CN116180065A - 一种表面改性的镍钛合金材料及其制备方法和应用 - Google Patents
一种表面改性的镍钛合金材料及其制备方法和应用 Download PDFInfo
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- CN116180065A CN116180065A CN202310138134.9A CN202310138134A CN116180065A CN 116180065 A CN116180065 A CN 116180065A CN 202310138134 A CN202310138134 A CN 202310138134A CN 116180065 A CN116180065 A CN 116180065A
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- Prior art keywords
- nickel
- titanium alloy
- cerium
- titanium
- alloy material
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- 239000000956 alloy Substances 0.000 title claims abstract description 41
- 238000002360 preparation method Methods 0.000 title claims abstract description 18
- UDZPMBOTTFFAME-UHFFFAOYSA-H nickel(2+) titanium(4+) hexahydroxide Chemical compound [OH-].[Ni+2].[Ti+4].[OH-].[OH-].[OH-].[OH-].[OH-] UDZPMBOTTFFAME-UHFFFAOYSA-H 0.000 claims abstract description 49
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- HSJPMRKMPBAUAU-UHFFFAOYSA-N cerium(3+);trinitrate Chemical compound [Ce+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O HSJPMRKMPBAUAU-UHFFFAOYSA-N 0.000 claims abstract description 12
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- Materials For Medical Uses (AREA)
Abstract
本发明涉及一种表面改性的镍钛合金材料及其制备方法和应用,该表面改性的镍钛合金材料包括由缺陷态镍钛氢氧化物层和生成于该缺陷态镍钛氢氧化物层的缺陷态氧化铈形成的复合涂层。该表面改性的镍钛合金材料的制备方法包括:使用氢氧化钾溶液对镍钛合金进行碱热预处理,制备纳米片状镍钛氢氧化物,随后沸水浴除去多余的氢氧化钾及金属离子;将预处理的含有镍钛氢氧化物的镍钛合金浸没于均苯三甲酸与硝酸铈混合溶液中,通过溶剂热反应在样品表面形核,并生长出铈基金属有机骨架改性层;再在氩气中进行热处理,从而获得表面改性后的镍钛合金。本发明提供的改性镍钛合金材料可用于制造与肿瘤组织接触的医用镍钛合金器件。
