CN111500183A - 一种具有普适性的液体灌注润滑涂层及其制备方法 - Google Patents

一种具有普适性的液体灌注润滑涂层及其制备方法 Download PDF

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CN111500183A
CN111500183A CN202010342036.3A CN202010342036A CN111500183A CN 111500183 A CN111500183 A CN 111500183A CN 202010342036 A CN202010342036 A CN 202010342036A CN 111500183 A CN111500183 A CN 111500183A
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layer
liquid
coating
lubricating oil
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赵莉芝
张玉忠
李日舜
佀迪迪
赵雅香
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Tianjin Polytechnic University
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Abstract

本发明公开了一种具有普适性的液体灌注润滑涂层及其制备方法，属于仿生材料化学领域。该涂层由多巴胺活化层、二氧化硅纳米粒子层、氟化层和润滑油层四部分组成，由以下方法制备得到：首先在聚乙烯亚胺辅助下由多巴胺氧化自聚形成聚多巴胺活化层，然后利用硅酸四甲酯的缩聚反应形成二氧化硅纳米粒子层，进一步利用含氟硅烷处理得到氟化层，并灌注润滑油形成润滑油层，得到具有普适性的液体灌注润滑涂层。本发明可以在小倾斜角下使污染液体在其表面滑落，对蛋白质及细菌污染物的黏附量小，具有优异的抗污染特性和抗生物黏附特性，且对大部分固体基底可行，具有普适性。

Description

一种具有普适性的液体灌注润滑涂层及其制备方法
技术领域
本发明属于仿生材料化学领域，具体涉及一种具有普适性的液体灌注润滑涂层及其制备方法。
背景技术
表面污染是众多领域共同关注的核心问题，例如，在生物医学与组织工程领域，蛋白质和细胞在生物医用材料表面吸附产生的表面污染，会导致其效能降低，增加发生血栓、排异等副作用的风险；在海洋和工业设施领域，轮船或舰艇的表面污染造成增阻增耗和加速腐蚀损毁；在膜分离领域，膜污染造成膜的分离性能和渗透通量发生难以恢复的衰减。自然界中生物结构的精巧设计创造了丰富多样的低污染表面，为仿生抗污染表面的设计与合成提供了有益的借鉴和指导，仿荷叶效应的表面就是其中最为典型的仿生防污案例。水滴会悬挂在仿荷叶表面，形成Cassie-Baxter状态，所以很容易滚落并带走污染物，从而达到自清洁的效果。然而，这种抗污染表面仍然存在实际应用方面的问题：压力稳定性差，易吸附细菌和蛋白质，不抗物理损失等。猪笼草瓶状叶边缘由微观粗糙结构和亲水组分构成，表面可储存水形成一层润滑水膜，从而使昆虫滑落进瓶身。受其启发，科学家们尝试构筑仿猪笼草的液体灌注润滑表面，这种表面是在微/纳米粗糙结构的表面灌注润滑液而形成的一种动态油膜覆盖的光滑表面，它以液-液界面代替传统固-液界面，因此能够抵抗绝大多数液体的粘附，抑制细菌的附着，与仿荷叶表面相比，抗污染性能更为优异，且具有自修复性、压力稳定性好等特点(Nature 2011，477，443-447)。然而，针对不同的基底，液体灌注润滑表面构筑的策略也会有所不同，有的构筑方法步骤繁琐，为实际应用带来不便，亟需开发普适性好、制备工艺简单的液体灌注润滑涂层，以满足不同应用场合的抗污染需求。
