CN114395759B - 一种钛表面柠檬酸-含钙化学转化膜及其制备方法和应用 - Google Patents
一种钛表面柠檬酸-含钙化学转化膜及其制备方法和应用 Download PDFInfo
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- CN114395759B CN114395759B CN202111511359.1A CN202111511359A CN114395759B CN 114395759 B CN114395759 B CN 114395759B CN 202111511359 A CN202111511359 A CN 202111511359A CN 114395759 B CN114395759 B CN 114395759B
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- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 title claims abstract description 67
- 239000010936 titanium Substances 0.000 title claims abstract description 67
- 229910052719 titanium Inorganic materials 0.000 title claims abstract description 66
- 239000000126 substance Substances 0.000 title claims abstract description 42
- 238000006243 chemical reaction Methods 0.000 title claims abstract description 39
- QXDHJHQRJCJRAU-UHFFFAOYSA-N calcium;2-hydroxypropane-1,2,3-tricarboxylic acid Chemical compound [Ca].OC(=O)CC(O)(C(O)=O)CC(O)=O QXDHJHQRJCJRAU-UHFFFAOYSA-N 0.000 title claims abstract description 13
- 238000002360 preparation method Methods 0.000 title claims abstract description 9
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims abstract description 27
- 238000000034 method Methods 0.000 claims abstract description 12
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- BHPQYMZQTOCNFJ-UHFFFAOYSA-N Calcium cation Chemical compound [Ca+2] BHPQYMZQTOCNFJ-UHFFFAOYSA-N 0.000 claims description 10
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 7
- KRKNYBCHXYNGOX-UHFFFAOYSA-K Citrate Chemical compound [O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O KRKNYBCHXYNGOX-UHFFFAOYSA-K 0.000 claims description 5
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- 239000001354 calcium citrate Substances 0.000 claims description 2
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- 239000011575 calcium Substances 0.000 abstract description 13
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- 230000004069 differentiation Effects 0.000 abstract description 5
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 abstract description 4
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- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 abstract description 3
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- RBLGLDWTCZMLRW-UHFFFAOYSA-K dicalcium;phosphate;dihydrate Chemical compound O.O.[Ca+2].[Ca+2].[O-]P([O-])([O-])=O RBLGLDWTCZMLRW-UHFFFAOYSA-K 0.000 description 2
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- QORWJWZARLRLPR-UHFFFAOYSA-H tricalcium bis(phosphate) Chemical compound [Ca+2].[Ca+2].[Ca+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O QORWJWZARLRLPR-UHFFFAOYSA-H 0.000 description 2
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- SFLSHLFXELFNJZ-UHFFFAOYSA-N norepinephrine Natural products NCC(O)C1=CC=C(O)C(O)=C1 SFLSHLFXELFNJZ-UHFFFAOYSA-N 0.000 description 1
