本文選題：鈦材 + 表面改性��； 參考：《重慶大學(xué)》2012年博士論文

【摘要】：生物材料的表面拓?fù)浣Y(jié)構(gòu)和化學(xué)成分在調(diào)節(jié)蛋白質(zhì)吸附、細(xì)胞粘附、遷移、鋪展、增殖和分化等生物學(xué)行為中起著至關(guān)重要的作用。隨著微/納米技術(shù)的快速發(fā)展，通過在材料表面構(gòu)建微/納米結(jié)構(gòu)來調(diào)控相關(guān)生物學(xué)行為被廣泛研究。同時(shí)，從仿生學(xué)角度出發(fā)，在生物醫(yī)用材料表面構(gòu)建微/納復(fù)合結(jié)構(gòu)可以達(dá)到與骨組織機(jī)械鎖合的目的。 由于其優(yōu)越的理化性能，鈦及鈦合金已被廣泛應(yīng)用為骨科、牙科及心血管支架等植入體。然而，，鈦材表面生物惰性，無法與周邊骨組織形成有效的骨整合。因此，改善鈦植入體表面性能具有重大臨床應(yīng)用的現(xiàn)實(shí)意義。適宜的表面改性不但可以保留鈦材優(yōu)良的力學(xué)性能，而且可以根據(jù)特定臨床應(yīng)用需求而改善相關(guān)性質(zhì)，如生物相容性、骨整合能力、抗細(xì)菌感染和抗癌等性質(zhì)。本論文主要研究鈦材表面微納米結(jié)構(gòu)的構(gòu)建、改性及其生物學(xué)評(píng)價(jià)，為鈦材在臨床骨科應(yīng)用提供理論基礎(chǔ)。本論文的主要研究?jī)?nèi)容和結(jié)論包括： 1.陽極氧化法制備二氧化鈦納米管及機(jī)理研究 本文利用陽極氧化法在鈦材表面原位構(gòu)建了不同管徑的二氧化鈦納米管，并對(duì)二氧化鈦納米管的形成機(jī)理進(jìn)行了研究。首先，我們研究了不同氟電解液對(duì)二氧化鈦納米管形成的影響，結(jié)果表明0.27摩爾/升氟化銨丙三醇水溶液（丙三醇/水=1:1，體積比）作為電解液可以制備尺度可控且高度有序的二氧化鈦納米管；其次，我們研究了0.27摩爾/升氟化銨丙三醇/水電解液中水含量對(duì)二氧化鈦納米管形成的影響，結(jié)果表明該電解液體系中水的含量對(duì)二氧化鈦納米管的形成有重大影響；最后，本文以0.27摩爾/升氟化銨丙三醇水溶液（丙三醇/水=1:1，體積比）作為電解液研究了不同陽極氧化電壓（10-35伏）對(duì)二氧化鈦納米管管徑的影響，結(jié)果表明納米管的管徑隨著陽極氧化電壓的增加而增大，制備了不同管徑的系列二氧化鈦納米管（27-110納米）。當(dāng)電壓增加到35伏時(shí)，在該電解液條件下無法形成高度有序的二氧化鈦納米管。 2.鈦材表面微/納復(fù)合結(jié)構(gòu)對(duì)骨髓間充質(zhì)干細(xì)胞分化的影響 為了研究鈦材表面微/納復(fù)合結(jié)構(gòu)對(duì)骨髓間充質(zhì)干細(xì)胞分化的影響，本文通過雙酸腐蝕和陽極氧化法在鈦材表面構(gòu)建了三種不同結(jié)構(gòu)：微米結(jié)構(gòu)、二氧化鈦納米管結(jié)構(gòu)和微/納復(fù)合結(jié)構(gòu)。分別以場(chǎng)發(fā)射掃描電子顯微鏡和接觸角測(cè)量?jī)x對(duì)材料進(jìn)行了表征。在體外研究了不同結(jié)構(gòu)對(duì)骨髓間充質(zhì)干細(xì)胞增殖和分化的影響。結(jié)果表明：與未處理的鈦材相比，具有微/納復(fù)合結(jié)構(gòu)的鈦材提高了骨髓間充質(zhì)干細(xì)胞的礦化和堿性磷酸酶的分泌。更為重要的是，骨鈣素和骨橋素的表達(dá)證明了微/納復(fù)合結(jié)構(gòu)的鈦材在誘導(dǎo)骨髓間充質(zhì)干細(xì)胞分化方面具有較大的潛力。本研究為提高鈦植入體的骨整合性提供了一種的潛在選擇。 3.具有長(zhǎng)效抗菌性能和良好生物相容性的鈦材納米結(jié)構(gòu)的構(gòu)建 為研發(fā)具有長(zhǎng)效抗菌性能的納米結(jié)構(gòu)化鈦植入體，本文將3-（三甲氧基硅基）丙基-二甲基十八烷基氯化銨（季銨鹽）接枝到銀沉積的二氧化鈦納米管上。利用加載X射線能譜的場(chǎng)發(fā)射掃描電子顯微鏡、傅里葉變換紅外分光光度計(jì)、薄膜X射線衍射儀以及接觸角測(cè)量?jī)x分別對(duì)材料進(jìn)行了表征。結(jié)果表明，我們成功地制備了季銨鹽修飾的銀納米顆粒加載的二氧化鈦納米管納米結(jié)構(gòu)化鈦材。利用大腸桿菌抑菌圈和抗菌率實(shí)驗(yàn)檢測(cè)了該材料的抗菌性能，并通過體外細(xì)胞實(shí)驗(yàn)評(píng)價(jià)了材料的細(xì)胞毒性。結(jié)果表明，季銨鹽修飾的銀納米顆粒加載的二氧化鈦納米管納米結(jié)構(gòu)化鈦材表現(xiàn)出了長(zhǎng)效抗菌性能及良好的生物相容性。本研究為我們提供了一種有發(fā)展前景的制備抗菌鈦基植入體的方法。 4.兼具抗癌和抗菌性能的鈦材納米結(jié)構(gòu)的構(gòu)建 為研發(fā)具有抗癌和抗菌性能的納米結(jié)構(gòu)化鈦植入體，本文首先通過陽極氧化法在鈦材表面制備二氧化鈦納米管，然后將硒電沉積到二氧化鈦納米管中，最后用旋轉(zhuǎn)涂布技術(shù)涂覆多層殼聚糖。利用配備有X射線能譜的場(chǎng)發(fā)射掃描電子顯微鏡和接觸角測(cè)量?jī)x分別對(duì)材料進(jìn)行了表征。結(jié)果表明，我們成功地制備了殼聚糖多層修飾的載硒二氧化鈦納米管納米結(jié)構(gòu)化鈦材。進(jìn)而，以該基材體外研究其對(duì)成骨細(xì)胞與骨癌細(xì)胞生長(zhǎng)的影響。結(jié)果表明，該殼聚糖多層修飾的載硒二氧化鈦納米管納米結(jié)構(gòu)化鈦材有促進(jìn)成骨細(xì)胞生長(zhǎng)同時(shí)抑制骨癌細(xì)胞生長(zhǎng)的巨大潛力。通過大腸桿菌的抗菌率實(shí)驗(yàn)檢測(cè)材料的抗菌性能。結(jié)果表明，殼聚糖多層修飾的載硒二氧化鈦納米管納米結(jié)構(gòu)化鈦材具有良好的抗菌性能。本文提供了一種制備臨床醫(yī)用抗癌抗菌鈦植入體的新方法。 5.不同拋光鈦材表面類金剛石薄膜的制備及細(xì)胞/血液相容性評(píng)價(jià) 為提高鈦材植入體的細(xì)胞相容性和血液相容性，本文首先分別用機(jī)械拋光、化學(xué)拋光和電化學(xué)拋光法對(duì)鈦材表面進(jìn)行處理，然后以磁控濺射法在經(jīng)不同拋光處理的鈦材表面制備類金剛石薄膜。利用場(chǎng)發(fā)射掃描電子顯微鏡和原子力顯微鏡分別對(duì)鈦材表面拓?fù)浣Y(jié)構(gòu)和表面粗糙度進(jìn)行了表征，并通過拉曼光譜研究了類金剛石薄膜的結(jié)構(gòu)。結(jié)果表明，我們成功地構(gòu)建了系列類金剛石薄膜沉積的不同粗糙度的鈦材。利用體外成骨細(xì)胞活性和細(xì)胞增殖實(shí)驗(yàn)評(píng)價(jià)了材料的細(xì)胞相容性。同時(shí)，通過血小板粘附和血溶率實(shí)驗(yàn)檢測(cè)了材料的血液相容性。體外成骨細(xì)胞實(shí)驗(yàn)結(jié)果表明，具有相對(duì)粗糙表面的鈦材表面可促進(jìn)細(xì)胞功能，如細(xì)胞活性和細(xì)胞增殖。更為重要的是，濺射了類金剛石薄膜的鈦材相比未濺射類金剛石薄膜的鈦材顯示出了良好的血液相容性。結(jié)合細(xì)胞實(shí)驗(yàn)和血液相容性實(shí)驗(yàn)的結(jié)果發(fā)現(xiàn)，以化學(xué)及電化學(xué)拋光并沉積類金剛石薄膜的兩種材料同時(shí)顯示出了良好的細(xì)胞相容性和血液相容性。
