CN107441564A - 一种纳米抗菌材料及其制备方法 - Google Patents
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Abstract
本发明提供了一种纳米抗菌材料及其制备方法。所述的纳米抗菌材料，包括硅片，其特征在于，所述的硅片的表面形成有能够刺破细菌的细胞壁的针状纳米结构。上述的纳米抗菌材料的制备方法，其特征在于，包括：清洗硅片，去除硅片表面的氧化层，通过金属辅助化学刻蚀在硅片的表面形成有能够刺破细菌的细胞壁的针状纳米结构。本发明通过金属辅助化学刻蚀制备具有特殊表面形貌的硅片，硅片的表面形成有尺寸与细菌细胞接近的针尖状的纳米结构。该纳米结构能够刺破细菌的细胞壁，具有较高的杀菌效果。
Description
技术领域
本发明属于纳米材料科学领域，具体涉及一类特殊形貌的硅纳米线阵列结构。
背景技术
细菌感染一直以来严重威胁着人类的健康，并增加了全球医疗卫生成本。医生为病人选择的人体植入材料易导致细菌在其表面附着和繁殖，增加了以医疗设备为源的细菌感染率，进而增加了医疗系统里的患病率和死亡率。附着在医疗设备表面的微生物群落数目为浮游细菌的近1000倍，这些细菌的生物膜通过触发人体免疫系统反应，释放有害的毒素对人体造成严重伤害。此外，抗生素的滥用引起微生物变异，这些变异的微生物对治疗它的抗生素产生耐药性进而演化为耐药菌，增加了抗菌的难度。发展具有阻止生物膜的形成或者抑制细菌在材料表面附着或直接将细菌杀死的生物医学材料，将会极大的降低医院内致病菌感染率以及治疗费用。
发明内容
本发明的目的是提出一种新型的纳米结构材料及其制备方法，该材料能够利用表面机械应力杀死附着在表面的细菌，目的是为了解决药物杀菌技术局限性的缺点，该研究可使卫生医疗系统以经济高效的技术抵御细菌污染，进一步促进新型纳米抗菌材料的研究发展。
为了达到上述目的，本发明提供了一种纳米抗菌材料，包括硅片，其特征在于，所述的硅片的表面形成有能够刺破细菌的细胞壁的针状纳米结构。
优选地，所述的针状纳米结构的顶端呈针尖状，高度为4-7μm、直径为 150-250μm，针尖间距为1-3μm。
本发明还提供了上述的纳米抗菌材料的制备方法，其特征在于，包括：清洗硅片，去除硅片表面的氧化层，通过金属辅助化学刻蚀在硅片的表面形成有能够刺破细菌的细胞壁的针状纳米结构。
优选地，所述的清洗硅片的具体步骤包括：将硅片浸泡于浓度为95％-98％以上的H2SO4和30wt％-40wt％H2O2以4∶1体积比混合的溶液中，10-15分钟后取出并用去离子水清洗，然后将硅片依次用丙酮、酒精和去离子水超声清洗10-15 分钟。
更优选地，所述的硅片为采用提拉法制备的单晶硅晶圆片。
优选地，所述的去除硅片表面的氧化层的具体步骤包括：将清洗干净的硅片浸泡于5-10％HF中3-5min。
优选地，所述的金属辅助化学刻蚀的具体步骤包括：将硅片用去离子水清洗后浸泡于镀银溶液中40s-50s，取出后用去离子水冲洗，放入含有4.8M-5M HF 和0.3M H2O2的溶液中5min-10min，得到刻蚀后的硅片；将刻蚀后的硅片浸泡于浓硝酸中5min-20min，以去除硅表面残留的Ag纳米颗粒，用去离子水清洗并用氮气吹干；配制浓度为7％-10％的KOH溶液，将硅片浸泡该KOH溶液中10-15 s，得到纳米抗菌材料。
更优选地，所述的镀银溶液含有4.8M-5M HF和0.01M-0.015MAgNO3。
与现有技术相比，本发明的有益效果是：
