CN110896607A - 一种表面超电容修饰的材料及其制备方法和应用 - Google Patents

一种表面超电容修饰的材料及其制备方法和应用 Download PDF

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CN110896607A
CN110896607A CN201980001600.0A CN201980001600A CN110896607A CN 110896607 A CN110896607 A CN 110896607A CN 201980001600 A CN201980001600 A CN 201980001600A CN 110896607 A CN110896607 A CN 110896607A
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capacitance
super
layer
alloys
preparation
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CN110896607B (zh
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王国敏
王怀雨
胡良胜
朱剑豪
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China Morefound Technology Ltd Shenzhen
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China Morefound Technology Ltd Shenzhen
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Abstract

本发明公开了一种表面超电容修饰的材料及其制备方法和应用。具体而言，本发明向材料表面引入具有可控超电容特性材料并进行充电，充满电后的材料与细菌相互作用，短时间内实现对细菌呼吸链电子传递的干扰而抑制其生长繁殖，通过循环充放电可以在不损坏电容特性的前提下提高杀菌率，并且抑制生物膜的形成。该抗菌体系可以在不影响材料生物相容性前提下对抗菌过程进行定量控制，具有环保可控的优势。

Description

一种表面超电容修饰的材料及其制备方法和应用
技术领域
本发明涉及一种表面改性材料，具体涉及一种表面超电容修饰的材料及其制备方法和应用。
背景技术
随着临床医学和材料科学的不断发展，新的医用金属植入材料不断应用于临床，特别在骨科领域中，作为骨内金属植入体和硬组织修复材料的接骨板、髓内针、钉-棒系统以及人工关节假体等等医用金属植入材料得到了广泛的临床应用。但是对于生物有机体而言，医用金属植入材料毕竟还是异物，在物理和化学性能方面与体内环境还存在着巨大的区别。
医用合金植入材料在使用过程中特别容易出现以下三个问题：①合金材料中的微量元素的析出导致的潜在细胞生物毒性及组织器官的损伤；②随着使用年限的增加，潜在的关节假体材料的表面金属磨削导致的局部炎症反应；③植入材料的相关感染的风险，细菌生物膜的形成等等导致假体的松动等等。而植入物相关感染对外科医生来说，尤为棘手，一旦出现，便会导致灾难性后果。
