CN107190300B - 介孔羟基磷灰石/二氧化钛纳米管阵列复合材料的制备方法 - Google Patents
介孔羟基磷灰石/二氧化钛纳米管阵列复合材料的制备方法 Download PDFInfo
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- CN107190300B CN107190300B CN201710421705.4A CN201710421705A CN107190300B CN 107190300 B CN107190300 B CN 107190300B CN 201710421705 A CN201710421705 A CN 201710421705A CN 107190300 B CN107190300 B CN 107190300B
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- titanium dioxide
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- mesoporous hydroxyapatite
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- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 title claims abstract description 92
- 239000002071 nanotube Substances 0.000 title claims abstract description 53
- 229910052588 hydroxylapatite Inorganic materials 0.000 title claims abstract description 50
- XYJRXVWERLGGKC-UHFFFAOYSA-D pentacalcium;hydroxide;triphosphate Chemical compound [OH-].[Ca+2].[Ca+2].[Ca+2].[Ca+2].[Ca+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O XYJRXVWERLGGKC-UHFFFAOYSA-D 0.000 title claims abstract description 50
- 239000004408 titanium dioxide Substances 0.000 title claims abstract description 41
- 238000002360 preparation method Methods 0.000 title claims abstract description 15
- 239000002131 composite material Substances 0.000 title claims abstract description 14
- 239000002105 nanoparticle Substances 0.000 claims abstract description 45
- 239000010936 titanium Substances 0.000 claims abstract description 25
- 229910052719 titanium Inorganic materials 0.000 claims abstract description 25
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims abstract description 22
- 239000006185 dispersion Substances 0.000 claims abstract description 20
- 239000007788 liquid Substances 0.000 claims abstract description 19
- 230000003647 oxidation Effects 0.000 claims abstract description 14
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- 230000004048 modification Effects 0.000 claims abstract description 4