[Abstract]:The surface topology and chemical composition of biomaterials play an important role in regulating biological behaviors such as protein adsorption, cell adhesion, migration, spreading, proliferation and differentiation. With the rapid development of micro / nano technology, the construction of micro / nano structures on the surface of materials has been widely studied. From the perspective of bionics, the construction of micro / nano composite structure on the surface of biomedical materials can achieve mechanical locking with bone tissue.
Because of its excellent physical and chemical properties, titanium and titanium alloys have been widely used as an implant in the Department of orthopedics, dental and cardiovascular stents. However, the surface inertness of the titanium material can not form an effective bone integration with the surrounding bone tissue. Therefore, it is of great significance to improve the surface properties of the titanium implants. The suitable surface modification is not only possible. To retain the excellent mechanical properties of titanium materials, and to improve the related properties according to the specific clinical application requirements, such as biocompatibility, bone integration, anti bacterial infection and anticancer. This paper mainly studies the construction, modification and bioevaluation of the micro and nano structure on the surface of titanium material, providing a theory for the application of titanium in clinical department of orthopedics. The main contents and conclusions of this paper include:
Preparation and mechanism of titanium dioxide nanotubes by 1. anodization
In this paper, titanium dioxide nanotubes with different pipe diameters were constructed on the surface of titanium by anodizing, and the formation mechanism of titanium dioxide nanotubes was studied. First, we studied the effect of different fluorine electrolyte on the formation of titanium dioxide nanotube. The results showed that 0.27 mole / liter ammonium fluoride aqueous solution (glycerol / water) =1:1, volume ratio) can be used as electrolyte to prepare scale controlled and highly ordered titanium dioxide nanotubes. Secondly, we studied the effect of water content on the formation of titanium dioxide nanotubes in 0.27 mole / HCF / hydroelectric solution. The results show that the content of water in this electrolyte system is heavy on the formation of titanium dioxide nanotubes. In the end, the effect of different anodic oxidation voltage (10-35 volts) on the tube diameter of TiO2 nanotube was studied with 0.27 mole / 0.27 HCF (10-35 volt / water =1:1, volume ratio). The results showed that the tube diameter increased with the increase of the voltage of the tube, and the series of tube diameters were prepared. Titania nanotubes (27-110 nm) can not form highly ordered titania nanotubes when the voltage increases to 35 volts.