多巴胺在一定条件下会发生自聚合形成聚多巴胺，聚多巴胺能够在多种基底材料表面黏附形成聚多巴胺涂层，其表面可以进行二次修饰从而制备功能性材料表面。利用聚多巴胺的黏附特性将固体表面活化，以二氧化硅纳米粒子为粗糙结构，然后氟化并灌注润滑油，制备出一种液体灌注润滑涂层，实施方法简单，适用范围宽，具有优异的抗污染特性和抗生物黏附特性。迄今为止，尚未有利用聚多巴胺的黏附特性与润滑表面相结合制备液体灌注润滑涂层的公开报道。
发明内容
为了克服现有技术的缺点与不足，本发明的首要目的在于提供一种具有普适性的液体灌注润滑涂层。
本发明的另一目的在于提供一种具有普适性的液体灌注润滑涂层的制备方法。
本发明所述的液体灌注润滑涂层形成于固体基底表面，由聚多巴胺活化层、二氧化硅纳米粒子层、氟化层和润滑油层四部分组成；首先在聚乙烯亚胺辅助下由多巴胺氧化自聚形成聚多巴胺活化层，然后利用硅酸四甲酯在表面发生缩聚反应，形成二氧化硅纳米粒子层，占涂层总重量的56～65％，二氧化硅纳米粒子平均直径为20～35nm，使表面粗糙度Ra(轮廓算术平均偏差)增加50～80nm，；进一步利用含氟硅烷处理，得到氟化层，其表面含氟量占该层表面元素总含量的18～39％；润滑油通过毛细作用稳定于二氧化硅纳米粒子的粗糙结构中形成最外层的润滑油层，占涂层重量的23～30％；
所述的液体灌注润滑涂层的制备方法，包括以下内容：
(1)清洗固体基底：使用无水乙醇超声清洗固体基底30min后干燥备用；
(2)聚多巴胺活化层：将聚乙烯亚胺和多巴胺分别溶于Tris缓冲液(pH＝8.5)，充分混合后二者浓度均为1mg/mL，得到多巴胺/聚乙烯亚胺沉积液；然后，将清洗后的固体基底浸入沉积液中，接触空气反应4～6h，取出并用纯水多次洗涤，得到聚多巴胺活化层；
(3)二氧化硅纳米粒子层：搅拌下将硅酸四甲酯加入到盐酸(1mM)中，持续搅拌10min，然后与等体积的磷酸缓冲液(pH＝6.0)混合，形成硅化液，将步骤(2)处理后的固体基底浸于硅化液中反应3～6h，取出清洗后得到二氧化硅纳米粒子层；
(4)疏水性氟化层：将(3)处理后的固体基底浸入到含氟硅烷的无水乙醇溶液中，含氟硅烷与无水乙醇体积比为1∶99，氟化处理8～15min，清洗后在100～140℃下干燥，得到氟化层；
(5)润滑油层：将润滑油滴加到(4)处理后的固体基底表面，再以约15～20°的角度倾斜1h使多余的润滑油从样品表面流出，形成润滑油层，最终得到液体灌注润滑涂层。
步骤(2)中所述的聚乙烯亚胺，其作用是破坏聚多巴胺聚集体中的非共价相互作用，抑制颗粒的形成，从而得到均匀的聚多巴胺活化层；
步骤(3)中所述的硅酸四甲酯、盐酸和磷酸缓冲液的体积比为3∶200∶200；
步骤(4)中所述的含氟硅烷为全氟辛基三甲氧基硅烷或全氟辛基三乙氧基硅烷；
步骤(5)中所述的润滑油包括乙基硅油、液体石蜡、Krytox GPL系列润滑油、机油、离子液体中的一种或多种。