钛合金因其具有卓越的生物相容性、抗腐蚀性以及适当的机械性能而作为植入体基底广泛应用于生物医学领域，但是现有的基于钛合金的生物医用材料自身不具有抗菌特性，而在体内，细菌滋生后往往容易形成具有胞外多聚物基质、有特定结构、抗性更强的生物膜，这一缺陷会导致外科植入手术失败，造成严重的术后感染，给患者带来病痛甚至死亡的风险，因此具有抗菌特性钛合金材料表面设计将有效解决困扰临床医生及患者的以上难题。最初的抗菌材料设计通常是向材料表面接枝抗生素或者抗菌肽而实现有效抗菌，除此之外，在材料表面修饰纳米金、银、石墨烯也可以实现表面的有效抗菌，进一步研究表明材料与细菌之间的电子传递应该在该类抗菌过程中起着关键作用。少部分研究表明修饰有电荷的材料表面也可以依赖于电子传递而有效抗菌。以上这些方法都在一步步推进抗菌材料的发展(Wang,G.et al.Extracellular electron transfer from aerobic bacteria toAu-loaded TiO2semiconductor without light:a new bacteria-killing mechanismother than localized surface plasmon resonance or microbial fuel cells.ACSAppl.Mater.Interfaces 8,24509-24516(2016).Chernousova,S.,Epple,M.Silver asantibacterial agent:ion,nanoparticle,and metal.Angew.Chem.Int.Ed.52,1636-1653(2013))。
通过对钛合金材料的表面设计可以实现有效抗菌因而提高其生物医学应用的成功率，但是目前的抗菌材料设计有以下缺陷，例如向材料表面接枝抗生素以及抗菌肽会引起严重的细菌耐药性，而耐药菌株的突变会加重临床感染。同时各种肽类材料易与机体发生免疫反应而增加了植入手术失败的风险。尽管上述依赖于纳米材料的抗菌表面设计以及向材料表面修饰电荷的方法因其直接干扰细菌呼吸链的电子传递来抑制细菌生长可以有效避免耐药菌株的突变以及降低免疫反应，但是目前这些抗菌表面的设计不能做到对电子传递的定量控制，且抗菌体系无法循环利用，同时，银纳米颗粒以及季铵盐的引入会降低材料的生物相容性而导致其体内应用推广进程缓慢。
发明内容
本发明的目的在于设计一种依赖于超电容特性材料的抗菌体系，用具有超电容特性的材料修饰材料表面，充满电荷的材料在无任何其他外界物质介入的情况下与细菌之间发生电子传递而可实现对材料与细菌之间电子传递的定量控制而更精准地实现抗菌。这一清洁环保的抗菌体系克服了现有抗菌表面设计引起安全隐患以及无法定量控制的缺陷。
本发明所采取的技术方案是：
本发明包括三部分内容。首先设计和制备具有超电容特性的材料表面，将材料接入电路而使其满载电荷，然后将材料断电并与细菌相互作用，短时间内实现对细菌呼吸链电子传递的干扰而抑制其生长繁殖。
具体而言，本发明的第一个方面涉及一种表面超电容修饰的材料，包括材料本体及表面的超电容层；其特征在于，所述材料本体选自金属材料或其它导体；其中，所述金属材料优选钛或其合金、铝或其合金、不锈钢、镍或其合金、锰或其合金、钨或其合金、锌或其合金；所述其它导体包括但不限于导电聚合物，导电聚合物的例子包括聚吡咯、聚乙炔、聚噻吩、聚苯胺等等。
所述超电容层是指表面电容大于10mF+cm-2的功能层；所述超电容层的表面电容大于50mF+cm-2，优选大于100mF+cm-2。
进一步地，所述金属材料更优选钛合金、铝合金、不锈钢、镍合金、锌合金；且所述超电容层优选二氧化钛纳米管阵列层、氧化锌纳米棒层或还原的氧化石墨烯。
根据本发明的超电容层，其中所述二氧化钛纳米管或氧化锌纳米棒的直径在10nm-1000nm之间，优选20-800nm，最优选50-500nm之间；所述纳米管或纳米棒的长度在500nm-10μm之间；优选800nm-5μm；最优选1-3μm。
更优选地，所述二氧化钛纳米管阵列层内还包括碳沉积；所述的氧化锌纳米棒层掺杂有银、金、铜或铂纳米颗粒。
