礎(chǔ)上,最終確定以HPF6、AgN03和Zn(NO3)2·6H2O作為氟引入劑和銀、鋅的添加劑。將一定量的Ca(NO3)2和P205分別溶于乙醇中經(jīng)攪拌后充分溶解。制備出Ca(NO3)2和P205的乙醇溶液后,將兩種溶液按照一定的比例混合。然后將三種添加劑按照嚴格的順序加入上述混合液中,回流24小時后形成涂膜液,采用浸漬-提拉技術(shù),在鈦合金基板上涂覆一層有特定氟、鋅、銀含量的羥基磷灰石薄膜,以滿足理想生物材料的需求。 本論文在研究含三種元素的羥基磷灰石(X-HA)的薄膜的同時,對含氟羥基磷灰石(FHA)、載鋅羥基磷灰石(Zn-HA)、載銀羥基磷灰石(Ag-HA)的制備和相關(guān)性能也做了一定的研究。 本實驗采用XRD、XPS、SEM等技術(shù)對所有制備的薄膜材料進行了薄膜晶相組成、表面形貌以及微量元素的加入對HA的影響和微量元素相互之間的影響進行了分析。用模擬體液浸泡來觀察新材料的抗溶解性能、用MTT比色法測定新材料對成骨細胞增殖的刺激作用、用材料對大腸埃希菌的抗菌性測定新材料的抗菌性能。 本論文獲得的具體結(jié)果如下： 1)通過溶膠-凝膠法能夠成功制備出理想的新型生物材料X-HA。 2)微量添加劑的加入并未影響到HA分子的形成。 3)氟離子成功進入到HA分子中取代了羥基的位置,鋅離子和銀離子部 分進入到HA分子中取代了HA分子中鈣離子的位置。 4)新材料中銀離子、鋅離子的加入并未影響新材料的抗溶解性能。 5)新材料中鋅離子、氟離子的加入并未影響到新材料的抗菌性能。 6)新材料的刺激成骨細胞增殖作用受到一定影響,但是較純HA,還是有明顯的改進。
[Abstract]:The biological material is the most promising material, in which the hydroxyapatite (Ca10 (PO4)6 (OH) 2HA) is the most representative bone repair and bone substitute material with its excellent biocompatibility and molecular structure and the molecular structure of human bone tissue. A surface-modified coating[1], which is often used for medical metallic materials. In many metal materials, titanium alloy has been widely used in the fields of hard tissue implants such as artificial joint and fracture fixer, such as Ti6A14V, Ti6A17Nb, etc. Therefore, at most, the HA is applied to the surface of the titanium alloy in the form of a thin film, and the novel material[4] with excellent biological activity and excellent mechanical property and corrosion resistance is prepared. But the new material has a series of new questions in the practical application Problems. For example, the rate of degradation of the hydroxyapatite in the human body is too fast[5], resulting in premature failure in the body, partial implantation of the material and the presence of symptoms of infection in the patient after the replacement of the bone, leading to surgical loss by adding some of the trace elements, it is possible to improve the above-mentioned deficiency to a large extent A trace element fluorine is added to replace the hydroxyl in the hydroxyapatite, so that the solubility of the material can be greatly reduced, the service life of the material is prolonged, the trace element silver is added, the calcium of the small-part hydroxyapatite is replaced with silver, and the antibacterial property of the material can be improved. The addition of the zinc element has direct stimulation to the proliferation of the osteoblast, and at the same time, the osteoclast has a certain inhibition effect, and the biological activity of the hydroxyapatite can be improved. Therefore, three elements are added into the hydroxyapatite, a novel biological material is prepared, and the novel biological material has good application prospect and practical meaning. It is defined that HPF6, AgN03 and Zn (NO3) 2.6H2O are used as the fluorine-introducing agent and the silver and the zinc on the basis of consulting a large number of documents and relevant professional data. adding a certain amount of Ca (NO3)2 and P205 in ethanol, stirring, and charging; And dissolving. After the ethanol solution of Ca (NO3)2 and P205 is prepared, the two solutions are mixed according to a certain ratio. mixing, adding the three additives into the mixed solution in a strict sequence, refluxing for 24 hours to form a coating solution, and coating a layer of the hydroxyapatite film with a specific fluorine, zinc and silver content on the titanium alloy substrate to meet the ideal biological material by adopting the dipping-pulling technology The preparation and related properties of hydroxyapatite (HA), zinc-loaded hydroxyapatite (Zn-HA) and silver-loaded hydroxyapatite (Ag-HA) were also studied. The film phase composition, surface morphology and trace element addition to HA and the effect of trace elements on HA were studied by XRD, XPS and SEM. The effect of the new material on the proliferation of the osteoblast was measured by means of the MTT colorimetric method, and the antibacterial activity of the new material was determined by MTT colorimetric method. The antibacterial properties of the material. The specific results obtained are as follows:1) It can be successfully prepared by the sol-gel method A new type of biological material X-HA. the in did not affect the formation of the HA molecule.3) The fluoride ion was successfully removed from the HA molecule the position of the hydroxyl group, the zinc ion and the silver ion part enter the HA, in that molecule, the position of the calcium ion in the HA molecule is replace, and 4) the silver ion in the new material, The addition of zinc ions does not affect the anti-dissolution performance of the new material. The addition of fluorine ions does not affect the antibacterial performance of the new material.6) The stimulation of the new material stimulates the proliferation of the osteoblast.