本发明所述的液体灌注润滑涂层适用于多种固体基底，包括玻璃片、石英片、棉布、无纺布、滤纸、金属片、塑料片、木材，具有良好的普适性；
所述的液体灌注润滑涂层具有优异的抗污染特性和抗生物黏附特性：倾斜角10～15°时，即可使污染液体的液滴(10～50μL)从其表面滑落，不留下污染的痕迹，与蛋白质溶液接触24h后，蛋白质在其表面黏附量小于50μg/cm2，与细菌培养液接触24h后，细菌在其表面黏附量与疏水性表面相比减少98％以上；
所述的污染液体为与润滑油层不互溶的液体，包括豆浆、咖啡、盐溶液、甘油、亚甲基蓝水溶液和甲基橙水溶液，所述的蛋白质为牛血清蛋白，所述的细菌为大肠杆菌或金色葡萄球菌，所述的疏水性表面其水接触角大于90°。
附图说明
图1.甲基橙水溶液(1)、氯化钠和甲基橙混合水溶液(2)、亚甲基蓝水溶液(3)、甘油(4)、豆浆(5)和咖啡(6)在聚酯无纺布的液体灌注润滑涂层表面上的滑动过程及甲基橙水溶液在空白聚酯无纺布表面上的滑动过程(7)；
图2.表面经氟化处理的聚酯无纺布的疏水性表面(A)和聚酯无纺布的液体灌注润滑涂层(B)浸泡于荧光标记的牛血清蛋白溶液24h后的激光共聚焦显微镜图片；
图3.表面经氟化处理的聚酯无纺布的疏水性表面(A1)与聚酯无纺布的液体灌注润滑涂层(B1)的扫描电镜图片及其浸泡于大肠杆菌培养液中24h后的扫描电镜图片(A2和B2)。
具体实施方式
下面结合具体实施方式对本发明作进一步详细说明，但本发明的保护范围并不限于所述内容。
实施例1：一种具有普适性的液体灌注润滑涂层及其制备方法，具体步骤为：
(1)清洗固体基底：以聚酯无纺布为固体基底，用无水乙醇超声清洗30min，干燥备用。
(2)聚多巴胺活化层：0.4g聚乙烯亚胺和0.4g多巴胺分别溶于200mL Tris缓冲液(pH＝8.5)，充分混合后制得多巴胺/聚乙烯亚胺沉积液。然后，将(1)清洗后的聚酯无纺布浸入沉积液中，接触空气反应4h，最后取出样品用纯水洗涤，去除表面残余的沉积液，放入真空干燥箱60°干燥，在基底表面得到聚多巴胺活化层。
(3)二氧化硅纳米粒子层：搅拌下将1.5mL硅酸四甲酯加入到100mL盐酸(1mM)中，持续搅拌10min，使硅酸四甲酯完全水解后形成原硅酸溶液，然后与100mL磷酸缓冲液(pH＝6.0)混合，形成硅化液，将步骤(2)处理后的聚酯无纺布浸泡于硅化液中反应4h。然后取出样品用去离子水洗涤。
(4)氟化层：将全氟辛基三甲氧基硅烷和无水乙醇按体积比为1∶99的比例混合得到氟化液。将步骤(3)处理后的聚酯无纺布浸入到氟化液中氟化处理10min，然后将样品取出用乙醇冲洗后，在120℃的真空干燥箱中干燥。
(5)润滑油层：将过量的乙基硅油滴加到步骤(4)处理后的聚酯无纺布表面，再以20°的角度倾斜1h使多余的润滑油从样品表面流出。
经过上述步骤便得到以聚酯无纺布为固体基底的液体灌注润滑涂层。其中，聚多巴胺活化层表面均匀，二氧化硅纳米粒子平均直径为25nm，使表面粗糙度Ra(轮廓算术平均偏差)增加70nm，占涂层总重量的60％；氟化层含氟量占该层元素总量的29％；润滑油层占涂层重量的30％。