根据本发明的另一方面涉及表面超电容修饰的材料的制备方法，其具体包括，对金属材料的表面进行阳极氧化。
根据本发明的制备方法，优选在阳极氧化之前先对金属材料进行抛光打磨，及清洗。
根据本发明的制备方法，其中所述清洗是依次用丙酮、酒精、去离子水超声清洗。
根据本发明的制备方法，其中所述阳极氧化使用的电解液为铵盐、低级醇、水以及多元醇的混合液。
根据本发明的制备方法，其中所述电解液中铵盐、低级醇、水以及多元醇的质量体积比为(1-10％)：(1-10％)：(1-10％)：(70-95％)。
根据本发明的制备方法，其中所述铵盐选自卤化铵，优选氟化铵、氯化铵、溴化铵。
根据本发明的制备方法，其中所述低级醇选自甲醇、乙醇、正丙醇、异丙醇、正丁醇、异丁醇、叔丁醇中的一种或多种。
根据本发明的制备方法，其中所述水使用去离子水。
根据本发明的制备方法，其中所述多元醇选自乙二醇或丙三醇。
根据本发明的制备方法，其中所述阳极氧化所用电压为10-100V，优选15-80V，最优选30-60V。
根据本发明的制备方法，其中所述阳极氧化的反应时间为20-1000min；优选30-800min；最优选40-500min。
根据本发明的方法，还可以进一步包括，将阳极氧化后得到的纳米管阵列放入真空管式炉进行真空退火实现碳沉积以增强电容特性。碳沉积所利用碳源为阳极氧化过程中的有机物质，将阳极氧化后的样品在高温下真空退火而实现碳沉积。
所述真空退火的退火温度优选为500-800℃，退火时间为1-5h，升温速率为1-20℃min-1。
根据本发明的另一方面涉及一种表面超电容修饰的材料的制备方法，其具体包括，通过水热方法在金属材料表面生长氧化锌纳米棒并通过磁控溅射修饰掺杂银、金、铜或铂纳米颗粒来实现，具体步骤如下：
氧化锌晶种制备：将醋酸锌和强碱溶于低级醇中，高速旋涂在金属材料表面，获得湿膜，加热，挥发溶剂和热解，得到带有晶种层的金属材料；
氧化锌纳米棒的生长：将(1)中样品置于反应釜中，加入锌盐和碱的混合水溶液，封闭反应，加热；后用磁控溅射方法溅射银、金、铜或铂纳米颗粒；所述碱优选六亚甲基四胺、氢氧化钠、氢氧化钾、氢氧化钙、氨水或其组合。
所述低级醇选自甲醇、乙醇、正丙醇、异丙醇、正丁醇、异丁醇、叔丁醇中的一种或多种；优选甲醇、乙醇或其组合。
所述锌盐选自硝酸锌、硫酸锌、醋酸锌、磷酸锌或其组合。
根据本发明的另一方面涉及一种表面超电容修饰的材料的制备方法，其具体包括，将金属材料作为电沉积的工作电极；将氧化石墨烯加入醇水溶液作为电沉积溶液，接入参比电极和对电极，以直流电进行电沉积，得到氧化石墨烯层；后将其置于联氨溶液中水热处理，得到还原的氧化石墨烯-金属复合材料。
根据本发明的另一方面涉及一种杀菌方法，其特征在于，使用上述的表面超电容修饰的材料。
根据本发明的杀菌方法，其具体步骤包括，将所述材料接入直流或者交流电路，对其进行充电，然后使所述材料与菌液接触。
所述充的电荷优选为正电。
根据本发明的杀菌方法，其中，当接入交流电路时，其电压峰峰值为2-40V，频率在1Hz-1MHz之间。
根据本发明的杀菌方法，其中，所述电路的电压设置参照电容响应区间，优选在0.1-50V之间；充电时间为5-180min，与菌液接触的时间在一分钟以上。
根据本发明的杀菌方法，其中，优选进行多次充电杀菌过程，更优选两次以上。
根据本发明的杀菌方法，其特征在于，可以利用机体运动过程中的机械能转化为电能进行反复充放电而实现循环杀菌。
根据本发明的杀菌方法，其中，进行循环杀菌还可以抑制生物膜的形成。
在本抗菌体系建立过程中，首先设计具有超电容特性的材料，将材料接入电路而使其满载电荷，然后将材料断电并与细菌相互作用，短时间内实现对细菌呼吸链电子传递的干扰而抑制其生长繁殖，通过循环充放电可以在不损坏电容特性的前提下提高杀菌率，并且抑制生物膜的形成。
