摘要
纳米TiO_2是一种新型的高性能无机材料,具有独特的物理和化学特性。如优良的光催化活性、光电性能、光致超亲水性以及很好的生物相容性和诱导类骨质矿物沉积的能力等。
本文基于纳米TiO_2涂层本身具有良好的生物相容性,加上涂层表面的光致超亲水特性,研究了可光致亲水-憎水转换的自立的TiO_2纳米球表面层的制备与表征。并初步探索TiO_2纳米球表面层这种非连续的结构作为生物医用材料应用,以及表面层的本征性能及光照等外部条件对其生物学应用的影响等。
首先,采用溶胶-凝胶法和旋涂分相法相结合的方法制备出了TiO_2纳米球表面层。然后以硅基板为载体,研究了TiO_2纳米球表面层的结构性能以及光致亲水-憎水转换的性能,最后以钛植入体为载体,研究了TiO_2纳米球表面层的生物学应用,以及光致亲水-憎水转换对这一应用的影响。表征手段包括X射线衍射、扫描电镜、透射电镜、X光电子能谱仪、傅立叶红外光谱分析仪、接触角分析仪、模拟体液浸泡以及细胞培养等。结果表明:
1.在硅基板表面上成功制备出了一层大小基本一致,分布均匀,致密的TiO_2纳米球表面层,该表面层为单层结构,且厚度与纳米球的直径(50-100nm)相当。分别掺杂La离子,Fe离子,N离子均可以成功地进入TiO_2球状纳米点中,且不会改变TiO_2纳米球表面层的形貌特征。
2.硅基板上TiO_2纳米球表面层具有在光照条件下润湿性能转变的特性,并且这一特性能够通过实验条件、离子浓度和离子掺杂得到一定程度的调控。
3.在经过硅基板上的模拟,又成功将TiO_2纳米球表面层生长在Ti植入体上。经模拟体液浸泡和细胞培养实验后,发现具有比较优异的磷灰石沉积特性和invitro细胞相容性,表明TiO_2纳米球表面层具有良好的生物活性。同时,在紫外光照射前后,由于表面的憎水/亲水特性的智能化转换,TiO_2纳米球表面层的生物活性随之发生了有规律的变化。具体而言,紫外光的照射有使生物活性增强的趋势。
As a new high-performance inorganic material,Nano-TiO_2 shows many unique physical and chemical properties.Such as excellent photocatalytic activity, photoelectric property,photo induced super-hydrophilicity,good biocompatibility and capability of inducing bone mineral deposition.
In this thesis,based on the good biocompatibility of nano-TiO_2 coating and photo-induced super-hydrophilicity of the surface,free-standing TiO_2 nanospheres layers with photo switchable hydrophilicity and hydrophobicity were prepared and characterized.The possible biological application of such layers,as well as the effects of material intrinsic property and photo excitation,are explored and discussed.
Firstly,TiO_2 nanoparticles are prepared on a Si wafer substrate through a combined method of sol gel processing and spinodal phase separation.Then,on Si wafer substrate,the structure and photo-induced hydrophilic-hydrophobic conversion performance of TiO_2 nanospheres are studied.Finally,on Ti substrate,the in vitro property of TiO_2 nanospheres and the impact of hydrophilicity and hydrophobicity are discussed.Means of characterization include X-ray diffraction,scanning electron microscopy,transmission electron microscopy,X photoelectron spectroscopy,Fourier transform infrared spectroscopy,contact angle measurement,simulated body fluid immersion,as well as in vitro cell culture,etc.The research results show as below:
1.The compact layer with randomly distributed TiO_2 nanospheres is formed on the Si substrate.It has single-layer structure.And corresponding to the diameter of nanoparticle,the thickness of TiO_2 nanospheres is 50-100nm.When doping La ions, Fe ions,N ions respectively,they are able to successfully enter the spherical TiO_2, and the surfacing morphology of TiO_2 nanoparticles remains the same.
2.TiO_2 nanospheres layer on Si wafer substrate has characteristics of hydrophilic-hydrophobic conversion with photo excitation.Such feature can be regulated by experimental conditions,ion concentration and ion doping to certain extent.
3.The compact layer with randomly distributed TiO_2 nanospheres is also formed on the Ti substrate successfully.Through simulated body fluid immersion and cell culture, TiO_2 nanospheres show excellent characteristics of apatite deposition and in vitro cell compatibility.Meanwhile,after UV irradiation,the biological activity of such surface layers improved due to enhanced hydrophilicity.