制备出的以聚酯无纺布为固体基底的液体灌注润滑涂层具有优异的抗污染性和抗生物黏附性。当液体灌注润滑涂层接触各种与乙基硅油不互溶的污染液体时，如豆浆，咖啡，氯化钠和甲基橙混合水溶液，甘油，亚甲基蓝溶液和甲基橙溶液，污染液体的液滴(20μL)均能从倾斜角为15°的液体灌注润滑涂层表面上滑落，没有留下任何污染的痕迹。相比之下，在空白聚酯无纺布表面，污染物浸润并粘附在聚酯无纺布上不能自由地滑落(图1)。将带有液体灌注润滑涂层的聚酯无纺布和表面经氟化处理的疏水性聚酯无纺布浸泡于荧光标记的牛血清蛋白溶液24h，利用紫外可见分光光度计测量牛血清蛋白在278nm处的吸光度的变化，计算得到液体灌注润滑涂层表面对牛血清蛋白的黏附量为45μg/cm2，利用激光共聚焦显微镜观察到氟化处理后的聚酯无纺布疏水性表面黏附较多蛋白质(图2A)，液体灌注润滑涂层表面黏附蛋白质明显少于疏水性表面(图2B)。将带有液体灌注润滑涂层的聚酯无纺布和表面经氟化处理的疏水性聚酯无纺布浸泡于大肠杆菌培养液中培养24h，通过扫描电子显微镜可以明显看出，氟化处理后的聚酯无纺布疏水性表面黏附较多大肠杆菌(图3A2，箭头标记处为黏附的大肠杆菌)，而液体灌注润滑涂层表面没有明显变化(图3B1和B2)，经对比计算菌落数，大肠细菌在液体灌注润滑涂层表面黏附量与氟化处理的疏水性表面相比减少99.4％。
实施例2：一种具有普适性的液体灌注润滑涂层及其制备方法，具体步骤为：
(1)清洗固体基底：以一次性餐盒塑料片为固体基底，用无水乙醇超声清洗30min，干燥备用。
(2)聚多巴胺活化层：0.2g聚乙烯亚胺和0.2g多巴胺分别溶于100mL Tris缓冲液(pH＝8.5)，充分混合后制得多巴胺/聚乙烯亚胺沉积液。然后，将(1)清洗后的塑料片浸入沉积液中，接触空气反应5h，最后取出样品用纯水洗涤，去除表面残余的沉积液，放入真空干燥箱60°干燥，在基底表面得到聚多巴胺活化层。
(3)二氧化硅纳米粒子层：搅拌下将3mL硅酸四甲酯加入到200mL盐酸(1mM)中，持续搅拌10min，使硅酸四甲酯完全水解后形成原硅酸溶液，然后与200mL磷酸缓冲液(pH＝6.0)混合，形成硅化液，将步骤(2)处理后的塑料片浸泡于硅化液中反应5h。然后取出样品用去离子水洗涤。
(4)氟化层：将全氟辛基三甲氧基硅烷和无水乙醇按体积比为1∶99的比例混合得到氟化液。将步骤(3)处理后的塑料片浸入到氟化液中氟化处理12min，然后将样品取出用乙醇冲洗后，在100℃的真空干燥箱中干燥。
(5)润滑油层：将过量的Krytox GPL101滴加到步骤(4)处理后的塑料片表面，再以15°的角度倾斜1h使多余的润滑油从样品表面流出。
经过上述步骤便得到以塑料片为固体基底的液体灌注润滑涂层。其中，聚多巴胺活化层表面均匀；二氧化硅纳米粒子平均直径为28nm，使表面粗糙度Ra(轮廓算术平均偏差)增加76nm，占涂层总重量的62％；氟化层含氟量占该层元素总量的35％；润滑油层占涂层重量的25％。
制备出的以塑料片为固体基底的液体灌注润滑涂层具有优异的抗污染性和抗生物黏附性。当液体灌注润滑涂层接触各种与Krytox GPL101不互溶的污染液体时，如豆浆，咖啡，氯化钠和甲基橙混合水溶液，甘油，亚甲基蓝溶液和甲基橙溶液，污染液体的液滴(20μL)均能从倾斜角为12°的液体灌注润滑涂层表面上滑落，且其表面没有留下任何污染的痕迹。将带有液体灌注润滑涂层的塑料片浸泡于荧光标记的牛血清蛋白溶液24h后，利用紫外可见分光光度计测量牛血清蛋白在278nm处的吸光度的变化，计算得到液体灌注润滑涂层表面对牛血清蛋白的黏附量为34μg/cm2。将带有液体灌注润滑涂层的塑料片和表面经氟化处理的塑料片浸泡于大肠杆菌培养液中培养24h后，通过扫描电子显微镜可以明显看出氟化处理后的塑料片疏水性表面黏附较多大肠杆菌，而液体灌注润滑涂层表面没有明显黏附大肠杆菌，经对比计算菌落数，大肠细菌在液体灌注润滑涂层表面黏附量与氟化处理的疏水性表面相比减少99.1％。