Description
技术领域
本发明涉及生物医用金属材料表面改性技术领域,尤其涉及一种表面改性的镍钛合金材料及其制备方法和应用,具体包括镍钛合金支架表面构建缺陷态镍钛氢氧化物和氧化铈复合涂层。
背景技术
胃肠道(GI)癌症是指胃肠道及其附属器官的恶性肿瘤,主要包括食道、胃、肝脏、胆道系统、胰腺和结肠等,在全球范围内具有很高的发病率和死亡率。然而,由于缺乏独特的早期症状,消化道恶性肿瘤通常在晚期才被诊断出来,此时姑息治疗是延长患者生存时间和改善患者生活质量的最佳治疗选择。镍钛合金支架由于其良好的生物相容性和特殊的形状记忆效应在临床上被广泛用于缓解消化道癌症引起的梗阻的姑息治疗。
如CN209695473U公开了一种刚度自适应型镍钛合金食道支架,其是由镍钛合金丝编织而成的变间距的柱形网状支撑结构,该柱形网状支撑结构由多股镍钛合金丝分成两组后分别以顺时针和逆时针方向缠绕而成,顺时针缠绕的镍钛合金丝和逆时针缠绕的镍钛合金丝相互交叉地以一压一平的方式缠绕,形成多个菱形网格;且按照两组镍钛合金丝的缠绕角度不同形成多个不同刚度的区域。
然而,镍钛合金不具备抗肿瘤能力,术后支架周围的肿瘤侵袭和肿瘤过度生长可能导致管腔的再次阻塞。因此,镍钛合金支架缺乏的抗肿瘤能力限制了其在胃肠道癌症姑息治疗中的应用。
CN105343941B公开了一种表面改性生物医用镍钛合金,其材料表面主要成分为硒掺杂的镍钛层状双氢氧化物。镍钛层状双氢氧化物本身可以产生羟基自由基,具有一定的选择性抑癌抗菌作用。掺杂硒以后,硒具有一定的还原性,会与镍钛层状双氢氧化物产生的羟基自由基发生反应,因此通过调节硒的掺杂量可实现对材料羟基自由基释放量的调控,进而调节材料的抑癌抗菌能力。
现有技术大多将化疗药物加载到支架表面,以赋予支架抗肿瘤能力。然而,药物的早期突释将不可避免地对腔内的正常组织造成严重损害,而且很难实现药物在肿瘤部位的长期释放,以达到临床治疗所需的剂量。因此,如何改善镍钛合金表面性能,使其具有智能响应性和低副作用高效抗肿瘤功能,提高其实际应用价值,仍是本领域技术人员的研究方向之一。
此外,一方面由于对本领域技术人员的理解存在差异;另一方面由于申请人做出本发明时研究了大量文献和专利,但篇幅所限并未详细罗列所有的细节与内容,然而这绝非本发明不具备这些现有技术的特征,相反本发明已经具备现有技术的所有特征,而且申请人保留在背景技术中增加相关现有技术之权利。
发明内容
针对现有技术之不足,本发明提供了一种表面改性的镍钛合金材料及其制备方法和应用,旨在解决现有技术中存在的至少一个或多个技术问题。
为实现上述目的,本发明提供了一种表面改性的镍钛合金材料,包括铈掺杂的缺陷镍钛氢氧化物层,铈以缺陷态氧化物的形式掺杂于缺陷镍钛氢氧化物层。
优选地,本发明涉及另一种表面改性的镍钛合金材料,包括由碱热处理制备的镍钛氢氧化物经热还原形成的缺陷态镍钛氢氧化物层和铈基金属有机骨架热解形成的缺陷态氧化铈形成的复合涂层。
优选地,本发明涉及又一种表面改性的镍钛合金材料,包括由缺陷态镍钛氢氧化物层和生成于缺陷态镍钛氢氧化物层的缺陷态氧化铈形成的复合涂层。特别地,缺陷态氧化铈原位生成于缺陷态镍钛氢氧化物层表面。
优选地,本发明所涉及的缺陷态镍钛氢氧化物层为纳米片层结构。具体地,该纳米片层结构的尺寸约为100~500nm。
优选地,本发明所涉及的金属有机骨架为纳米棒状结构。具体地,该金属有机骨架(铈基)的直径约为100~200nm。