- 229910000392 octacalcium phosphate Inorganic materials 0.000 description 1
- 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 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 229940085991 phosphate ion Drugs 0.000 description 1
- -1 phosphate ion modified titanium Chemical class 0.000 description 1
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- 108700038288 rhodamine-phalloidin Proteins 0.000 description 1
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- AJPJDKMHJJGVTQ-UHFFFAOYSA-M sodium dihydrogen phosphate Chemical compound [Na+].OP(O)([O-])=O AJPJDKMHJJGVTQ-UHFFFAOYSA-M 0.000 description 1
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- CIOAGBVUUVVLOB-UHFFFAOYSA-N strontium atom Chemical compound [Sr] CIOAGBVUUVVLOB-UHFFFAOYSA-N 0.000 description 1
- 229910052715 tantalum Inorganic materials 0.000 description 1
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 description 1
- YIGWVOWKHUSYER-UHFFFAOYSA-F tetracalcium;hydrogen phosphate;diphosphate Chemical compound [Ca+2].[Ca+2].[Ca+2].[Ca+2].OP([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O YIGWVOWKHUSYER-UHFFFAOYSA-F 0.000 description 1
- 210000001519 tissue Anatomy 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
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- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
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- C23C22/48—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6 not containing phosphates, hexavalent chromium compounds, fluorides or complex fluorides, molybdates, tungstates, vanadates or oxalates
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Abstract
一种钛表面柠檬酸‑含钙化学转化膜及其制备方法和应用，属于钛基表面处理技术领域，包括如下步骤：配制化学转化基础液，其中含有柠檬酸和氢氧化钙；对经大颗粒喷砂酸蚀（SLA）处理后的医用纯钛片浸泡于化学转化基础液中进行化学转化处理，转化温度为80‑100℃，转化时间为20‑30min。该方法原料简单，易于操作，方便控制，稳定性佳；经该方法制备的钛表面有良好的生物学活性，明显促进钙磷的沉积，有利于成骨细胞的粘附、增殖和分化，有效提高钛基牙种植体的早期骨整合能力，改善其临床应用效果。
Description
技术领域
本发明属于生物医用金属材料表面改性技术领域，具体涉及一种钛表面柠檬酸-含钙化学转化膜及其制备方法和应用。
背景技术
钛及钛合金具有良好的生物相容性和稳定性，是目前医学领域最广泛使用的牙种植体。钛种植体的初始稳定性是即刻负载的首要因素，在随后的骨愈合过程中，新骨沉积在种植体表面形成二次骨接触，迅速获得种植体的二次稳定性，实现种植体与骨的骨结合，是即刻负载成功的关键。然而，钛种植体属于生物惰性材料，表面缺乏生物活性表面，二级稳定形成缓慢，导致减少种植体和组织之间的骨整合界面，严重影响种植体的整体稳定性，并最终导致种植失败。
为了克服这一限制，投入了大量的科学努力来改善钛表面的生物活性。目前已采用喷砂、酸蚀刻、等离子喷涂、仿生矿化、仿生沉积、电泳沉积、电化学沉积等技术对人体骨骼的生物化学环境和纳米结构进行了模拟。这些技术不仅改变了钛基底的表面形态，还引入了多种生物活性物质，如生长因子(骨形态发生蛋白-2,BMP-2；血管内皮生长因子；成纤维细胞生长因子(FGF)、细胞外基质蛋白和多肽(RGD多肽；人体β防御素(HBDs)、矿物元素(钙、磷、镁、锌、银、锶、钽、钴)。最受欢迎的生物活性物质是矿物质钙，它是一种非炎症、无毒、非免疫原性的材料，具有骨传导和生物活性特性。
钛种植体表面各种形式的含钙涂层类似于矿钙库，有效释放钙离子，在种植体周围形成局部高钙浓度环境，促进BMSCs分化。所述含钙涂层形成于钛基体上，包括羟基磷灰石、无定形磷酸钙、磷酸八钙和二水磷酸二钙，提供了丰富的钙离子来源，但物理涂层的力学性能和残余应力较差，阻碍了物理涂层的应用前景。从这个角度来看，使用含钙的化学涂层更有利，具有更好的粘结强度，避免了负应力屏蔽。