Effect of surface micro / nano composite structure of titanium 2. on differentiation of bone marrow mesenchymal stem cells
In order to study the effect of micro / nano composite structure on the differentiation of bone marrow mesenchymal stem cells (MSCs), three different structures, microstructures, titanium dioxide nanotube structures and micro / nano composite structures were constructed on the surface of titanium by diacid corrosion and anodic oxidation. The field emission scanning electron microscope and contact angle measuring instrument were used respectively. The material was characterized. The effects of different structures on the proliferation and differentiation of bone marrow mesenchymal stem cells were investigated in vitro. The results showed that the mineralization and alkaline phosphatase secretion of bone marrow mesenchymal stem cells were improved by the titanium materials with micro / nano composite structure compared with untreated titanium materials. It is proved that the titanium materials with micro / nano composite structure have great potential in inducing bone marrow mesenchymal stem cells differentiation. This study provides a potential choice for improving the bone integration of titanium implants.
3. construction of titanium nanostructures with long-acting antibacterial properties and good biocompatibility
In order to develop a nano structured titanium implant with long-acting antibacterial properties, the 3- (trimethoxy silicyl) propyl - two methyl eighteen alkyl ammonium chloride (quaternary ammonium salt) was grafted onto silver coated titanium dioxide nanotubes. The field emission scanning electron microscopy, Fourier transform infrared spectrophotometer, and X ray film were used to load the X ray energy spectrum. The material was characterized by the diffractometer and the contact angle measuring instrument. The results showed that we successfully prepared the nanoscale titanium dioxide nanotube loaded with quaternary ammonium modified silver nanoparticles. The antibacterial properties of the material were detected by the bacteriostasis circle and the antibacterial rate of Escherichia coli, and the results were evaluated by the cell test in vitro. The results showed that the quaternary ammonium modified silver nanoparticles loaded with TiO 2 nanotube nanostructured titanium showed long effective antibacterial properties and good biocompatibility. This study provides a promising method for preparing antibacterial titanium based implant.
4. construction of titanium nanostructures with both anti-cancer and antibacterial properties