优选地,本发明涉及一种表面改性的镍钛合金材料的制备方法,包括如下步骤:
将镍钛合金进行碱热预处理以制备含有镍钛氢氧化物的镍钛合金前驱体;
将含有镍钛氢氧化物的镍钛合金前驱体浸没于含有铈的酸溶液中以原位生成铈基金属有机骨架;
在惰性保护气体中对生成铈基金属有机骨架的含有镍钛氢氧化物的镍钛合金前驱体进行热处理以制备缺陷态镍钛氢氧化物和金属有机骨架衍生氧化铈复合涂层。
优选地,热处理温度为300~600℃。进一步地,热处理温度为600℃。较佳地,热处理温度为450℃。
优选地,本发明中,含有铈的酸溶液为均苯三甲酸与硝酸铈的混合溶液。
优选地,本发明还涉及一种表面改性的镍钛合金材料,或利用本发明所述的制备方法制备的表面改性的镍钛合金材料在制造与肿瘤组织接触的医用镍钛合金器件中的应用。
优选地,本发明还涉及一种用于与肿瘤组织部位接触的镍钛合金支架,该镍钛合金支架可以利用前述的表面改性的镍钛合金材料,或前述制备方法制备的表面改性的镍钛合金材料制成。
本发明的有益技术效果包括:经本发明的改性处理后,镍钛合金表面缺陷态镍钛氢氧化物具有优良的光热转化能力,可有效吸收并将近红外光转变成热能,对材料周围的癌细胞造成热损伤,且产生的局部高温可促进氧化铈的催化能力,使铈基金属有机骨架衍生的缺陷态氧化铈具备过热增强的类氧化物酶催化性,对周围癌细胞造成严重的氧化损伤,从而展现出良好的近红外光增强抗肿瘤能力;另外,本发明提供了一种易于操作的表面改性的镍钛合金材料的制备方法,该制备方法稳定,成本低,尤其是通过该方法制备的镍钛合金材料材料性能稳定,且其具备的光热转换能力可赋予镍钛合金支架优异的抗肿瘤能力,可用于与肿瘤组织接触的医用镍钛合金器件的制造,具有良好的市场应用前景。
附图说明
图1示出了不同状态下的镍钛合金(NiTi)的表面扫描电镜(SEM)图,其中,(a)示出了未处理的镍钛合金(NiTi)表面扫描电镜(SEM)图;(b)示出了镍钛合金表面铈基金属有机骨架样品(标记为Ce-BTC)的表面扫面电镜(SEM)图;(c)示出了Ce-BTC在第一温度下热处理之后样品(第一温度为450℃,标记为Ce-BTC-450)的表面扫描电镜(SEM)图;(d)示出了Ce-BTC在第二温度下热处理之后样品(第二温度为600℃,标记为Ce-BTC-600)的表面扫描电镜(SEM)图;
图2示出了镍钛合金(NiTi)碱热处理后样品(标记为AHT-NiTi)的表面的扫描电镜(SEM)图;
图3示出了各组样品表面的X射线衍射(XRD)全谱图;
图4示出了各组样品表面的拉曼(Raman)光谱图;
图5示出了Ce-BTC、Ce-BTC-450和Ce-BTC-600样品表面的Ce 3dXPS高分辨谱;
图6示出了AHT-NiTi及其热处理后样品(标记为AHT-NiTi-450)表面的Ti 2pXPS高分辨谱;
图7示出了NiTi、Ce-BTC、Ce-BTC-450和Ce-BTC-600样品表面的紫外-可见-近红外(UV-VIS-NIR)吸收光谱;
图8示出了NiTi、Ce-BTC、Ce-BTC-450和Ce-BTC-600样品在近红外光(NIR)辐照下在水中的升温曲线;
图9示出了NiTi、Ce-BTC、Ce-BTC-450和Ce-BTC-600样品在弱碱性缓冲液中催化产生TMBox的吸收光谱;
图10示出了NiTi、Ce-BTC、Ce-BTC-450和Ce-BTC-600样品在弱酸性缓冲液中催化产生TMBox的吸收光谱;
图11示出了近红外光(NIR)辐照下各组样品在pH为6的缓冲液中催化产生TMBox的吸收光谱;