化学转化是一种通过金属与溶液界面发生化学和电化学反应从而在金属表面生成完整不溶性转化膜的方法,由于该方法操作简单、用时短、成本低而被广泛用于工业领域。Sunarso等利用磷酸二氢钠(NaH2PO4)水溶液进行水热处理制备磷酸离子改性钛表面，然后用氯化钙溶液进行水热处理，通过钙离子与磷酸盐离子的化学结合构建磷酸钙涂层（摘自Sunarso, R. Toita, K. Tsuru, K. Ishikawa, Immobilization of calcium andphosphate ions improves the osteoconductivity of titanium implants, Mater SciEng C Mater Biol Appl 68 (2016) 291-8.）；Toita等人首先用聚去甲肾上腺素(PNE)包覆聚醚醚酮(PEEK)，然后在氢氧化钙[Ca(OH)2]水溶液中浸泡（摘自R. Toita, S.A.N.Rashid, K. Tsuru, K. Ishikawa, Modulation of the osteoconductive property andimmune response of poly(ether ether ketone) by modification with calciumions, #N/A 3(44) (2015) 8738-8746.）。柠檬酸具有很强的螯合能力和有限的酸刻蚀能力，螯合产物柠檬酸钛复合物是促进成纤维细胞分化的有效物质。因此，柠檬酸也可以作为钛基板与钙离子之间的桥梁。本专利采用柠檬酸/氢氧化钙饱和溶液进行水热处理，在钛表面构建含钙涂层。
发明内容
解决的技术问题：本发明提供一种钛表面柠檬酸-含钙化学转化膜及其制备方法和应用。该方法原料简单，易于操作，方便控制，稳定性佳；经该方法制备的钛表面有良好的生物学活性，明显促进钙磷的沉积，有利于成骨细胞的粘附、增殖和分化，有效提高钛基牙种植体的早期骨整合能力，改善其临床应用效果。
技术方案：一种钛表面柠檬酸-含钙化学转化膜的制备方法，包括如下步骤：配制化学转化基础液：在10wt.%柠檬酸溶液中添加[Ca(OH)2]至饱和；将经大颗粒喷砂酸蚀（SLA）处理后的医用纯钛片浸泡于化学转化基础液中进行化学转化处理；将所得钛片清洗、干燥，得到钛表面柠檬酸钙化学转化膜；其中，化学转化基础液中柠檬酸根浓度为100g/L，钙离子的浓度为22.3g/L。
优选的，化学转化的温度为80-100℃。化学转化的时间为20-30min。
优选的，钛片的清洗方法为依次用丙酮、乙醇、去离子水于室温下超声清洗10-15min。
优选的，钛片的干燥方法为在55℃的烘箱中晾干。
上述方法制得的钛表面柠檬酸-含钙化学转化膜。
钛表面柠檬酸-含钙化学转化膜在制备提升种植体在骨愈合过程中稳定性材料中的应用。
有益效果：利用本发明可在SLA处理的钛片表面获得柠檬酸-含钙化学转化膜，整个制备过程原料简单，易于操作，方便控制，稳定性佳，对环境不造成污染。经该方法制备的钛表面有良好的亲水性及生物学活性，在体外模拟体液浸泡中能有效促进钙磷的沉积。有利于成骨细胞的粘附、增殖和分化，有效提高钛基牙种植体的早期骨整合能力。
附图说明
图1为实施例1中制得的钛片试样进行XPS分析获得的元素图谱；
图2为实施例1中制得的钛片试样表面的扫描电镜照片（放大5000倍）；
图3为实施例1中制得的钛片试样表面的扫描电镜照片（放大10000倍）；
图4为经过SLA处理的钛片试样沉浸于模拟体液中1天获得的扫描电镜照片（放大1000倍）；
图5为实施例1中制得的钛片试样沉浸于模拟体液中1天获得的扫描电镜照片（放大1000倍）；
图6为经过SLA处理的钛片试样的水接触角；
图7为实施例1中制得的钛片试样的水接触角；
图8为实施例1中制得的钛片试样浸泡在PBS中钙离子释放的结果；
图9为经过SLA处理的钛片试样和实施例1中制得的钛片试样人骨髓干间充质细胞粘附12h罗丹明鬼笔环肽染色图片；
图10为经过SLA处理的钛片试样和实施例1中制得的钛片试样人骨髓干间充质细胞增殖3dEDU染色图片；
图11为经过SLA处理的钛片试样和实施例1、2、3中制得的钛片试样人骨髓干间充质细胞成骨诱导4d、7d碱性磷酸酶活性检测。
具体实施方式
下面的实施例可使本专业技术人员更全面地理解本发明，但不以任何方式限制本发明。
实施例1
（1）配制化学转化基础液：在10%柠檬酸溶液中添加Ca(OH)2·2H2O至饱和，柠檬酸根浓度为100g/L，钙离子的浓度为22.3g/L；
（2）将经大颗粒喷砂酸蚀（SLA）处理后的医用纯钛片浸泡于化学转化基础液中，在100℃的条件下处理20min；
（3）将处理后的钛片依次用丙酮、乙醇、去离子水于室温下超声清洗10-15min；
（4）将处理后的钛片在55℃的烘箱中晾干。
实施例2
（1）配制化学转化基础液：在10%柠檬酸溶液中添加Ca(OH)2·2H2O至饱和，柠檬酸根浓度为100g/L，钙离子的浓度为22.3g/L；
（2）将经大颗粒喷砂酸蚀（SLA）处理后的医用纯钛片浸泡于化学转化基础液中，在90℃的条件下处理25min；
（3）将处理后的钛片依次用丙酮、乙醇、去离子水于室温下超声清洗10-15min；
（4）将处理后的钛片在55℃的烘箱中晾干。
实施例3
（1）配制化学转化基础液：在10%柠檬酸溶液中添加Ca(OH)2·2H2O至饱和，柠檬酸根浓度为100g/L，钙离子的浓度为22.3g/L；
（2）将经大颗粒喷砂酸蚀（SLA）处理后的医用纯钛片浸泡于化学转化基础液中，在80℃的条件下处理30min；
（3）将处理后的钛片依次用丙酮、乙醇、去离子水于室温下超声清洗10-15min；
（4）将处理后的钛片在55℃的烘箱中晾干。
Claims (4)
1.一种钛表面柠檬酸-含钙化学转化膜的制备方法，其特征在于，包括如下步骤：配制化学转化基础液：在10wt.%柠檬酸溶液中添加Ca(OH)2至饱和；将经大颗粒喷砂酸蚀（SLA）处理后的医用纯钛片浸泡于化学转化基础液中进行化学转化处理；将所得钛片清洗、干燥，得到钛表面柠檬酸钙化学转化膜；其中，化学转化基础液中柠檬酸根浓度为100g/L，钙离子的浓度为22.3g/L；化学转化的温度为100℃；化学转化的时间为20min；钛片的干燥方法为在55℃的烘箱中晾干。
2.根据权利要求1所述钛表面柠檬酸-含钙化学转化膜的制备方法，其特征在于：钛片的清洗方法为依次用丙酮、乙醇、去离子水于室温下超声清洗10-15min。
3.权利要求1或2所述方法制得的钛表面柠檬酸-含钙化学转化膜。
4.权利要求3所述钛表面柠檬酸-含钙化学转化膜在制备提升种植体在骨愈合过程中稳定性材料中的应用。
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| CN105696054A (zh) * | 2016-01-18 | 2016-06-22 | 南京医科大学附属口腔医院 | 一种喷砂酸蚀钛表面形成含钙纳米薄片膜层的制备方法 |
| CN106823005A (zh) * | 2016-12-21 | 2017-06-13 | 南京航空航天大学 | 一种环保型超亲水牙种植体活化表面的制备方法 |
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| CN105696054A (zh) * | 2016-01-18 | 2016-06-22 | 南京医科大学附属口腔医院 | 一种喷砂酸蚀钛表面形成含钙纳米薄片膜层的制备方法 |
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