【學(xué)位授予單位】：蘭州大學(xué)
【學(xué)位級別】：碩士
【學(xué)位授予年份】：2012
【分類號】：R318.08
本文編號：2445165
[Abstract]:The biological material is the most promising material, in which the hydroxyapatite (Ca10 (PO4)6 (OH) 2HA) is the most representative bone repair and bone substitute material with its excellent biocompatibility and molecular structure and the molecular structure of human bone tissue. A surface-modified coating[1], which is often used for medical metallic materials. In many metal materials, titanium alloy has been widely used in the fields of hard tissue implants such as artificial joint and fracture fixer, such as Ti6A14V, Ti6A17Nb, etc. Therefore, at most, the HA is applied to the surface of the titanium alloy in the form of a thin film, and the novel material[4] with excellent biological activity and excellent mechanical property and corrosion resistance is prepared. But the new material has a series of new questions in the practical application Problems. For example, the rate of degradation of the hydroxyapatite in the human body is too fast[5], resulting in premature failure in the body, partial implantation of the material and the presence of symptoms of infection in the patient after the replacement of the bone, leading to surgical loss by adding some of the trace elements, it is possible to improve the above-mentioned deficiency to a large extent A trace element fluorine is added to replace the hydroxyl in the hydroxyapatite, so that the solubility of the material can be greatly reduced, the service life of the material is prolonged, the trace element silver is added, the calcium of the small-part hydroxyapatite is replaced with silver, and the antibacterial property of the material can be improved. The addition of the zinc element has direct stimulation to the proliferation of the osteoblast, and at the same time, the osteoclast has a certain inhibition effect, and the biological activity of the hydroxyapatite can be improved. Therefore, three elements are added into the hydroxyapatite, a novel biological material is prepared, and the novel biological material has good application prospect and practical meaning. It is defined that HPF6, AgN03 and Zn (NO3) 2.6H2O are used as the fluorine-introducing agent and the silver and the zinc on the basis of consulting a large number of documents and relevant professional data. adding a certain amount of Ca (NO3)2 and P205 in ethanol, stirring, and charging; And dissolving. After the ethanol solution of Ca (NO3)2 and P205 is prepared, the two solutions are mixed according to a certain ratio. mixing, adding the three additives into the mixed solution in a strict sequence, refluxing for 24 hours to form a coating solution, and coating a layer of the hydroxyapatite film with a specific fluorine, zinc and silver content on the titanium alloy substrate to meet the ideal biological material by adopting the dipping-pulling technology The preparation and related properties of hydroxyapatite (HA), zinc-loaded hydroxyapatite (Zn-HA) and silver-loaded hydroxyapatite (Ag-HA) were also studied. The film phase composition, surface morphology and trace element addition to HA and the effect of trace elements on HA were studied by XRD, XPS and SEM. The effect of the new material on the proliferation of the osteoblast was measured by means of the MTT colorimetric method, and the antibacterial activity of the new material was determined by MTT colorimetric method. The antibacterial properties of the material. The specific results obtained are as follows:1) It can be successfully prepared by the sol-gel method A new type of biological material X-HA. the in did not affect the formation of the HA molecule.3) The fluoride ion was successfully removed from the HA molecule the position of the hydroxyl group, the zinc ion and the silver ion part enter the HA, in that molecule, the position of the calcium ion in the HA molecule is replace, and 4) the silver ion in the new material, The addition of zinc ions does not affect the anti-dissolution performance of the new material. The addition of fluorine ions does not affect the antibacterial performance of the new material.6) The stimulation of the new material stimulates the proliferation of the osteoblast.
【學(xué)位授予單位】：蘭州大學(xué)
【學(xué)位級別】：碩士
【學(xué)位授予年份】：2012
【分類號】：R318.08
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