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- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims description 30
- 239000012153 distilled water Substances 0.000 claims description 18
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 15
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- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 12
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- 239000011575 calcium Substances 0.000 claims description 6
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- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 claims description 4
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- 229910052698 phosphorus Inorganic materials 0.000 claims description 3
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- DDFHBQSCUXNBSA-UHFFFAOYSA-N 5-(5-carboxythiophen-2-yl)thiophene-2-carboxylic acid Chemical compound S1C(C(=O)O)=CC=C1C1=CC=C(C(O)=O)S1 DDFHBQSCUXNBSA-UHFFFAOYSA-N 0.000 claims description 2
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- 235000019738 Limestone Nutrition 0.000 description 2
- DMGNFLJBACZMRM-UHFFFAOYSA-N O[P] Chemical compound O[P] DMGNFLJBACZMRM-UHFFFAOYSA-N 0.000 description 2
- LDDQLRUQCUTJBB-UHFFFAOYSA-N ammonium fluoride Chemical compound [NH4+].[F-] LDDQLRUQCUTJBB-UHFFFAOYSA-N 0.000 description 2
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- NJTGANWAUPEOAX-UHFFFAOYSA-N molport-023-220-454 Chemical compound OCC(O)CO.OCC(O)CO NJTGANWAUPEOAX-UHFFFAOYSA-N 0.000 description 2
- VSIIXMUUUJUKCM-UHFFFAOYSA-D pentacalcium;fluoride;triphosphate Chemical compound [F-].[Ca+2].[Ca+2].[Ca+2].[Ca+2].[Ca+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O VSIIXMUUUJUKCM-UHFFFAOYSA-D 0.000 description 2
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 2
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- HGWOWDFNMKCVLG-UHFFFAOYSA-N [O--].[O--].[Ti+4].[Ti+4] Chemical compound [O--].[O--].[Ti+4].[Ti+4] HGWOWDFNMKCVLG-UHFFFAOYSA-N 0.000 description 1