本发明通过金属辅助化学刻蚀制备具有特殊表面形貌的硅片，硅片的表面形成有尺寸与细菌细胞接近的针尖状的纳米结构。该纳米结构能够刺破细菌的细胞壁，具有较高的杀菌效果。
附图说明
图1为金属辅助下的化学刻蚀并经过10％KOH溶液处理后得到的Si纳米线阵列结构SEM图像。
图2为Si基片上细菌形貌SEM图像。(a)大肠杆菌在纳米针表面；(b)金黄色链球菌在纳米针表面；
图3为平板计数法统计Si片上培养后上清液中存活细菌数目的涂板情况。(a)大肠杆菌在纳米针表面；(b)金黄色链球菌在纳米针表面；(c)大肠杆菌在平滑Si片上；(d)金黄色链球菌在平滑Si上；
图4为细菌培养装置示意图。
具体实施方式
下面结合具体实施例，进一步阐述本发明。应理解，这些实施例仅用于说明本发明而不用于限制本发明的范围。此外应理解，在阅读了本发明讲授的内容之后，本领域技术人员可以对本发明作各种改动或修改，这些等价形式同样落于本申请所附权利要求书所限定的范围。
本发明中所述的各浓度，如无特殊说明，均为质量浓度。
实施例
一种纳米抗菌材料，包括硅片，所述的硅片的表面形成有能够刺破细菌的细胞壁的针状纳米结构。上述的纳米抗菌材料的制备方法为：
(1)清洗硅片：将40ml浓硫酸溶液(99％)和10ml 30wt％过氧化氢的混合溶液加入到250ml的玻璃器皿中，立即将4英寸提拉法制备的单晶硅晶圆片浸泡于混合溶液中，10min后取出，用大量去离子水清洗Si表面去除残留混合液。然后将Si片浸泡于50ml的丙酮中，并置于超声仪超声清洗10min，取出并用大量去离子水清洗后浸泡于50ml无水乙醇中，并超声清洗10min，最后置于50ml 去离子水中超声清洗10min，后取出在高纯氮气下吹干。
(2)去除硅片表面的氧化层：将100ml 5％HF加入300ml聚四氟乙烯器皿中，将清洗干净的Si片浸泡于该HF溶液中3min以去除表面氧化物；
(3)金属辅助化学刻蚀：将硅片取出后用大量去离子水快速冲洗后，并加入在盛有含有5M HF和0.01M AgNO3的镀银溶液的聚四氟乙烯器皿中反应浸泡1min，取出后去离子水快速冲洗以除去表面残留AgNO3溶液，并立即加入盛有含有4.8M HF和0.3M H2O2的溶液的聚四氟乙烯器皿中，浸泡10min后取出，得到刻蚀后的硅片，将其并浸泡于40ml(68％)浓HNO3中10min以去除硅表面残留的Ag纳米颗粒，最后用大量去离子水清洗并高纯氮气吹干，得到表面清洁的具有纳米线阵列结构的Si片。配制浓度为10％的KOH溶液，将得到的Si片浸泡该KOH溶液中10s，在硅片的表面形成有能够刺破细菌的细胞壁的针状纳米结构，即得纳米抗菌材料。
通过金属辅助化学刻蚀和KOH溶液的浸泡处理，本发明制备了形貌特征与细菌尺寸接近的硅纳米针结构。利用场发射扫描电子显微镜(FE-SEM)观察所得到的硅片微观表面形貌特征，包括空间分布，形状和尺寸等。图1所示为经过金属辅助化学刻蚀后又经过KOH溶液处理10s的样品微观形貌。这些以90°角拍摄的显微图片显示，KOH处理后的刻蚀硅片表面出现大量无规律紧密排列的纳米针阵列。纳米线的顶端呈尖锐的针尖状，并且排列稀疏，纳米针高度在约4 μm，针尖间距约2μm，直径约200nm。
将纳米抗菌材料与如图4所示的细菌培养装置结合，作为细菌培养基片用于细菌培养，以研究纳米针结构表面的抗菌性能。
如图4所示，所述的细菌培养装置，包括从下到上依次设置的不锈钢底板1、 PDMS缓冲层2和不锈钢顶板3，细菌培养基片5设于底板1和PDMS缓冲层2 之间，底板1和顶板3之间通过螺栓固定连接并将细菌培养基片5与PDMS缓冲层2夹持固定，PDMS缓冲层2和顶板3皆设有用于容纳含有细菌的培养液的半径相同的圆形的通孔4。且PDMS缓冲层2和顶板3上通孔4的位置相对应。