图12示出了有、无近红外光(NIR)辐照时各组样品表面胆囊癌细胞的相对细胞活性;
图13示出了有、无近红外光辐照(NIR)时各组样品表面胆囊癌细胞的胞内活性氧含量;
图14示出了各组样品表面胆囊上皮细胞的增殖情况;
图15示出了本发明所述的表面改性的镍钛合金材料的制备流程;
图16示出了AHT-NiTi及其热处理后样品(标记为AHT-NiTi-450)的XPS高分辨谱,其中,(a)示出了AHT-NiTi样品表面的Ni 2pXPS高分辨谱,(b)示出了AHT-NiTi样品表面的Ti 2pXPS高分辨谱,(c)示出了AHT-NiTi样品表面的O1sXPS高分辨谱,(d)示出了AHT-NiTi-450样品表面的Ni 2pXPS高分辨谱,(e)示出了AHT-NiTi-450样品表面的Ti 2pXPS高分辨谱,(f)示出了AHT-NiTi-450样品表面的O1sXPS高分辨谱。
具体实施方式
本发明提供了一种表面改性的镍钛合金材料,其包括由缺陷态镍钛氢氧化物层和原位生成于缺陷态镍钛氢氧化物层的缺陷态氧化铈形成的复合涂层。或者,本发明所述表面改性的镍钛合金材料主要成分为铈掺杂的缺陷态镍钛氢氧化物,其中,铈以缺陷态氧化铈的形式掺杂于该缺陷态镍钛氢氧化物。
具体地,该镍钛合金材料包括由碱热处理制备的镍钛氢氧化物经热还原形成的缺陷态镍钛氢氧化物层和铈基金属有机骨架热解形成的缺陷态氧化铈形成的复合涂层。
特别地,本发明所述的铈通过溶剂热反应在镍钛合金(NiTi)样品表面原位成核并生长出铈基金属有机骨架。
特别地,本发明中,缺陷态镍钛氢氧化物层为纳米片层结构,其尺寸约为100~500nm。铈基金属有机骨架纳米棒状结构,其直径约为100~200nm。
此外,本发明还提供一种表面改性的镍钛合金材料的制备方法,可以包括如下步骤:
将镍钛合金进行碱热预处理以制备镍钛氢氧化物;
将镍钛氢氧化物浸没于含有铈的酸溶液中以原位生成铈基金属有机骨架;
在惰性保护气体中对上述混合溶液进行热处理以制备缺陷态镍钛氢氧化物和金属有机骨架衍生氧化铈复合涂层。
进一步地,本发明所述的表面改性的镍钛合金材料的制备方法还包括将碱热处理后的镍钛氢氧化物进行沸水浴处理,以去除其中多余的氢氧化钾及金属离子等。
根据一种优选实施方式,除铈元素之外,可变价的过渡金属元素如锰、铁、钴、镍、铜、钼、钨等,以及贵金属元素铂、金、钯等具有较好的催化活性,可替代铈元素进行肿瘤的催化治疗。因此,针对改性镍钛合金材料,本发明提供的铈基金属有机骨架及其缺陷态氧化物也可以是由上述可变价的过渡金属和/或贵金属元素中的一个或多个形成。
下面结合附图对本发明的较佳实施例进行详细阐述,以使本发明的优点和特征能更易于被本领域技术人员理解,从而对本发明的保护范围做出更为清楚明确的界定。
实施例1
本实施例提供了表面改性的镍钛合金材料的具体制备过程。
(a)将镍钛片在HF、HNO3和水(体积比为1:5:4)的混合溶液中超声清洗两次,每次5分钟,然后用超纯水和乙醇先后超声清洗10分钟,自然晾干后,将镍钛片置于反应釜内,加入5M氢氧化钾溶液,80℃反应6h,自然冷却后取出样品,置于沸水中清洗30min;(b)将预处理后的镍钛片放入反应釜内,加入含约3.3mM均苯三甲酸和10mM硝酸铈的反应液,并在120℃反应12h,自然冷却后取出,使用乙醇和超纯水依次各清洗三次;(c)将上述样品置于管式炉内,在氩气氛围中热处理2h。