本发明的有益效果是：
向材料表面引入具有可控超电容特性材料并进行充电，充满电后的材料与细菌相互作用即可实现对细菌呼吸链的干扰而实现有效抗菌。该抗菌体系可以在不影响材料生物相容性前提下对抗菌过程进行定量控制，具有环保可控的优势。
具体而言，与以往抗菌表面设计相比，本发明具有以下优点：
1.将电容特性材料引入抗菌模型中，避免了抗生素引起的耐药性发生。
2.与抗菌肽等生物活性材料不同，该材料避免了生物安全隐患。
3.本发明直接在金属材料表面原位生长二氧化钛纳米管阵列，并用一步退火法进行碳沉积；或者基于水热方法制备的氧化锌纳米棒以及基于电沉积方法制备的还原氧化石墨烯；表面修饰与基材结合更牢，不会发生修饰物的泄露流失。
4.该抗菌体系杀菌机理基于材料与细菌之间的电子传递，与以往药物释放表面杀菌机理相比更为简便、清洁。
5.本发明所涉及抗菌体系为局部抗菌体系，依赖于与细菌的接触，与释放离子或药物的抗菌表面相比可以精准杀死植入手术创口附近细菌，达到高效抗感染。
6.本体系可以与可穿戴能源装置相结合，利用机体运动过程中的机械能转化为电能进行反复充放电而实现循环杀菌。
7.本材料设计过程简单，技术成熟，适合批量生产。
8.本设计不会引起材料生物相容性的改变，保证其应用于人体的安全性。
9.本材料可以有效抑制材料表面生物膜的生成。
附图说明
图1a扫描电子显微镜下阳极氧化60min后在15℃min-1升温速率下真空退火后的二氧化钛纳米管阵列(TNT-C-15)表面及截面微观形态(标尺＝500nm)；以及，TNT表示空气中退火处理的二氧化钛纳米管阵列。
图1b原子力显微镜下观察到的TNT-C-15表面及截面微观形态(阳极氧化时间60min，真空退火升温速率15℃min-1)。
图1c透射扫描电子显微镜-电子能量损失能谱对TNT-C-15进行分析(阳极氧化时间60min，真空退火升温速率15℃min-1)。
图1d TNT-C-15与TNT的XRD图谱对比(阳极氧化时间60min，真空或者空气退火升温速率15℃min-1)。
图1e样品表面高分辨率的碳电子能谱图(在空气中升温速率为15℃min-1(TNT)，真空退火升温速率为5，10，15和20℃min-1，分别对应TNT-C-5、TNT-C-10、TNT-C-15和TNT-C-20)。
图1f用Ar+剥离样品表面6min后高分辨率的碳元素X射线光电子能谱图，剥离速度21nmmin-1。
图2a不同升温速率退火所得样品的循环伏安图，(在空气中升温速率为15℃min-1，真空退火升温速率为5，10，15和20℃min-1)。
图2b不同升温速率退火所得样品的充放电曲线，(在空气中升温速率为15℃min-1，真空退火升温速率为5，10，15和20℃min-1)。
图3扫描电子显微镜下水热合成氧化锌纳米棒并磁控溅射喷金2min后的微观表面形态。
图4a电沉积方法与水热结合制备的还原的氧化石墨烯的电容特性循环伏安图。
图4b电沉积方法与水热结合制备的还原的氧化石墨烯的电容特性-充放电曲线。
图5对TNT-C样品充电示意图。
图6a不同样品充满电后20min内杀菌率，(在空气中升温速率为15℃min-1，真空退火升温速率为5，10，15和20℃min-1)；其中P表示接正极，即充正电荷，N表示接负极，即充负电荷。
图6b不同样品充满电后180min内杀菌率，(在空气中升温速率为15℃min-1，真空退火升温速率为5，10，15和20℃min-1)。
图7 TNT-C在充电后20min内对表皮葡萄球菌以及铜绿假单胞杆菌的抗菌效率。
图8对TNT-C-15循环充放电三次所达到的抗菌效果(阳极氧化时间60min，真空退火升温速率15℃min-1)。
图9对TNT-C-15循环充放电8次后对生物膜的荧光染色结果(阳极氧化时间60min，真空退火升温速率15℃min-1)；其中DC表示直流电。