- HRHBQGBPZWNGHV-UHFFFAOYSA-N azane;bromomethane Chemical compound N.BrC HRHBQGBPZWNGHV-UHFFFAOYSA-N 0.000 description 1
- 239000012620 biological material Substances 0.000 description 1
- 210000002449 bone cell Anatomy 0.000 description 1
- 201000011510 cancer Diseases 0.000 description 1
- 229910021393 carbon nanotube Inorganic materials 0.000 description 1
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- SZVJSHCCFOBDDC-UHFFFAOYSA-N iron(II,III) oxide Inorganic materials O=[Fe]O[Fe]O[Fe]=O SZVJSHCCFOBDDC-UHFFFAOYSA-N 0.000 description 1
- 239000002502 liposome Substances 0.000 description 1
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- 239000003981 vehicle Substances 0.000 description 1
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Abstract
本发明公开一种介孔羟基磷灰石纳米颗粒/二氧化钛纳米管阵列新型复合材料的制备方法，其特征在于：包括如下步骤：1）以钛片为阳极，阳极氧化制备二氧化钛纳米管阵列；2）用溶胶‑凝胶法制备介孔羟基磷灰石纳米颗粒；3）然后将二氧化钛纳米管阵列置于介孔羟基磷灰石纳米颗粒分散液中水热/溶剂热反应，在二氧化钛纳米管阵列表面修饰介孔羟基磷灰石纳米颗粒。本发明的特点在于：介孔羟基磷灰石纳米颗粒深入二氧化钛纳米管阵列内部，结合强度高，同时，复合材料具有良好的生物活性，可负载一些药物分子，作为药物缓释的载体。
Description
技术领域
本发明属于骨修复生物材料和药物缓释载体制备技术领域，具体是一种制备介孔羟基磷灰石纳米颗粒/二氧化钛纳米管阵列新型复合材料的方法。
背景技术
在最近的几十年里，纳米材料在生物医学研究、疾病诊断和治疗方面的应用吸引了越来越多人的兴趣。然而，传统的诊断和治疗药物(如药物或基因)在临床的应用受限于其稳定性差，副作用的几率高,缺乏药物动力学研究，快速清除、高剂量和无特异性靶向。纳米粒子被认为是有用的加载诊断和治疗药物的纳米载体。在过去几十年里，纳米材料已被用于治疗癌症、伤口和细菌感染。它们提高了药物的疗效，减少了副作用，许多纳米材料如石墨烯，氧化物、碳纳米管、金属氧化物、水凝胶、树枝状大分子、脂质体等常常用于药物传递。尽管纳米载体可以保护显像剂免于酶的催化降解，但纳米载体的毒性成了其生物医学应用的一个问题。在过去的几年里，无机纳米材料因其优异的稳定性、高的生物分子负载量和表面易于接合生物分子，被广泛的应用于纳米载体。
不同纳米结构的TiO2材料的制备和应用的研究得到了长足的发展。人们采用不同方法制备不同的纳米结构，包括纳米粒子、纳米棒、纳米纤维、纳米层和纳米管。其中，TiO2纳米管阵列具有许多优点，是吸附药物的良好载体。通过阳极氧化法在钛金属表面构建的高度有序的TiO2纳米管阵列，具有制备工艺相对简单、阵列高度有序、管径可控、纳米管与基底结合更加牢固等优点。其本身纳米级多孔形貌，适于多种细胞黏附和生长。因此TiO2纳米管有序阵列作为内置物表面修饰方法具有良好的应用前景。
羟基磷灰石(Ca10(PO4)6(OH)2或HA)具有良好的生物相容性，独特的机械性能，生物活性，以及和活骨组织形成化学键的优秀能力，并且无毒性、非炎症性质。人们研究它的各种形态和表面性质，将其作为药物载体负载药物甚至作为眼科内置物使用。但较低的比表面积限制了它在许多条件下的进一步应用。介孔羟基磷灰石能够在一定程度上克服这些缺点，并对骨头细胞和组织有好的生物相容性和生物活性。Negar等（Int. J. Pharm.,2016(509): 159-167）以介孔羟基磷灰石为涂层，修饰在超顺磁Fe3O4纳米粒子表面作为药物传输载体。
发明内容