根据一种优选实施方式,碱热处理镍钛合金(NiTi)所需氢氧化钾的浓度约为1~10M。优选地,氢氧化钾的浓度为5~7M。热处理镍钛合金(NiTi)所需的时间约为2~12h。优选地,热处理时间为6~8h。此外,碱热处理后,对碱热处理的镍钛合金(NiTi)材料需沸水浴处理10min(优选30min)以上以去除其中残留的氢氧化钾及金属离子。
根据一种优选实施方式,镍钛合金(NiTi)材料与均苯三甲酸和硝酸铈的混合溶液的溶剂热反应温度约为100~120℃,反应时间约为8~24h。其次,溶液中均苯三甲酸的浓度约为1~5mM,硝酸铈的浓度约为3~15mM,溶剂为DMF。
根据一种优选实施方式,氩气氛围中热处理的温度约为300~600℃。热处理时间约为1~3h。
根据一种优选实施方式,图1(a)~(d)为实施例中相关附图,根据图1可以看出酸洗后的镍钛合金(NiTi)表面较为粗糙,存在较大的沟壑;生长的铈基金属有机骨架(Ce-BTC)为纳米棒状结构,尺寸在100-200nm之间。在氩气氛围中热解后,Ce-BTC-450和Ce-BTC-600的表面纳米棒形貌无明显的变化。
根据一种优选实施方式,图2为本实施例中经过碱液及热处理的镍钛合金(NiTi)表面扫描电镜(SEM)图片。根据图2的结果显示出,碱热处理后,镍钛合金(NiTi)表面分布镍钛氢氧化物纳米片,其粗糙的表面结构为铈基金属有机骨架(Ce-BTC)的生长提供了大量的成核位点。
根据一种优选实施方式,图3为本实施例中NiTi、Ce-BTC、Ce-BTC-450和Ce-BTC-600样品的XRD谱图。结果显示,在所有样品表面均能检测到镍钛合金(NiTi)的特征衍射峰,Ce-BTC-450和Ce-BTC-600样品上还检测到Ni3Ti相的特征衍射峰,说明高温热处理促进了Ni3Ti相的生成。此外,在Ce-BTC样品表面检测到位于10.1°和17.2°的衍射峰,证实在镍钛合金(NiTi)表面成功制备了铈(Ce)基金属有机骨架。在Ar气氛中热解后,Ce-BTC的特征衍射峰消失,Ce-BTC-450和Ce-BTC-600样品表面并出现氧化铈(CeO2)的特征衍射峰,可能的原因是Ce-BTC热解生成的碳骨架抑制了铈氧团簇之间的聚集,因此未形成高结晶性的氧化铈晶粒。
根据一种优选实施方式,图4为本实施例中NiTi、Ce-BTC、Ce-BTC-450和Ce-BTC-600样品的拉曼(Raman)谱图。结果显示,Ce-BTC样品表面检测到的位于约462cm-1的拉曼峰,主要对应Ce-O键的F2g振动模式。特别地,Ce-BTC-450和Ce-BTC-600样品表面位于约462cm-1的拉曼峰逐渐增强,说明在Ar气氛下,随热解温度的升高,Ce-O团簇逐渐聚集长大。
根据一种优选实施方式,图5为本实施例中Ce-BTC、Ce-BTC-450和Ce-BTC-600样品表面的Ce 3d XPS高分辨谱。结果表明,铈(Ce)主要以氧化物的形式存在,相应的铈离子价态浓度定量结果表明,Ce-BTC、Ce-BTC-450和Ce-BTC-600样品中Ce3+的浓度分别为31.2%、42.6%和22.4%。以上结果证实,Ce-BTC-450样品表面Ce3+的浓度较低,意味着其铈氧团簇表面暴露更多的氧空位,将有利于催化反应的进行。
根据一种优选实施方式,图6为本实施例中AH-NiTi(碱热处理后的镍钛合金)和AH-NiTi-450样品表面Ti 2p XPS高分辨谱。结果表明,在氩气中热还原后,镍钛合金(NiTi)样品表面缺陷度(即Ti3+含量)明显上升,将有利于对近红外光的吸收。