将悬浮于PBS中的野生型大肠杆菌DH5α(诺唯赞，C502-03))和金黄色葡萄球菌(ATCC，43300))调节至OD600＝0.1，取5.0g酵母粉提取物(Oxoid，USA)， 10.0g胰胨(Oxoid，USA)，10.0g NaCl与1000mL H2O并调PH为7.2制备得到液体培养基，并取200μL菌液加入1800μL该液体培养基中，1∶10稀释。分别量取1mL菌液由通孔4加入固定好的细菌培养基片上，37℃条件下培养3h，所有过程在超净台完成。
该抗菌材料对在其表面培养3h的大肠杆菌DH5α(诺唯赞，C502-03)和金黄色葡萄球菌(ATCC，43300)的杀菌效率分别为85.12％，76.40％，表明该材料对革兰氏阳性和革兰氏阴性菌均有高的杀菌效果。
如图2所示，可观察到与纳米针阵列表面接触的细胞被完全破坏，细胞体塌陷并呈滩涂装分布在针尖上。当细菌细胞与其接触时，细胞壁在针尖的强大机械力下被刺破，导致细胞的完整性破坏，将细胞杀死。
如图3所示，采用标准平板计数法统计Si基片上培养3h后的上清液中存活细菌数目。涂板结果显示，在Si纳米针阵列表面培养后的两种细菌的菌落数明显少于参照样品光滑Si上培养得到的菌落数，证明了该纳米结构可以有效的将细菌杀死，达到机械杀菌的效果。
Claims (8)
1.一种纳米抗菌材料，包括硅片，其特征在于，所述的硅片的表面形成有能够刺破细菌的细胞壁的针状纳米结构。
2.如权利要求1所述的纳米抗菌材料，其特征在于，所述的针状纳米结构的顶端呈针尖状，高度为4-7μm、直径为150-250μm，针尖间距为1-3μm。
3.权利要求1所述的纳米抗菌材料的制备方法，其特征在于，包括：清洗硅片，去除硅片表面的氧化层，通过金属辅助化学刻蚀在硅片的表面形成有能够刺破细菌的细胞壁的针状纳米结构。
4.如权利要求3所述的纳米抗菌材料的制备方法，其特征在于，所述的清洗硅片的具体步骤包括：将硅片浸泡于浓度为95％-98％以上的H2SO4和30wt％-40wt％H2O2以4∶1体积比混合的溶液中，10-15分钟后取出并用去离子水清洗，然后将硅片依次用丙酮、酒精和去离子水超声清洗10-15分钟。
5.如权利要求3所述的纳米抗菌材料的制备方法，其特征在于，所述的硅片为采用提拉法制备的单晶硅晶圆片。
6.如权利要求3所述的纳米抗菌材料的制备方法，其特征在于，所述的去除硅片表面的氧化层的具体步骤包括：将清洗干净的硅片浸泡于5-10％HF中3-5min。
7.如权利要求3所述的纳米抗菌材料的制备方法，其特征在于，所述的金属辅助化学刻蚀的具体步骤包括：将硅片用去离子水清洗后浸泡于镀银溶液中40s-50s，取出后用去离子水冲洗，放入含有4.8M-5M HF和0.3M H2O2的溶液中5min-10min，得到刻蚀后的硅片；将刻蚀后的硅片浸泡于浓硝酸中5min-20min，以去除硅表面残留的Ag纳米颗粒，用去离子水清洗并用氮气吹干；配制浓度为7％-10％的KOH溶液，将硅片浸泡该KOH溶液中10-15s，得到纳米抗菌材料。
8.如权利要求7所述的纳米抗菌材料的制备方法，其特征在于，所述的镀银溶液含有4.8M-5M HF和0.01M-0.015M AgNO3。
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