本发明的目的在于利用水热法的原理，提供一种新的制备介孔羟基磷灰石纳米颗粒/二氧化钛纳米管阵列新型复合材料的方法，其特征在于：以经过预处理的钛片为阳极，以铂片为阴极，通过阳极氧化法在甘油/水体系的电解质溶液中于钛片表面形成二氧化钛纳米管阵列。将二氧化钛纳米管阵列置于介孔羟基磷灰石纳米颗粒分散液中，并通过水热法在二氧化钛纳米管阵列表面上修饰介孔羟基磷灰石纳米颗粒，形成一种新型的介孔羟基磷灰石纳米颗粒/二氧化钛纳米管阵列复合材料。
本发明的目的是这样实现的，所述的介孔羟基磷灰石纳米颗粒/二氧化钛纳米管阵列新型复合材料的制备方法，其特征在于：包括如下步骤：1）以钛片为阳极，阳极氧化制备二氧化钛纳米管阵列；2）用溶胶-凝胶法制备介孔羟基磷灰石纳米颗粒；3）然后将二氧化钛纳米管阵列置于介孔羟基磷灰石纳米颗粒分散液中水热/溶剂热反应，在二氧化钛纳米管阵列表面修饰介孔羟基磷灰石纳米颗粒。
上述步骤1）的阳极氧化制备二氧化钛纳米管阵列的方法为：以钛片为阳极，铂片为阴极，在含氟的甘油/水体系的电解质溶液中，以阳极氧化30~70V，电解液温度为20~50℃条件下阳极氧化2~24h。
上述步骤2）的介孔羟基磷灰石纳米颗粒溶胶-凝胶法制备方法为：以十六烷基三甲基溴化铵为模板剂，以（NH4）2HPO4为磷源，以Ca(NO3)2•4H2O为钙源，用氨水调pH值为10，搅拌2~4h，陈化24~48h，交替用乙醇和蒸馏水离心洗涤，在-50℃下冷冻干燥48h，于500~600℃温度下煅烧4~6h，即得介孔羟基磷灰石纳米颗粒。
所述的二氧化钛纳米管阵列置于介孔羟基磷灰石纳米颗粒分散液中水热反应步骤为：将二氧化钛纳米管阵列置于介孔羟基磷灰石纳米颗粒的分散液中，并在100~150℃温度下水热1~9h处理。
所述的二氧化钛纳米管阵列置于介孔羟基磷灰石纳米颗粒分散液中溶剂热反应步骤为：将二氧化钛纳米管阵列置于介孔羟基磷灰石纳米颗粒的乙醇分散液中，并在100~150℃温度下水热1~9h处理。
上述含氟的甘油/水体系的电解质溶液采用含氟化铵0.20~0.60 wt% 的甘油/水体系的电解质溶液，所述的甘油/水体系中的甘油与水的质量比是9:1。
本发明的上述复合材料的制备方法制得介孔羟基磷灰石纳米颗粒/二氧化钛纳米管阵列新型复合材料。
具体地说，本发明采用如下技术方案，步骤为：
1）钛片预处理：将钛片打磨至光滑，并在HF和 HNO3的混合酸溶液中刻蚀10~30s，用蒸馏水淋洗，50℃烘干。
2）二氧化钛纳米管阵列的制备：以预处理好的钛片为阳极，铂片为阴极，在含氟化铵0.20~0.60 wt% 的甘油/水体系的电解质溶液中进行阳极氧化2~24h，氧化电压为30~70V，电解液温度为20~50℃即得二氧化钛纳米管阵列。
3）介孔羟基磷灰石纳米颗粒的制备：以十六烷基三甲基溴化铵为模板剂，以（NH4）2HPO4为磷源，以Ca(NO3)2•4H2O为钙源，用氨水调pH值为10，搅拌2~4h，陈化24~48h，交替用乙醇和蒸馏水离心洗涤，在-50℃下冷冻干燥48h，于500~600℃温度下煅烧4~6h，即得介孔羟基磷灰石纳米颗粒。
4）水热/溶剂热制备：将阳极氧化的钛基体置于介孔羟基磷灰石纳米颗粒的分散液中进行水热反应，然后取出钛基体，用蒸馏水淋洗，烘干即得复合材料；或将阳极氧化的钛基体置于介孔羟基磷灰石纳米颗粒的乙醇分散液中进行溶剂热反应，然后取出钛基体，用蒸馏水淋洗，烘干即得复合材料。
本发明所述的水热/溶剂热制备反应步骤中，是将阳极氧化处理后的钛基体置于分散液中，在100~150℃温度下水热1~9h。其中分散液是指将介孔羟基磷灰石纳米颗粒分别分散在蒸馏水和乙醇中。
本发明采用上述方案得到的复合材料具有以下特点：介孔羟基磷灰石纳米颗粒深入二氧化钛纳米管阵列内部，结合强度高；TiO2纳米管阵列表面修饰介孔羟基磷灰石纳米颗粒后，能够较快的诱导沉积磷灰石，具有良好的生物活性，同时，复合材料表面的多孔性，有利于骨细胞的生长和黏附；介孔羟基磷灰石纳米颗粒修饰在二氧化钛纳米管阵列上，可以负载一些药物分子，作为药物缓释的载体。
附图说明
图1为本发明具体实施例1中阳极氧化得到的二氧化钛纳米管阵列的表面微观形貌图。
图2为本发明具体实施例1中二氧化钛纳米管阵列经水热在水热条件下沉积介孔羟基磷灰石纳米颗粒的表面微观形貌图。
图3a为本发明具体实施例2中二氧化钛纳米管阵列经溶剂热反应沉积介孔羟基磷灰石纳米颗粒的表面的微观形貌图。
图3b为本发明具体实施例2中二氧化钛纳米管阵列经溶剂热反应沉积介孔羟基磷灰石纳米颗粒的截面的微观形貌图。
具体实施方式
实施例1