图10用交流电对TNT-C-15进行充电后样品对大肠杆菌和金黄色葡萄球菌的杀菌率(阳极氧化时间60min，真空退火升温速率15℃min-1)。
图11不同电源，不同充电时间对20min抗菌率的影响(所用细菌为大肠杆菌)；其中AC表示交流电；On 0.5min、On 5min和On 15min分别表示充电0.5、5和15min。
图12不同ZnO样品充满电后与细菌作用20min的杀菌率，氧化锌表面喷金时间为0，2，4，6min(分别对应ZnO、ZnO-Au-2、ZnO-Au-4、ZnO-Au-6)。
图13对还原的氧化石墨烯-钛合金复合材料充电后与细菌作用不同时间的抗菌率。
具体实施方式
对钛合金预处理并对表面进行超电容特性改性
将钛合金加工成长宽高各为30mm、30mm、0.5mm的长方体并将其抛光打磨，然后依次在丙酮、乙醇、水中超声清洗10min，用氮气吹干备用。
电容特性的材料表面设计可以利用对钛合金表面进行阳极氧化而生成管径10nm-500nm的二氧化钛纳米管阵列，用于阳极氧化电解液为氟化铵(1-10％)、甲醇(1-10％)、去离子水(1-10％)以及乙二醇(70-95％)，阳极氧化所用电压为10-100V，反应时间为20-1000min，反应后将样品用5mL水冲洗2min并用氮气吹干。然后，将阳极氧化后的纳米管阵列放入真空管式炉进行退火实现碳沉积(命名为TNT-C)以增强电容特性，退火温度为500-800℃，退火时间为1-5h，升温速率为0.1-20℃min-1。材料的电容大小可以通过控制升温速率以及退火温度实现定量控制。
电容特性的材料表面设计还可以通过水热方法在钛合金表面修饰掺杂金纳米颗粒的氧化锌纳米棒来实现，具体操作如下：(1)氧化锌晶种制备：称量醋酸锌、氢氧化钠和甲醇配制0.001-1M混合溶液，50-70℃搅拌1-10h使其混匀。将以上溶液以500-3000r/min的速度在处理好的钛片上旋涂5-30s，获得湿膜，250度处理5-20min，用以挥发溶剂和热解，重复3-5次，冷却得到带有晶种层的钛片。(2)氧化锌纳米棒的生长：将(1)中样品置于10-1000mL容积的反应釜，配制0.001mM-1M的硝酸锌和六亚甲基四胺混合溶液加入反应釜8-800mL，封闭反应釜并将其置于马弗炉，在90-120℃反应8-48h。将样品拿出，超声清洗得到生长有氧化锌纳米棒的钛片。后用磁控溅射方法溅射粒径1-100nm的金颗粒，得到所需具有电容特性样品。
此外，还原的氧化石墨烯亦可以作为电容材料对钛合金进行修饰。将处理好的钛片依次在10％-30％硝酸和1-10M氢氧化钠溶液中浸泡5min后用去离子水清洗，室温下晾干作为电沉积的工作电极。将氧化石墨烯加入乙醇水溶液(浓度10％-80％)获得浓度为0.01-1mg/mL的电沉积溶液，接入参比电极和对电极，在40-50℃下接入1-20V直流电压进行电沉积，时间1-60min得到氧化石墨烯层。后将其置于盛有4％联氨溶液于95℃水热处理1h得到还原的氧化石墨烯-钛合金复合材料。
对超电容特性材料进行充电并进行杀菌应用
将上述碳沉积二氧化钛纳米管修饰的钛合金接入电化学工作站，测试其电容特性响应电压区间。然后将材料接入直流或者交流(峰峰值2-40，频率1Hz-1MHz)电路，电压设置参照电容响应区间(0.1-50V)，对电容进行充电，充电时间为5-180min。将充满电后的材料取出并在材料表面加入菌液，菌液浓度为10-106CFU mL-1。材料与细菌相互作用一定时间(1-180min)，对细菌进行涂板及生理活性检测以验证抗菌效果。
实施例1