引文
[1]Mo S D,Ching W Y.Electronic and optical properties of three phases of titanium dioxide:rutile,anatase,and brookite[J].Phys.Rev.B,1995,51(19):13023-13032
[2]罗鸣,翁文剑.基于基板的纳米点TiO_2结构的制备及性能研究.浙江大学博士学位论文.2009,06
[3]Wang C C,Ying J Y.Sol-gel synthesis and hydrothermal processing of anatase and rutile titania nanocrystals[J].Chem.Mater.,1999,11(11):3113-3120
[4]Pottier A,Chan e ac C,Tronc E,et al.Synthesis of brookite TiO_2 nanoparticles by thermolysis of TiCl_4 in strongly acidic aqueous media[J].J.Mater.Chem.,2001,11(4):1116-1121
[5]Asahi R,Morikawa T,Ohwaki T,et al.Visible-light photocatalysis in nitrogen-doped titanium oxides[J].Science,2001,293(5528):269-271
[6]Diebold U.The surface science of titanium dioxide[J].Surf.Sci.Rep.,2003,48(5-8):53-229
[7]Cheng Y J,Gutmann J S.Morphology phase diagram of ultrathin anatase TiO_2films templated by a single PS-b-PEO block copolymer[J].J.Am.Chem.Soc.,2006,128(14):4658-4674
[8]Yang H G,Sun C H,Qiao S Z,et al.Anatase TiO_2 single crystals with a large percentage of reactive facets[J].Nature,2008,453(7195):638-641
[9]Yoffe A D.Semiconductor quantum dots and related systems:electronic,optical,luminescence and related properties of low dimensional systems[J].Adv.Phys.,2001,50(1):1-208
[10]Yoffe A D.Low-dimensional systems:quantum size effects and electronic properties of semiconductor microcrystallites(zero-dimensional systems) and some quasi-two-dimensional systems[J].Adv.Phys.,2002,51(2):799-890
[11]Xia Y N,Yang P D,Sun Y G,et al.One-dimensional nanostructures:Synthesis, characterization,and applications[J].Adv.Mater.,2003,15(5):353-389
[12]Kavan L,O' Regan B,Kay A,et al.Preparation of TiO_2(anatase) films on electrodes by anodic oxidative hydrolysis of TiCl_3[J].J Electroanal Chem,1993,346:291-307
[13]Kavan L,Stoto T,Gratzel M.Quantum size effect in nanocrystalline semi-conducting TiO_2 layers prepared by anodic oxidative hydrolysis of TICl_3[J].J Phys Chem,1993,97:9493-9498
[14]黄昊,张永熙,杨锡良等.直流反应磁控溅射制备TiO_2薄膜的光催化性研究[J].真空科学与技术,2000,20(4):252-260
[15]罗谨,周静,祖延兵等.电沉积TiO_2纳米微粒膜的光电化学性能和表面形貌研究[J].高等学校化学学报,1998,19:1484-1487
[16]黄怀国,罗瑾,张红平等.Au/PATP/PANI膜电极和Au/PATP/PANI/TiO_2膜电极的光电化学[J].高等学校化学学报,2000,21(2):283-285
[17]Nataraja C,Nogami G.Cathodic electrodeposition of nanocrystalline titanium dioxide thin films[J].J Electrochem Soc,1996,143(5):1547-1550
[18]邱健斌,曹亚安,马颖等.担载材料对TiO_2薄膜光催化活性的影响[J].物理化学学报,2000,16(1):1-4
[19]沈杰,黄昊,张永熙等.溶胶凝胶法制备TiO_2薄膜的亲水性研究[J].真空科学与技术,2000,20(6):385-389
[20]Fujishima A,Rao T N,Tryk D A.Titanium dioxide photocatalysis[J].J Photochemistry and Photobiology C,2000,1:1-27
[21]Watanabe T,Nakajima A,Wang R,et al.Photocatalytic activity and photo induced hydrophilicity of titanium dioxide coated glass[J].Thin Solid Films,1999,351:260-263
[22]Ikezawa S,Homyara H,Kubota T,et al.Application of TiO_2 film for environmental purification deposite by controlled electron beam-excited plasma [J].Thin Solid Films,2001,386:173-176
[23]Song S,Jing L Q,Li S D,et al.Superhydrophilic analase TiO_2 film with the micro- and nanometer- scale hierarchical surface structure[J].Materials Letters,2008,62(20):3503-3505
[24]Zhao XT, Kenji S, Noto K, et al. Hydrophilicity of TiO_2 thin films obtained by RF magnetron sputtering deposition [J]. Current Applied Physics, 2006, 6(5):931-933