In order to develop nanostructured titanium implants with anti-cancer and antibacterial properties, titanium dioxide nanotubes were prepared by anodic oxidation on the surface of titanium. Then selenium was deposited into titanium dioxide nanotubes. Finally, the multilayer chitosan was coated with rotating coating technology. The field emission scanning electron microscopy with X ray energy spectrum was used. The material was characterized by the mirror and the contact angle measuring instrument. The results showed that we successfully prepared the chitosan multilayer modified titanium dioxide nanotube nanostructured titanium material. In addition, the effect of the substrate on the growth of osteoblasts and bone cancer cells was studied in vitro. The results showed that the chitosan multilayer modified selenium loaded two oxygen was used. The titania nanotube nanostructured titanium materials have great potential to promote osteoblast growth and inhibit the growth of bone cancer cells. The antibacterial properties of the materials are detected by the antibacterial rate test of Escherichia coli. The results show that the chitosan multilayer modified titanium dioxide nanotube nanostructured titanium materials have good antibacterial properties. A new method for preparing clinical medical anticancer antibacterial titanium implants is presented.
Preparation of 5. diamond-like carbon films on different polished titanium surfaces and evaluation of cell / blood compatibility
In order to improve the cellular compatibility and blood compatibility of the titanium implants, the surface of the titanium material was treated by mechanical polishing, chemical polishing and electrochemical polishing, and the diamond like films were prepared by magnetron sputtering on the surface of different polishing titanium materials. The field emission scanning electron microscope and atomic force microscopy were used. The surface topology and surface roughness of the titanium surface were characterized by microscope, and the structure of the diamond like film was studied by Raman spectroscopy. The results showed that we successfully constructed a series of titanium materials with different roughness deposited by a series of diamond like films. The cells were used to evaluate the cell viability and cell proliferation in vitro. At the same time, the blood compatibility of the material was detected by platelet adhesion and blood solubility test. In vitro osteoblast experimental results showed that the surface of the titanium material with relatively rough surface could promote cell function, such as cell activity and cell proliferation. The titanium materials of the stone film showed good blood compatibility. The results of cell experiments and blood compatibility experiments showed that two materials with chemical and electrochemical polishing and deposition of diamond like films showed good cytocompatibility and blood compatibility.