将长宽高各为30mm、30mm、0.5mm的钛片抛光打磨，并依次用丙酮、酒精、去离子水超声清洗干净。将样品接入直流电源正极进行阳极氧化反应，用于阳极氧化电解液为氟化铵(5.5％)、甲醇(5％)、去离子水(5％)以及乙二醇(70-90％)，阳极氧化所用电压为60V，反应时间为60min，反应后将样品用5ml水冲洗2min并用氮气吹干。然后，将阳极氧化后的纳米管阵列放入真空管式炉进行退火实现碳沉积，碳沉积可以提高半导体二氧化钛的电子传递速率降低正负电荷中和速率同时提高比表面积而增强电容特性，退火温度为500℃，退火时间为3h，升温速率为15℃min-1，相同条件下空气中退火的样品作为零碳沉积样品对照组。通过扫描电子显微镜对样品表面微观形态进行观察，得到如图1a所示微观形貌。由图可见，通过阳极氧化后的二氧化钛纳米管外径为160nm，管壁厚度为25nm，管长为10μm。原子力显微镜下得到相一致的结果(图1b)。与空气中退火的二氧化钛纳米管相比，氩气中退火后的二氧化钛纳米管不会造成形貌的显著改变。证明碳沉积不会造成二氧化钛纳米管阵列的微观形貌显著改变。
实施例2
对实施例1中处理得到的样品表面进行元素含量分析。电子能量损失能谱扫描得到图1c，表明碳均匀沉积在二氧化钛管壁上。X-射线电子衍射图(XRD)(图1d)谱图中可明显看到锐钛矿晶型二氧化钛的主峰(2θ＝25.3°(101),48.0°(200),70.3°(220))。进一步对表面元素组成进行X射线光电子能谱(XPS)分析发现碳元素的分布形式在样品表面以C-C键为主(图1e)，而6min剥离之后以C-Ti键为主(图1f)，表明在退火过程中碳逐渐取代二氧化钛中的氧而实现了均匀沉积。以上元素分析结果表明形成了均匀分布的碳沉积的二氧化钛纳米管阵列。
实施例3
利用电化学工作站对制备好的样品进行电容分析，15℃min-1退火条件下可明显检测到样品具有双电层电容特性(图2a)，且15℃min-1退火条件下样品可以积攒更多的电荷(图2b)，预示着其在之后进行抗菌时可以发生更多的电子转移。
实施例4
将长宽高各为30mm、30mm、0.5mm的钛片抛光打磨，并依次用丙酮、酒精、去离子水超声清洗干净备用。称量醋酸锌(0.219g)、氢氧化钠(0.12g)和甲醇(100mL)配制混合溶液，60℃搅拌2h使其混匀。将以上溶液以3000r/min的速度在处理好的钛片上旋涂20s，获得湿膜，250度处理5min，用以挥发溶剂和热解，重复3次，冷却得到带有晶种层的钛片。然后将样品置于20mL容积的反应釜，配制10mL浓度为100μM的硝酸锌和六亚甲基四胺混合溶液加入反应釜，封闭反应釜并将其置于马弗炉，在90℃反应10h。将样品拿出，超声清洗10s得到生长有氧化锌纳米棒的钛片。后用磁控溅射处理2min修饰金颗粒，得到所需具有电容特性样品。将样品用扫面电子显微镜进行观察得到图3微观形貌。
实施例5
将经过打磨、清洗处理好的钛片依次在20％硝酸和5M氢氧化钠溶液中浸泡5min后用去离子水清洗，室温下晾干作为电沉积的工作电极。将氧化石墨烯加入30％乙醇水溶液获得浓度为0.3mg/mL的电沉积溶液，接入参比电极和对电极，在40℃下接入10V直流电压进行电沉积，时间20min得到氧化石墨烯层。后将其置于盛有4％联氨溶液于95℃水热处理1h得到还原的氧化石墨烯-钛合金复合材料，将以上样品接入电化学工作站对其电容特性进行表征,循环伏安图及充放电曲线如图4a,4b所示。
实施例6
将实施例1中所得样品进行直流充电，充电电压为2V，充电时间为20min，充电示意图如图5。
实施例7
将实施例6中充满电后的样品取出并应用于抗菌(金黄色葡萄球菌和大肠杆菌)测试。用涂板计数方法进行抗菌效果评定，结果如图6所示。对于电容越大的样品，充满电后可实现更高的杀菌率，例如15℃min-1在充满电后与细菌作用20min可实现对大肠杆菌和金黄色葡萄球菌～80％和～70％的杀菌率(图6a)。延长材料与细菌的作用时间至180min并不会显著提高抗菌效果(图6b)，表明该抗菌过程发生在接触早期。此外，样品表面充正电荷的杀菌效率显著高于负电荷。