[25]Shunsuke N, Atsushi K, Zhang XT, et al. Novel hydrophilic / hydrophobic patterning process by photoeatalytic Ag nucleation on TiO_2 thin films and electroless Cu deposition [J]. Applied Surface Science, 2008, 254(18): 5891-5894
[26]Han JB, Wang X, Wang N, et al. Effect of plasma treatment on hydrophilic properties of TiO_2 thin films [J]. Surface & Coating Technology, 2006, 200(16): 4876-4 878
[27]Gunter R, Sabine M, Horst B. Investigation into the photo induced change in wettability of hydrophobized TiO_2 films [J]. Applied Surface Science, 2008,254(18): 5994-6001
[28]Satoh N, Nakashima T, Kamikura K, et al. Quantum size effect in TiO_2 nanoparticles prepared by finely controlled metal assembly on dendrimer templates [J]. Nat. Nanotechnol., 2008, 3(2): 106-111
[29]Zou B S, Xiao L Z, Li T J, et al. Absorption red shift in TiO_2 ultrafine particles with surfacial dipole laye r[J]. Appl. Phys. Lett., 1991, 59(15): 1826-1828
[30]Serpone N, Lawless D, Khairutdinov R. Size effects on the photophysical properties of colloidal anatase TiO_2 particles - size quantization or direct transitions in this indirect semiconductor [J]. J. Phys. Chem., 1995, 99(45):16646-16654
[31]Liu Y J, Claus R O. Blue light emitting nanosized TiO_2 colloids [J]. J. Am. Chem.Soc, 1997, 119(22): 5273-5274
[32]Ghosh H N, Adhikari S. Trap state emission from TiO_2 nanoparticles in microemulsion solutions [J]. Langmuir, 2001, 17(13): 4129-4130
[33]Niederberger M, Bartl M H, Stucky G D. Benzyl alcohol and titanium tetrachloride - A versatile reaction system for the nonaqueous and low-temperature preparation of crystalline and luminescent titania nanoparticles [J]. Chem. Mater.,2002, 14(10): 4364-4370
[34]Kim D H, Kim S H, Lavery K, et al. Inorganic nanodots from thin films of block copolymers [J]. Nano Lett., 2004, 4(10): 1841-1844
[35]Chen P L, Huang W J, Chang J K, et al. Fabrication and field emission characteristics of highly ordered titanium oxide nanodot arrays [J]. Electrochem.Solid-State Lett., 2005, 8(10): H83-H86
[36]Lei Y, Zhang L D, Meng G W, et al. Preparation and photoluminescence of highly ordered TiO_2 nanowire arrays [J]. Appl. Phys. Lett., 2001, 78(8): 1125-1127
[37]Xiang B, Zhang Y, Wang Z, et al. Field-emission properties of TiO_2 nanowire arrays [J]. J. Phys. D: Appl. Phys., 2005, 38(8): 1152-1155
[38]Wu J M, Shih H C, Wu W T. Electron field emission from single crystalline TiO_2 nanowires prepared by thermal evaporation [J]. Chem. Phys. Lett., 2005, 413(4-6):490-494
[39]Wen B M, Liu C Y, Liu Y. Solvothermal synthesis of ultralong single-crystalline TiO_2 nanowires [J]. New J. Chem., 2005, 29(7): 969-971
[40]Varghese O K, Gong D W, Paulose M, et al. Extreme changes in the electrical resistance of titania nanotubes with hydrogen exposure [J]. Adv. Mater., 2003,15(7-8): 624-627
[41]Zhang Z H, Zhong X H, Liu S H, et al. Aminolysis route to monodisperse titania nanorods with tunable aspect ratio [J]. Angew. Chem. Int. Ed., 2005, 44(22):3466-3470
[42]Legrand-Buscema C, Malibert C, Bach S. Elaboration and characterization of thin films of TiO_2 prepared by sol-gel process [J]. Thin Solid Films, 2002, 418(2):79-84
[43]Lotnyk A, Senz S, Hesse D. Epitaxial growth of TiO_2 thin films on SrTiO_3,LaAlO_3 and yttria-stabilized zirconia substrates by electron beam evaporation [J].Thin Solid Films, 2007, 515(7-8): 3439-3447