根据一种优选实施方式,图15示出了本发明所述的表面改性的镍钛合金材料的制备流程。具体而言,参见图15,该制备流程包括:步序一:将镍钛合金进行碱热预处理以制备含有镍钛氢氧化物的镍钛合金前驱体;步序二:将该含有镍钛氢氧化物的镍钛合金前驱体浸没于含有铈的酸溶液中以原位生成铈基金属有机骨架;步序三:在惰性保护气体中对原位生成有铈基金属有机骨架的含有镍钛氢氧化物的镍钛合金前驱体进行热处理以制备缺陷态镍钛氢氧化物和金属有机骨架衍生氧化铈复合涂层。进一步地,通过该方法获得的改性镍钛合金材料具有良好的生物相容性,并具备过热增强的类氧化物酶催化性,能够癌细胞造成氧化损伤,并持续抑制肿瘤细胞的扩散,特别是在近红外光(NIR)辐射下能够增强对肿瘤细胞的抑制。
根据一种优选实施方式,本发明提供的改性镍钛合金材料的各层结构的物质组成可通过XPS分析得到,结果如下:
具体地,改性镍钛合金材料的下层主要是镍钛氢氧化物/氧化物,主要包含Ni、Ti、O元素,C元素主要为改性镍钛合金材料表面吸附的碳酸盐或污染物。改性镍钛合金材料的上层主要为铈基金属有机骨架衍生的氧化铈和有机配体衍生的碳骨架,主要包含Ni、Ti、O、C、Ce元素。百分比含量如上表所示。
根据一种优选实施方式,本发明提供的镍钛合金材料的下层可由化学式NixTiyCmOn表述,其中,17.4≤x≤39.1,11.4≤y≤30.6,13.0≤m≤27.7,29.4≤n≤32.4,其中x、y、m和n对应于质量分数。进一步地,该镍钛合金材料的上层可由化学式CoOpCeq表述,其中,35.6≤o≤37.4,21.1≤p≤25.4,33.3≤q≤38.2,其中o、p和q对应于质量分数。特别地,由于材料表面吸附空气中的碳或有机物污染可能会导致镍钛基底表面碳含量升高,所以XPS分析数据中镍钛基底表现出较高碳含量。此外,此结果仅表示表面元素组成,不能表示上下层整体的元素组成。
根据一种优选实施方式,镍钛氢氧化物热还原后会转变为缺陷态镍钛氢氧化物/氧化物(具有大量的Ti3+和氧空位)。因为生成的氢氧化物层较薄,或结晶性较差,XRD并未表征出其相应的特征峰。XPS分析结果如图16所示,可见热还原后会镍钛氢氧化物中Ti3+比例升高,氧空位含量增加(表面氧/晶格氧比例升高)。XPS分析结果虽未区分出氢氧化物和氧化物,但由于高温会促进氢氧化物脱水转变成氧化物,故基于文献的研究结果,热还原后的产物认为是缺陷态镍钛氢氧化物/氧化物。
实施例2
本实施例示出了不同样品于不同光线照射下的光吸收能力和光热转换能力的表征结果。
具体地,采用紫外可见吸收光谱仪(Lambda 750,PerkinElmer,USA)分别检测NiTi、Ce-BTC、Ce-BTC-450和Ce-BTC-600样品表面的吸收光谱。将各组样品分别放置去离子水中(24孔板,1mL),并用0.5W/cm2近红外光照射各样品表面,以测试样品的光热效果。
根据一种优选实施方式,图7为本实施例中各样品的吸收光谱。结果表明,NiTi在400~850nm波长范围内具有较低的吸收系数。Ce-BTC的吸收系数略有上升,而Ce-BTC-450与Ce-BTC-600具有较高的光吸收系数。
根据一种优选实施方式,图8为本实施例中各组样品在近红外光(NIR)辐照下在水中的升温曲线。结果表明,在超纯水中,用功率密度为0.50W/cm2的近红外光(NIR)辐照各组样品10分钟,NiTi、Ce-BTC、Ce-BTC-450和Ce-BTC-600样品表面温度可分别达到39.8℃、44.9℃、50.8℃和50.6℃,说明Ce-BTC-450和Ce-BTC-600具有较强的光热转换能力。