【學(xué)位授予單位】：重慶大學(xué)
【學(xué)位級(jí)別】：博士
【學(xué)位授予年份】：2012
【分類號(hào)】：R318.08;TB383.1

【相似文獻(xiàn)】

相關(guān)期刊論文 前10條

1 鮑曉;肖衍宇;牛江秀;平其能;;生物黏附性環(huán)孢素納米脂質(zhì)載體的制備及其兔淚液消除動(dòng)力學(xué)[J];中國(guó)新藥與臨床雜志;2011年07期

2 ;[J];;年期

3 ;[J];;年期

4 ;[J];;年期

5 ;[J];;年期

6 ;[J];;年期

7 ;[J];;年期

8 ;[J];;年期

9 ;[J];;年期

10 ;[J];;年期

相關(guān)會(huì)議論文 前10條

1 劉剛;趙江;;納米結(jié)構(gòu)化三相接觸線的新效應(yīng)[A];中國(guó)化學(xué)會(huì)第二十五屆學(xué)術(shù)年會(huì)論文摘要集（上冊(cè)）[C];2006年

2 江雷;;仿生智能多尺度界面材料[A];中國(guó)化學(xué)會(huì)第28屆學(xué)術(shù)年會(huì)第4分會(huì)場(chǎng)摘要集[C];2012年

3 王菲;梁金生;湯慶國(guó);;海泡石環(huán)境礦物材料的納米結(jié)構(gòu)及應(yīng)用[A];第七屆中國(guó)功能材料及其應(yīng)用學(xué)術(shù)會(huì)議論文集（第7分冊(cè)）[C];2010年

4 李素梅;劉文彬;李常亮;;納米結(jié)構(gòu)二氧化錳的合成及其對(duì)持久性有機(jī)污染物熱降解的研究[A];持久性有機(jī)污染物論壇2011暨第六屆持久性有機(jī)污染物全國(guó)學(xué)術(shù)研討會(huì)論文集[C];2011年

5 楊建輝;王海水;張洪杰;逯樂慧;施偉東;;貴金屬(Au、Pt、Pd)空心納米結(jié)構(gòu)的研究[A];中國(guó)化學(xué)會(huì)第十屆膠體與界面化學(xué)會(huì)議論文摘要集[C];2004年

6 楊策;曾瑤;吳佳佳;侯仰龍;;Fe_3O_4各向異性納米結(jié)構(gòu)的控制合成及其相關(guān)性質(zhì)[A];2011中國(guó)材料研討會(huì)論文摘要集[C];2011年

7 黃逸凡;朱紅平;趙劉斌;吳德印;任斌;田中群;;金、銀納米結(jié)構(gòu)上的對(duì)巰基苯胺的表面增強(qiáng)拉曼光譜研究[A];第十六屆全國(guó)光散射學(xué)術(shù)會(huì)議論文摘要集[C];2011年

8 侯建國(guó);;納米結(jié)構(gòu)與性能調(diào)控[A];中國(guó)化學(xué)會(huì)第二十四屆學(xué)術(shù)年會(huì)論文摘要集[C];2004年

9 賈薇娜;賈博祥;曲鳳玉;武祥;;形貌可控的硫化鋅納米結(jié)構(gòu)自組裝及其黃光發(fā)射和疏水性質(zhì)[A];中國(guó)化學(xué)會(huì)第28屆學(xué)術(shù)年會(huì)第4分會(huì)場(chǎng)摘要集[C];2012年

10 周麗麗;劉讓蘇;田澤安;劉全慧;;凝固條件對(duì)液態(tài)Ca_7Mg_3合金納米結(jié)構(gòu)演變影響的模擬研究[A];第七屆中國(guó)功能材料及其應(yīng)用學(xué)術(shù)會(huì)議論文集（第7分冊(cè)）[C];2010年