[44] Sasaki T, Watanabe M, Hashizume H, et al. Macromolecule-like aspects for a colloidal suspension of an exfoliated titanate. Pairwise association of nanosheets and dynamic reassembling process initiated from it[J].J.Am.Chem.Soc.,1996,118(35):8329-8335
[45]Sakai N,Ebina Y,Takada K,et al.Electronic band structure of titania semiconductor nanosheets revealed by electrochemical and photoelectrochemical studies[J].J.Am.Chem.Soc.,2004,126(18):5851-5858
[46]Yang P D,Zhao D Y,Margolese D I,et al.Generalized syntheses of large-pore mesoporous metal oxides with semicrystalline frameworks[J].Nature,1998,396(6707):152-155
[47]Yang P D,Zhao D Y,Margolese D I,et al.Block copolymer templating syntheses of mesoporous metal oxides with large ordering lengths and semicrystalline framework[J].Chem.Mater.,1999,11(10):2813-2826
[48]Crepaldi E L,Soler-Illia G J D A,Grosso D,et al.Controlled formation of highly organized mesoporous titania thin films:From mesostructured hybrids to mesoporous nanoanatase TiO_2[J].J.Am.Chem.Soc.,2003,125(32):9770-9786
[49]Dong W T,Bongard H,Tesche B,et al.Inverse opals with a skeleton structure:Photonic crystals with two complete bandgaps[J].Adv.Mater.,2002,14(20):1457-1460
[50]Arabatzis I M,Falaras P.Synthesis of porous nanocrystalline TiO_2 foam[J].Nano Lett.,2003,3(2):249-251
[51]Cheyssac P,Sacilotti M,Patriarche G.Vapor-liquid-solid mechanisms:Challenges for nanosized quantum cluster/dot/wire materials[J].Journal of Applied Physics,2006,100(44):315-315
[52]胡黎明,李春忠,姚光辉等.化学气相淀积反应器中的超细粒子的形态控制[J].华东化工学院学报,1992,18(4):417-422
[53]Mo R S,Yasutakae T,Kobata A,et al.A mechanism for the production of ultrafine particles of T iO_2 by a gas phase reaction[J].International Chemical Engineering,1989,29(1):119-126
[54]Okuyama K,Kousaka Y,W u J,et al.Production of Ultrafine Metal Oxide Aero so Particles by Thermal Decomposition of Metal Al oxide Vapors[J].A ICHE Journal,1986,32(12):2010-2019
[55]Pradhan S K,Reucroft P J,Yang F Q,et al.Growth of TiO_2 nanorods by metalorganic chemical vapor deposition[J].J.Crystal Growth,2003,256(1-2):83-88
[56]Backman U,Auvinen A,Jokiniemi J K.Deposition of nanostructured titania films by particle-assisted MOCVD[J].Surface and Coatings Technology,2005,192:81-87
[57]Patrick R M,Laura J S,Sandeep K,et al.Investigation of the PECVD TiO_2-Si (100)interface[J].Applied Surface Science,2004,233:69-79
[58]Ashworth T V,Muryn C A,Thornton G.Nanodots and other low-dimensional structures of titanium oxides[J].Nanotechnology,2005,16(12):3041-3044
[59]Sung W O,Sang H P,Yang K S.Power Sources[J].2006,161:1314-1318
[60]Eran R,David R,Reichman,et al.Drying-mediated Self-assembly of nanoparticles[J].Nature,2003,426:271-274
[61]Cheng Y J,Gutmann J S.Morphology Phase Diagram of Ultrathin Anatase TiO_2Films Templated by a Single PS-b-PEO Block Copolymer[J].Journal of the American Chemical Society,2006,128:4658-4674
[62]Meretoja V V,Tirri T,Aaritalo V,et al.Titania and titania-silica coatings for titanium:comparison of ectopic bone formation within cell-seeded scaffolds[J].Tissue Engineering,2007,13:855-863
[63]孙猛,田中敏,李新建.旋涂法制备二氧化钛纳米薄膜的光催化性能研究[J].科学技术与工程,2005,5(14):931-934
[64]Mitrev P,Benvenuti G,Hofman P.Phase transitions in thin titanium oxide film under the action of excimer laser radiation[J].Technical Physics Letters,2005,31(11):908-911