实施例3
本实施例示出了不同样品于不同缓冲液中催化产生TMBox的吸收表征结果。
具体地,使用TMB作为显色底物分别检测NiTi、Ce-BTC、Ce-BTC-450和Ce-BTC-600样品的类氧化物酶活性,并研究近红外光(NIR)辐照对各组样品类氧化物酶活性的影响。
特别地,铈基金属骨架衍生的缺陷态氧化铈具有较强的类氧化物酶活性,可催化氧气产生活性氧,而且在近红外光(NIR)辐照产生的高温可进一步提高其催化活性。
根据一种优选实施方式,图9为本实施例中改性后样品在弱碱性缓冲液下的催化活性。结果表明,在弱碱性缓冲液中,各组样品均不具有类氧化物酶活性。
根据一种优选实施方式,图10为本实施例中改性后样品在弱酸性缓冲液下的催化活性。结果表明,在弱酸性条件下,Ce-BTC-450具有最高的类氧化物酶活性,这与氧化铈(CeO2)的缺陷程度相关。
根据一种优选实施方式,图11为本实施例中近红外光(NIR)辐照对各组样品催化活性的影响。结果表明,在近红外光(NIR)辐照下,样品产生的高温可促进催化反应的进行,特别是Ce-BTC-450催化活性提升较大。
实施例4
本实施例示出了不同样品对于癌细胞抑制的表征结果。
在NiTi、Ce-BTC、Ce-BTC-450和Ce-BTC-600样品表面以2×105/孔密度接种胆囊癌细胞(GBC-SD),培养36h后采用近红外光辐照。
根据一种优选实施方式,图12为本实施例中在有、无近红外光(NIR)辐照时各组样品表面胆囊癌细胞的相对细胞活性。结果显示,近红外光(NIR)辐照前,相比于镍钛合金(NiTi)样品,Ce-BTC、Ce-BTC-450和Ce-BTC-600样品对人胆囊癌细胞(GBC-SD)具有明显的抑制作用,其中Ce-BTC-450样品表面细胞活性最低。近红外光(NIR)辐照后,NiTi样品表面细胞活性无明显变化。Ce-BTC、Ce-BTC-450和Ce-BTC-600样品表面细胞活性都有下降,但Ce-BTC样品在近红外光(NIR)辐照下温度升高有限,对人胆囊癌细胞(GBC-SD)的杀伤作用较弱。Ce-BTC-450和Ce-BTC-600样品在近红外光(NIR)辐照下能升到50℃左右,可对其表面的细胞产生热损伤,明显降低人胆囊癌细胞(GBC-SD)的细胞活性。具体地,近红外光(NIR)辐照5~10min,改性表面癌细胞活性降低80%以上。
根据一种优选实施方式,图13为本实施例中在有、无近红外光(NIR)辐照时各组样品表面胆囊癌细胞的胞内相对活性氧含量。近红外光(NIR)辐照前,Ce-BTC、Ce-BTC-450和Ce-BTC-600样品表面细胞的胞内活性氧水平约为NiTi样品表面的2.8、5.8和1.7倍,细胞内活性氧含量与材料本身的类氧化物酶活性相对应。
特别地,在近红外光(NIR)辐照后,Ce-BTC、Ce-BTC-450和Ce-BTC-600样品表面细胞内活性氧水平分别约为NiTi样品表面的5.5、16.4和6.1倍。近红外光(NIR)辐照能明显促进样品表面细胞内活性氧的产生,可能的原因有两个,一个是光热能增强样品的类氧化物酶活性能够促使胞内产生更多的活性氧;另一个是过热造成细胞功能紊乱,氧化还原平衡受到破坏。
实施例5
根据一种优选实施方式,图14为本实施例中改性样品表面胆囊上皮细胞的增值活性。具体地,分别在NiTi、Ce-BTC、Ce-BTC-450和Ce-BTC-600样品表面以5×104/孔密度接种胆囊上皮细胞(HGBEC),分别培养1、4、7天。结果显示,改性后样品对胆囊上皮细胞具有良好的细胞相容性。