相關(guān)重要報(bào)紙文章 前10條

1 記者 劉霞;科學(xué)家首次用不同粒子合成出復(fù)雜納米結(jié)構(gòu)[N];科技日?qǐng)?bào);2009年

2 李晶;打造鈦材新貴 西部材料購(gòu)西部鈦業(yè)[N];第一財(cái)經(jīng)日?qǐng)?bào);2009年

3 證券時(shí)報(bào)記者 鄭彥;西部材料 打造中國(guó)鈦材新旗艦[N];證券時(shí)報(bào);2009年

4 記者陳巖;探討鈦材應(yīng)用 推動(dòng)鈦業(yè)發(fā)展[N];中國(guó)有色金屬報(bào);2009年

5 本報(bào)記者 甘泉;鈦谷科技 鈦材研制取得突破[N];寶雞日?qǐng)?bào);2009年

6 記者 秦菲菲;應(yīng)用空間廣闊 鈦材需求或井噴[N];上海證券報(bào);2011年

7 記者 楊德祥 石含明;聯(lián)手打造楚雄州鈦材加工基地[N];云南經(jīng)濟(jì)日?qǐng)?bào);2009年

8 文言;鈦材競(jìng)爭(zhēng)越演越烈[N];中國(guó)有色金屬報(bào);2010年

9 ;吉林開發(fā)出環(huán)保型納米結(jié)構(gòu)漆(27)[N];今日信息報(bào);2003年

10 ;吉林開發(fā)出環(huán)保型納米結(jié)構(gòu)漆(30)[N];今日信息報(bào);2003年

相關(guān)博士學(xué)位論文 前10條

1 王君禮;金屬磷化物納米結(jié)構(gòu)的設(shè)計(jì)合成與形成機(jī)理[D];中國(guó)科學(xué)技術(shù)大學(xué);2010年

2 蔣蓉蓉;納米結(jié)構(gòu)二氧化錳的制備及其作為電化學(xué)電容器電極材料的研究[D];復(fù)旦大學(xué);2010年

3 李強(qiáng);ZnO、MnO_2、氧化硅納米結(jié)構(gòu)的合成及其物理化學(xué)性能研究[D];合肥工業(yè)大學(xué);2011年

4 楊海峰;片狀介孔材料的制備及其在納米結(jié)構(gòu)模板合成中的應(yīng)用[D];復(fù)旦大學(xué);2004年

5 萬青;零維Ge和一維ZnO納米結(jié)構(gòu)與器件[D];中國(guó)科學(xué)院研究生院（上海微系統(tǒng)與信息技術(shù)研究所）;2004年

6 霍子揚(yáng);過渡金屬氧化物納米結(jié)構(gòu)的調(diào)控合成、組裝及其性能研究[D];清華大學(xué);2009年

7 鄭先鋒;鎳基磷化物新型納米結(jié)構(gòu)的合成、組裝和磁性質(zhì)[D];華中科技大學(xué);2010年

8 薛鵬沖;手性小分子有機(jī)凝膠劑的合成、組裝及其模板構(gòu)筑無機(jī)納米結(jié)構(gòu)[D];吉林大學(xué);2005年

9 王辰光;幾種金屬氧化物和空心納米結(jié)構(gòu)的形貌控制合成[D];浙江大學(xué);2009年

10 楊松林;AlN和ZnO納米結(jié)構(gòu)的電弧放電法制備及生長(zhǎng)機(jī)制研究[D];清華大學(xué);2010年

相關(guān)碩士學(xué)位論文 前10條

1 林鋒;ZrO_2/Y_2O_3納米結(jié)構(gòu)粉末及熱障涂層的研制[D];中南大學(xué);2004年

2 陶鵬;納米結(jié)構(gòu)MgZnO的制備和表征[D];蘭州大學(xué);2010年

3 閆麗麗;納米結(jié)構(gòu)Cu_2O陣列薄膜的銅陽極氧化法制備及其光電化學(xué)性能研究[D];華中師范大學(xué);2011年

4 楊曉輝;納米結(jié)構(gòu)TiO_2的制備、組裝機(jī)理及光催化性能的研究[D];河北師范大學(xué);2004年

5 薛秀冬;二氧化鈦及鈦酸鹽雜化納米結(jié)構(gòu)的設(shè)計(jì)合成[D];蘇州大學(xué);2010年

6 張彬;磁性納米結(jié)構(gòu)的微磁學(xué)研究[D];蘭州大學(xué);2010年

7 程威;水溶性超順磁鐵氧體單分散納米結(jié)構(gòu)的合成[D];中國(guó)科學(xué)技術(shù)大學(xué);2010年

8 何雙虎;電化學(xué)法制備ZnO納米結(jié)構(gòu)及其性能研究[D];上海交通大學(xué);2010年

9 張莉;非水體系下聚苯胺納米結(jié)構(gòu)的合成及氣敏性質(zhì)研究[D];東北師范大學(xué);2010年

10 劉文軍;共濺法制備Mn摻雜GaN薄膜和納米結(jié)構(gòu)的研究[D];山東師范大學(xué);2010年

本文編號(hào)：1828532