[65]Won D J,Wang C H,Jang H K,et al.Effects of thermally induced anatase -to-rutile phase transition in MOCVD-grown TiO_2 films on structural and optical properties[J].Applied Physics A,2001,73:595-600
[66]Choi Y,Yamamoto S,Umebayashi T,et al.Fabrication and characterization of anatase TiO_2 thin film on glass substrate grown by pulsed laser deposition[J].Solid State Ionics,2004,172:105-108
[67]Patrick R M,Laura J S,Sandeep K,et al.Investigation of the PECVD TiO_2-Si (100) interface[J].Applied Surface Science,2004,233:69-79
[68]Gr(a|¨)itzel M.Photoelectrochemical cells[J].Nature,2001,414(6861):338-344
[69]林元华,张中太,袁方利等.化学沉淀法制备纳米金红石型TiO_2粉体及其性能表征[J].材料科学与工艺,1999,7(2):60-64
[70]陈玲,李晓玺,高尧来.超声强化溶胶-凝胶反应制备氧化锆纳米粉体[J].化学工业与工程,2005,2(22):87-91
[71]闫鹏飞,周德瑞,王建强等.水热法制备掺杂铁离子的TiO_2纳米粒子及其光催化反应研究[J].高等学校化学学报,2002,23(12):2317-2321
[72]徐伟,李新军,郑少健等.锰离子控制掺杂二氧化钛薄膜光催化[J].高等学校化学学报,2005,26(12):2297-2301
[73]He J X,Yang P J,Akihiko Y,et al.Effects of Ag-Photodeposition on Photocurrent of an ITO Electrode Modified by a Hybrid Film of TiO_2 Nanosheets [J].Journal of Electroanalytical Chemistry,2004,566:227-233
[74]Masashi I,Li J G,Takamasa I,et al.Phase Formation and Luminescence Properties in Eu~(3+)-doped TiO_2 Nanoparticles Prepared by Thermal Plasma Pyrolysis of Aqueous Solutions[J].Thin Solid Films,2007:1-5
[75]关鲁雄,李家元,王婷等.掺杂铜和钒的纳米二氧化钦的光催化性能[J].中南大学学报(自然科学版),2006,37(4):731-737
[76]黄东升,曾人杰,陈朝凤等.铁、氮共掺杂二氧化钦薄膜的亲水性能[J].物理化学学报,2007,23(7):1037-1041
[77]Sha J,Fumihide S.Photocatalytic activities enhance for decompositions of organic compounds over metal-photodepositing titanium dioxide[J].Chemical Engineering Journal,2004,97:203-211
[78]符小荣,张校刚,宋世庚等.TiO_2/Pt/glass纳米薄膜的制备及对可溶性染料的光电催化降解[J].应用化学,1997,14(4):77-79
[79]Sasaki T,Koshizaki N,Yoon J W,et al.Preparation of Pt/TiO_2 nano-composite thin films by pulsed laser deposition and their photoelectron-chemical behaviors [J].Journal of Photochemistry and Photobiology A:Chemistry,2001,145(1/2):11-16
[80]Marta I,Litter.Heterogeneous photocatalysis transition metal ions in photocatalytic systems[J].Applied Catalysis B:Environmental,1999,23:89-114
[81]张玉红,熊国兴,杨维慎等.溶胶-凝胶法制备复合M_xO_y-TiO_2光催化剂[J].物理化学学报,2001,17(3):273-277
[82]苏文悦,付贤智,魏可镁等.SO_4~(2-)表面修饰对TiO_2结构及其光催化性能的影响[J].物理化学学报,2001,17(1):28-31
[83]Fujishiro Y,Uchida S,Sato T.Synthesis and photochemical properties of semiconductor pillared layered compounds[J].Journal of Inorganic Materials,1999,1:67-72
[84]Sonawane R S,Kale B B,Dongare M K.Preparation and photo-catalytic activity of Fe-TiO_2 thin films prepared by sol-gel dip-coating[J].Materials Chemistry and Physics,2005,85:52-57
[85]赵德明,史慧祥.复合纳米TiO_2光催化氧化苯酚的动力学[J].中国给水排水,2004,20(1):48-49
[86]赵秀峰,孟宪峰,张志红等。Pb掺杂TiO_2薄膜的制备及光催化活性研究[J].无机材料学报,2004,19(1):140-146
[87]王幼平,余家国,赵修建等.溶胶-凝胶工艺制备掺铅TiO_2纳米薄膜及其光催化性能的研究[J].中国环境科学,1998,18(3):244-247
[88]崔鹏,徐南平,时钧等.Ag/TiO_2光催化膜降解高浓度对氯苯粉溶液的研究[J].太阳能学报,2003,24(1):64-67
[89]卢萍,姚明,张颖等.钼离子掺杂对TiO_2薄膜光催化性能的研究[J].硅酸盐通报,2003,15(2):34-37
[90]晏太红,崔海霞,林志东等.稀土掺杂TiO_2薄膜的制备及光催化特性[J].复旦学报,2003,42(6):999-1002
[91]邹旭华,齐世学,贺红军等.掺杂金属离子改性的TiO_2薄膜光催化剂的研制[J].分子催化,2003,17(6):456-460
[92]傅宏刚,王建强,王哲等.TiO_2光催化剂表面修饰研究进展[J].黑龙江大学自然科学学报,2001,18(3):85-89
[93]Asahi R,Morikawa T,Ohwaki T,et al.Visible-light photo catalysis in nitrogen-doped titanium oxides[J].Science,2001,293(5528):269-273
[94]赵明,方玲,张弓等.反应溅射TiO_(2-x)N_x膜的可见光吸收性能[J].材料研究学报,2004,18(1):108-112.