实施例6
本发明提供的一种表面改性的镍钛合金材料,其具有优异的光热性能及纳米酶催化活性,能在近红外光(NIR)辐射增强下实现良好的肿瘤的抑制作用。鉴于此,本实施例还提供一种利用该表面改性的镍钛合金材料制成的镍钛合金支架,该镍钛合金支架可用于患者肿瘤组织部位的支撑。
具体地,本实施例所述的镍钛合金支架可以是食管支架、肠道支架、气管支架、胆道支架、尿道支架、外周血管支架和心内血管支架等。进一步地,上述例举的支架都可以采用本发明所述的改性镍钛合金材料制成。特别地,因上述支架的具体结构现有技术已十分成熟,因此各支架所涉及的具体结构在本实施例中不做详细介绍,本实施例意在提供镍钛合金材料方面的改进,而非对具体支架结构的改进。
另外,应当理解的是,上述所例举的支架类型不应理解为是对本发明具体应用的限制,本领域技术人员参照本发明公开的内容完全可以将其应用至包含镍钛合金支架在内的其他镍钛合金器件中。
需要注意的是,上述具体实施例是示例性的,本领域技术人员可以在本发明公开内容的启发下想出各种解决方案,而这些解决方案也都属于本发明的公开范围并落入本发明的保护范围之内。本领域技术人员应该明白,本发明说明书及其附图均为说明性而并非构成对权利要求的限制。本发明的保护范围由权利要求及其等同物限定。本发明说明书包含多项发明构思,诸如“优选地”、“根据一个优选实施方式”或“可选地”均表示相应段落公开了一个独立的构思,申请人保留根据每项发明构思提出分案申请的权利。
Claims (10)
1.一种表面改性的镍钛合金材料,其特征在于,包括铈掺杂的缺陷镍钛氢氧化物层,其中,所述铈以缺陷态氧化物的形式掺杂于所述缺陷镍钛氢氧化物层。
2.一种表面改性的镍钛合金材料,其特征在于,包括由镍钛氢氧化物还原的缺陷态镍钛氢氧化物层和铈基金属有机骨架衍生的缺陷态氧化铈形成的复合涂层。
3.一种表面改性的镍钛合金材料,其特征在于,包括由缺陷态镍钛氢氧化物层和生成于所述缺陷态镍钛氢氧化物层的缺陷态氧化铈形成的复合涂层。
4.根据权利要求1~3任一项所述的表面改性的镍钛合金材料,其特征在于,所述缺陷态镍钛氢氧化物层为纳米片层结构。
5.根据权利要求1~3任一项所述的表面改性的镍钛合金材料,其特征在于,所述缺陷态氧化铈由铈基金属骨架热解形成。
6.一种表面改性的镍钛合金材料的制备方法,其特征在于,包括:
将镍钛合金进行碱热预处理以制备含有镍钛氢氧化物的镍钛合金前驱体;
将所述含有镍钛氢氧化物的镍钛合金前驱体浸没于含有铈的酸溶液中以原位生成铈基金属有机骨架;
在惰性保护气体中对原位生成有铈基金属有机骨架的含有镍钛氢氧化物的镍钛合金前驱体进行热处理以制备缺陷态镍钛氢氧化物和金属有机骨架衍生氧化铈复合涂层。
7.根据权利要求6所述的制备方法,其特征在于,所述热处理温度为300~600℃,优选为600℃,更优选为450℃。
8.根据权利要求6所述的制备方法,其特征在于,所述含有铈的酸溶液为均苯三甲酸与硝酸铈的混合溶液。
9.根据权利要求1~3任一项所述的表面改性的镍钛合金材料,或根据权利要求6~8任一项所述的制备方法制备的表面改性的镍钛合金材料在制造与肿瘤组织接触的医用镍钛合金器件中的应用。
10.一种镍钛合金支架,用于与肿瘤组织部位接触,其特征在于,利用如权利要求1~3任一项所述的表面改性的镍钛合金材料,或权利要求6~8任一项所述的制备方法制备的表面改性的镍钛合金材料制成。
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