以钛金属为基底，用金相砂纸打磨至光滑，于丙酮中超声清洗并在4wt%HF-5mol/LHNO3的混合酸溶液中刻蚀，用蒸馏水淋洗并超声，50℃烘干。以预处理好的钛片为阳极，铂片为阴极，以0.50wt%NH4F+10wt%H2O+丙三醇为电解质溶液，所述的甘油（丙三醇）与水的质量比是9:1，在60V电压下阳极氧化24h后，取出，用蒸馏水淋洗，空气中晾干，即得二氧化钛纳米管阵列，微观形貌图如图1所示，纳米管排列紧密，规整，管径约为210nm。
将0.05%的十六烷基三甲基溴化铵溶于50ml蒸馏水，加入3.96g（NH4）2HPO4，搅拌2h，用25wt%氨水调pH值为10。将11.83gCa(NO3)2•4H2O溶于50ml蒸馏水，用25wt%氨水调 pH值为10，在剧烈搅拌的条件下，逐滴缓慢滴入上述溶液中，搅拌4h，陈化24h，用乙醇和蒸馏水洗涤，在-50℃下冷冻干燥48h，于550℃煅烧6h，得到介孔羟基磷灰石纳米颗粒样品。
精确称取一定量的介孔羟基磷灰石纳米颗粒，加入一定量的蒸馏水配置成浓度为1.0×10-2（wt%）的分散液，将二氧化钛纳米管阵列——钛基体置于上述分散液中于150℃条件下水热反应1h，取出二氧化钛纳米管阵列——钛基体，用蒸馏水淋洗，50℃烘干，即得复合材料，其表面形貌如图2所示，纳米管表面覆盖了一层介孔羟基磷灰石颗粒，管径变小。
实施例2
以钛金属为基底，用金相砂纸打磨至光滑，于丙酮中超声清洗并在4wt%HF-5mol/LHNO3的混合酸溶液中刻蚀，用蒸馏水淋洗并超声，50℃烘干。以预处理好的钛片为阳极，铂片为阴极，以0.50wt%NH4F+10wt%H2O+丙三醇为电解质溶液，所述的甘油（丙三醇）与水的质量比是9:1，在60V电压下阳极氧化24h后，取出，用蒸馏水淋洗，空气中晾干，即得二氧化钛纳米管阵列，微观形貌图如图1所示，纳米管排列紧密，规整，管径约为210nm。
将0.05%的十六烷基三甲基溴化铵溶于50ml蒸馏水，加入3.96g（NH4）2HPO4，搅拌2h，用25wt%氨水调pH值为10。将11.83gCa(NO3)2•4H2O溶于50ml蒸馏水，用25wt%氨水调 pH值为10，在剧烈搅拌的条件下，逐滴缓慢滴入上述溶液中，搅拌4h，陈化24h，用乙醇和蒸馏水洗涤，在-50℃下冷冻干燥48h，于550℃煅烧6h，得到介孔羟基磷灰石纳米颗粒样品。
精确称取一定量的介孔羟基磷灰石纳米颗粒，加入一定量的乙醇配置成浓度为6.0×10-2（wt%）的分散液，将二氧化钛纳米管阵列——钛基体置于上述分散液中于120℃条件下溶剂热反应9h，取出钛基体，用蒸馏水淋洗，50℃烘干，即得复合材料，其表面形貌如图3a所示，表面覆盖了一层介孔羟基磷灰石纳米颗粒，孔径变小，从其截面图3b可以看出，介孔二氧化硅纳米颗粒已深入纳米管内部。
上述的具体实施方式是对本发明申请的进一步详细说明，但本发明权利要求保护的范围并不局限于实施方式中所描述的范围，凡采用同效变形等的技术方案，均落在本发明权利要求的保护范围。
Claims (3)
1.一种介孔羟基磷灰石纳米颗粒/二氧化钛纳米管阵列复合材料的制备方法，其特征在于：包括如下步骤：1）以钛片为阳极，阳极氧化制备二氧化钛纳米管阵列；2）用溶胶-凝胶法制备介孔羟基磷灰石纳米颗粒；3）然后将二氧化钛纳米管阵列置于介孔羟基磷灰石纳米颗粒分散液中水热/溶剂热反应，在二氧化钛纳米管阵列表面修饰介孔羟基磷灰石纳米颗粒；
步骤1）的阳极氧化制备二氧化钛纳米管阵列的方法为：以钛片为阳极，铂片为阴极，在含氟的甘油/水体系的电解质溶液中，以阳极氧化30~70V，电解液温度为20~50℃条件下阳极氧化2~24h；
步骤2）的介孔羟基磷灰石纳米颗粒溶胶-凝胶法制备方法为：以十六烷基三甲基溴化铵为模板剂，以（NH4）2HPO4为磷源，以Ca(NO3)2•4H2O为钙源，用氨水调pH值为10，搅拌2~4h，陈化24~48h，交替用乙醇和蒸馏水离心洗涤，在-50℃下冷冻干燥48h，于500~600℃温度下煅烧4~6h，即得介孔羟基磷灰石纳米颗粒；
所述的二氧化钛纳米管阵列置于介孔羟基磷灰石纳米颗粒分散液中水热反应步骤为：将二氧化钛纳米管阵列置于介孔羟基磷灰石纳米颗粒的分散液中，并在100~150℃温度下水热1~9h处理；
所述的二氧化钛纳米管阵列置于介孔羟基磷灰石纳米颗粒分散液中溶剂热反应步骤为：将二氧化钛纳米管阵列置于介孔羟基磷灰石纳米颗粒的乙醇分散液中，并在100~150℃温度下水热1~9h处理。
2.如权利要求1所述的复合材料的制备方法，其特征在于含氟的甘油/水体系的电解质溶液采用含氟化铵0.20~0.60 wt% 的甘油/水体系的电解质溶液，所述的甘油/水体系中的甘油与水的质量比是9:1。
3.权利要求1-2任一所述的复合材料的制备方法制得介孔羟基磷灰石纳米颗粒/二氧化钛纳米管阵列复合材料。
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