[95]余灯华,廖世军.TiO_2结构对光催化性能的影响及其提高的途径[J].环境污染治理技术与设备,2003,4(2):44-48
[96]张彭义,余刚,蒋展鹏.半导体光催化剂及其改性技术进展[J].环境科学进展,1007,5(3):1-10
[97]尚华美,王承遇,王继红等.CdS复合TiO_2薄膜的制备及其太阳光催化性能[J].大连轻工业学院学报,2001,20(3):157-160
[98]Kang M G,Han H E,Kim K J.Enhanced photodecomposition of 4-chlorophenol in aqueous solution by deposition of CdS on TiO_2[J].Journal of Photochemistry and Photobiology A:Chemistry,1999,125:119-125
[99]向刚,王聪,郑树凯等.Sr离子注入改善纳米二氧化钛薄膜光催化性能[J].功能材料与器件学报,2002,8(1):23-26
[100]Asahi R,Morikawa T,Ohwaki T,etal.Visible-light photo catalysis in nitrogen-doped titanium oxides[J].Science,2001,293(5528):269-273
[101]Wang R,Hashimoto K,Fujishima A,et al.Light induced amphiphilic surface[J].Nature,1997,388:431-432
[102]高铁,钱朝勇,于向阳.材料导报,2000,14(7):27-29
[103]刘平,凌岚,林华香等.光催化抗雾膜材料的制备及其亲水性研究[J].高等学校化学学报,2000,21(3):462-465
[104]余耀庭,张兴栋编.生物医用材料.天津:天津大学出版社,2000
[105]Jia J,Duan Y Y,Chen Y S,et al.Preparation of collagen grafted PLGA electrospun ultrafine fibers and its biocompatibility test[J].Journal of Clinical Stomatology,2007,23(6):323-325
[106]Hu M X,Yang Q,Xu Z K.Enhancing the hydrophilicity of polypropylene microporous membranes by the grafting of 2-hydroxyethyl methacrylate via a synergistic effect of photoinitiators[J].J Membrane Sci,2006,285(1-2):196-205
[107]李伯刚.生物碳素材料血液相容性的可行性研究[J].生物医学工程学,2005,22(3):452-455
[108]杨晓庆,李玉宝.医用羟基磷灰石/二氧化钛纳米复合材料的制备及性能研究[J].中国现代医学杂志,2003,13(5):26-28
[109]赵迪,王君.TiO_2系列光催化抗菌材料的开发与应用[J].辽宁大学学报,2000,27(2):173-176
[110]李章先,吴基球.TiO_2纳米颗粒水热法制备研究进展及反应机理的初步研究[J].中国陶瓷工业,2001,8(2):29-33
[111]Perkas N,Palchik O,Brukental I,et al.A mesoporous iron- titanium oxide composite prepared sonochemically[J].J Phys Chem B,2003,107(34):8772-8778
[112]张玉梅,郭天文,李佐臣.钛及钛合金在口腔科应用的研究方向[J].生物学工程学杂志,2000,17(2):206-208
[113]赵树萍,吕双坤,郝文杰编.钛合金及其表面处理.哈尔滨:哈尔滨工业大学出版社,2003
[114]李德华.医用钛表面的微观改造[J].国外医学生物医学分册,1997,20(1):24-27
[115]Sandrini E,Morris C,Chiesa R.In vitro assessment of the osteointegrative potential of a novel multiphase anodic spark deposition coating for orthopaedic and dental implants[J].J Biomed Mater Res B Appl Biomater,2005,73B(2):392-399
[116]Das K,Bose S,Bandyopadhyay A.Surface modifications and cellmaterials interactions with anodized Ti[J].Acta Biomater,2007,3(4):573-585
[117]Zhang Y M,Bataillon-Linez P,Huang P,et al.Surface analyses of micro-arc oxidized and hydrothermally treated titanium and effect on osteoblast behavior [J].J Biomed Mater Res,2004,68A(2):383-391
[118]Habibovic P,Barrere F,Blitterswijk C A,et al.Biometric hydroxyapatite coating on metal implants[J].J Am Ceram Soc,2002,85:5172-5221
[119]何福明,陈松,刘丽等.纯钛表面快速沉积羟基磷灰石涂层的实验研究[J].口腔材料学研究,2004,41(4):240-241