实施例8
将实施例7中的抗菌操作应用于另外两种细菌(铜绿假单胞菌和表皮葡萄球菌)以进一步验证其抗菌效果，结果显示，充满正电后TNT-C-15可在20min内实现对铜绿假单胞菌和表皮葡萄球菌～75％和～45％的抗菌效果(图7)。与实例7中的抗菌结果对比可以看出该基于超电容材料的抗菌体系对革兰氏阴性细菌的抗菌效果要显著高于对革兰氏阳性菌。
实施例9
为提高抗菌效率，将实施例7中杀菌20min后细菌收集，对样品进行再充电(正电)，然后将收集的细菌加入材料表面进行二次杀菌，抗菌结果如图8所示。结果表明，第二个循环充电过程中可以将对四种细菌的杀菌率提高到～90％左右，循环充电三次可以实现大于90％的抗菌率。
实施例10
将实施例7中杀菌20min后的材料上的细菌在细菌培养基中至于37℃进行培养，每6h对材料进行充电，共培养至48h，用荧光染色方法观察生物膜形成情况如图9所示。未充电二氧化钛纳米管上有坚固的生物膜形成，直流充电处理的钛片上也有生物膜形成但是厚度显著低于未充电二氧化钛组，充放电处理的二氧化钛和碳沉积二氧化钛上明显检测到死亡细菌且未形成连续生物膜，这些结果证明该基于超电容材料的钛合金在充放电过程中可以有效抑制生物膜的形成，且抑制效果与电容大小成正相关。
经实验证实，利用氧化还原方法制备直径为160nm的二氧化钛纳米管阵列并在氩气中退火(退火温度500℃，退火时间3h，升温速率15℃min-1)得到碳沉积的二氧化钛纳米管阵列具有超电容特性。用直流电源(2V)对其充电15min，可在20min内实现80％以上的杀菌率，循环充电三次可以实现90％以上杀菌率并有效抑制生物膜的生成。在体内，细菌滋生后往往容易形成具有胞外多聚物基质、有特定结构、抗性更强的生物膜，导致严重的术后感染，本发明的抗生物膜功效可以显著降低术后感染风险。
实施例11
将实施例1中的TNT-C-15样品进行交流充电，电压峰峰值为2V，频率50Hz，充电时间15min，充满电后的样品取出并应用于抗菌(金黄色葡萄球菌和大肠杆菌)测试。用涂板计数方法进行抗菌效果评定，结果如图10所示。结果显示充电15min过程中可以达到对大肠杆菌和金黄色葡萄球菌～80％和60％抗菌率，断电后与细菌接触依然可以在20min和180min内实现超过40％的抗菌率，这说明交流电可以对本发明中的材料进行充电利用其电容达到杀菌效果。
实施例12
将实施例1中的样品充电(交流直流参数同上)不同时间以获得载有不同电荷密度的样品，之后将样品与大肠杆菌(浓度同上)接触，用涂板计数法评判杀菌20min内杀菌效果。结果如图11所示。对于用交流电和直流正电处理后的样品，随着充电时间延长，样品在20min内可以实现更高的杀菌率，这一结果表明具有电容特性材料充电时间越长，表面积攒电荷越多，杀菌效率越高。
实例13
将实施例4中所得ZnO样品进行直流充电，充电电压为2V，充电时间为20min，充电示意图如图5(将TNT-C样品更换为ZnO样品)。将充满电后的样品取出并应用于抗菌(金黄色葡萄球菌和大肠杆菌)测试。用涂板计数方法进行抗菌效果评定，结果如图12所示，对于电容越大的样品，充满电后可实现更高的杀菌率，例如ZnO-Au-6在充满电后与细菌作用20min可实现对大肠杆菌和金黄色葡萄球菌～90％和～80％的杀菌率(图12)。
实例14
将实施例5中所得样品进行直流充电，充电电压为1.5V，充电时间为20min，充电示意图如图5(将TNT-C样品更换为还原的氧化石墨烯-钛合金复合材料样品)。将充满电后的样品取出并应用于抗菌(金黄色葡萄球菌和大肠杆菌)测试。用涂板计数方法进行抗菌效果评定，结果如图13所示，充电后样品与细菌作用前20min杀菌效果逐渐增大，在20-360min处理时间内杀菌效果缓慢上升，最终可实现杀菌率90％以上。