[120]谢雷,王小祥.钛在H_2O_2溶液中的腐蚀特性研究[J].稀有金属材料与工程,2006,35(8):1219-1222
[121]Takeshi U,Masahiro Y,Takeo S,et al.Enhancement of bone titanium integration profile with UV-photofunctionalized titanium in a gap healing model[J].Biomaterials,2010,31:1546-1557
[122]Fuminori I,Norio H,Takeshi U,et al.Enhancement of osteoblast adhesion to UV-photofunctionalized titanium via an electrostatic mechanism[J].Biomaterials,2010,31:2717-2727
[123]Luo M,Cheng K,Weng W J,et al.Size-and density-controlled synthesis of TiO_2nanodots on a substrate by phase-separation-induced self-assembly[J].Nanotechnology,2009,20(21):215605
[124]Luo M,Cheng K,Weng W J,et al.Size-dependent ultraviolet luminescence and low-field electron emission of TiO_2 nanodots formed by phase-separation-induced self-assembly[J].J Phys D Appl Phys,2009,42(10):105414
[125]Bullen H A,Garrett S J.TiO_2 nanoparticle arrays prepared using a nanosphere lithography technique[J].Nano Lett.,2002,2(7):739-745
[126]Chen P L,Kuo C T,Tsai T G,et al.Self-organized titanium oxide nanodot arrays by electrochemical anodization[J].Appl.Phys.Lett.,2003,82(17):2796-2798
[127]Kim D H,Sun Z C,Russell T P,et al.Organic-inorganic nanohybridization by block copolymer thin films[J].Adv.Funct.Mater.,2005,15(7):1160-1164
[128]Ashworth T V,Muryn C A,Thornton G.Nanodots and other low-dimensional structures of titanium oxides[J].Nanotechnology,2005,16(12):3041-3044
[129]Nishida K,Yamato M,Hayashida Y,et al.Corneal Reconstruction with Tissue-Engineered Cell Sheets Composed of Autologous Oral Mucosal Epithelium[J].New England Journal of Medicine,2004,351(12):1187-1196
[130]Shiroyanagi Y,Yamato M,Yamazaki Y,et al.Transplantable Urothelial Cell Sheets Harvested Noninvasively from Temperature-Responsive Culture Surfaces by Reducing Temperature [J]. Tissue Engineering, 2003, 9:1005-1012
[131]Hasegawa M, Yamato M, Kikuchi A, et al. Human Periodontal Ligament Cell Sheets Can Regenerate Periodontal Ligament Tissue in an Athymic Rat Model [J]. Tissue Engineering, 2005, 11: 469-478
[132]Haraguchi Y, Shimizu T, Yamato M et al. Electrical coupling of cardiomyocyte sheets occurs rapidly via functional gap junction formation [J]. Biomaterials,2006, 27: 4765-4774
[133]Akiyama Y, Kikuchi A, Yamato M, et al. Ultrathin Poly(N-isopropylacrylamide) Grafted Layer on Polystyrene Surfaces for Cell Adhesion/Detachment Control [J]. Langmuir, 2004, 20: 5506-5511
[134]Kokubo T, Kushitani H, Sakka S, et al. Solutions able to reproduce in vivo surface-structure changes in bioactive glass-ceramic A-W [J]. J. Biomed. Mater.Res., 1990,24:721-734