Claims (15)

1.一种表面超电容修饰的材料，包括材料本体及表面的超电容层；其特征在于，所述材料本体选自金属材料或其它导体；所述超电容层是指表面电容大于10mF+cm-2的功能层。
2.根据权利要求1所述的材料，其特征在于，所述金属材料选自钛或其合金、铝或其合金、不锈钢、镍或其合金、锰或其合金、钨或其合金、锌或其合金；所述其它导体选自导电聚合物，包括聚吡咯、聚乙炔、聚噻吩、聚苯胺；所述超电容层的表面电容大于50mF+cm-2，优选大于100mF+cm-2。
3.根据权利要求2所述的材料，其特征在于，所述金属材料选自钛合金、铝合金、不锈钢、镍合金、锌合金；所述超电容层选自二氧化钛纳米管阵列层、氧化锌纳米棒层或还原的氧化石墨烯。
4.根据权利要求3所述的材料，其特征在于，所述二氧化钛纳米管或氧化锌纳米棒的直径在10nm-1000nm之间，优选20-800nm，最优选50-500nm之间；管径500nm-10μm。
5.根据权利要求4所述的钛合金材料，其特征在于，所述二氧化钛纳米管阵列层内还包括碳沉积；所述的氧化锌纳米棒层掺杂有银、金、铜或铂纳米颗粒。
6.一种表面超电容修饰的材料的制备方法，其特征在于，包括如下步骤，对金属材料的表面进行阳极氧化；且阳极氧化使用的电解液为铵盐、低级醇、水以及多元醇的混合液。
7.根据权利要求6所述的制备方法，其特征在于，所述铵盐选自卤化铵，优选氟化铵；所述低级醇选自甲醇或乙醇；所述多元醇选自乙二醇；所述阳极氧化所用电压为10-100V，反应时间为20-1000min。
8.根据权利要求6所述的制备方法，其特征在于，将阳极氧化后得到的纳米管阵列放入真空管式炉进行真空退火实现碳沉积以增强电容特性；所述真空退火的退火温度为500-800℃，退火时间为1-5h，升温速率为1-20℃min-1。
9.一种表面超电容修饰的材料的制备方法，其特征在于包括，通过水热方法在金属材料表面生长氧化锌纳米棒并通过磁控溅射修饰掺杂银、金、铜或铂纳米颗粒来实现，具体步骤如下：
(1)氧化锌晶种制备：将醋酸锌和强碱溶于低级醇中，高速旋涂在金属材料表面，获得湿膜，加热，挥发溶剂和热解，得到带有晶种层的金属材料；
(2)氧化锌纳米棒的生长：将(1)中样品置于反应釜中，加入锌盐和碱的混合水溶液，封闭反应，加热；后用磁控溅射方法溅射银、金、铜或铂纳米颗粒；所述碱优选六亚甲基四胺、氢氧化钠、氢氧化钾、氢氧化钙、氨水。
10.一种表面超电容修饰的材料的制备方法，其特征在于包括，将金属材料作为电沉积的工作电极；将氧化石墨烯加入醇水溶液作为电沉积溶液，接入参比电极和对电极，以直流电进行电沉积，得到氧化石墨烯层；后将其置于联氨溶液中水热处理，得到还原的氧化石墨烯-金属复合材料。
11.一种杀菌方法，其特征在于，使用权利要求1-5任一项所述的表面超电容修饰的材料。
12.根据权利要求11所述的杀菌方法，其特征在于，所述方法包括将所述材料接入直流或者交流电路，对其进行充电，然后使所述材料与菌液接触；所述充电中充的电荷优选为正电。
13.根据权利要求12所述的杀菌方法，其特征在于，所述电路的电压设置参照电容响应区间，充电时间为5-180min，与菌液接触的时间在一分钟以上。
14.根据权利要求11-13任一项所述的杀菌方法，其特征在于，进行多次充电杀菌过程，优选两次以上。
15.根据权利要求14所述的杀菌方法，其特征在于，利用机体运动过程中的机械能转化为电能进行反复充放电而实现循环杀菌。
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