实施例3：一种具有普适性的液体灌注润滑涂层及其制备方法，具体步骤为：
(1)清洗固体基底：以玻璃片为固体基底，用无水乙醇超声清洗30min，干燥备用。
(2)聚多巴胺活化层：0.3g聚乙烯亚胺和0.3g多巴胺分别溶于150mL Tris缓冲液(pH＝8.5)，充分混合后制得多巴胺/聚乙烯亚胺沉积液。然后，将(1)清洗后的玻璃片浸入沉积液中，接触空气反应4h，最后取出样品用纯水洗涤，去除表面残余的沉积液，放入真空干燥箱60°干燥，在基底表面得到聚多巴胺活化层。
(3)二氧化硅纳米粒子层：搅拌下将1.5mL硅酸四甲酯加入到100mL盐酸(1mM)中，持续搅拌10min，使硅酸四甲酯完全水解后形成原硅酸溶液，然后与100mL磷酸缓冲液(pH＝6.0)混合，形成硅化液，将步骤(2)处理后的玻璃片浸泡于硅化液中反应6h。然后取出样品用去离子水洗涤。
(4)氟化层：将全氟辛基三甲氧基硅烷和无水乙醇按体积比为1∶99的比例混合得到氟化液。将步骤(3)处理后的玻璃片浸入到氟化液中氟化处理14min，然后将样品取出用乙醇冲洗后，在120℃的真空干燥箱中干燥。
(5)润滑油层：将过量的液体石蜡滴加到步骤(4)处理后的玻璃片表面，再以15°的角度倾斜1h使多余的润滑油从样品表面流出。
经过上述步骤便得到以玻璃片为固体基底的液体灌注润滑涂层。其中，聚多巴胺活化层表面均匀；二氧化硅纳米粒子平均直径为30nm，使表面粗糙度Ra(轮廓算术平均偏差)增加80nm，占涂层总重量的65％；氟化层含氟量占该层元素总量的38％；润滑油层占涂层重量的27％。
制备出的以玻璃片为固体基底的液体灌注润滑涂层具有优异的抗污染性和抗生物黏附性。当液体灌注润滑涂层接触各种与液体石蜡不互溶的污染液体时，如豆浆，咖啡，氯化钠和甲基橙混合水溶液，甘油，亚甲基蓝溶液和甲基橙溶液，污染液体的液滴(40μL)均能从倾斜角为10°的液体灌注润滑涂层表面上滑落，且其表面没有留下任何污染的痕迹。将带有液体灌注润滑涂层的玻璃片浸泡于荧光标记的牛血清蛋白溶液24h后，利用紫外可见分光光度计测量牛血清蛋白在278nm处的吸光度的变化，计算得到液体灌注润滑涂层表面对牛血清蛋白的黏附量为30μg/cm2。将带有液体灌注润滑涂层的玻璃片和表面经氟化处理的玻璃片浸泡于大肠杆菌培养液中培养24h后，通过扫描电子显微镜可以明显看出氟化处理后的玻璃片疏水性表面黏附较多大肠杆菌，而液体灌注润滑涂层表面没有明显黏附大肠杆菌，经对比计算菌落数，大肠细菌在液体灌注润滑涂层表面黏附量与氟化处理的疏水性表面相比减少98.8％。
实施例4：一种具有普适性的液体灌注润滑涂层及其制备方法，具体步骤为：
(1)清洗固体基底：以铝片为固体基底，用无水乙醇超声清洗30min，干燥备用。
(2)聚多巴胺活化层：0.2g聚乙烯亚胺和0.2g多巴胺分别溶于100mL Tris缓冲液(pH＝8.5)，充分混合后制得多巴胺/聚乙烯亚胺沉积液。然后，将(1)清洗后的铝片浸入沉积液中，接触空气反应6h，最后取出样品用纯水洗涤，去除表面残余的沉积液，放入真空干燥箱60°干燥，在基底表面得到聚多巴胺活化层。
(3)二氧化硅纳米粒子层：搅拌下将3mL硅酸四甲酯加入到200mL盐酸(1mM)中，持续搅拌10min，使硅酸四甲酯完全水解后形成原硅酸溶液，然后与200mL磷酸缓冲液(pH＝6.0)混合，形成硅化液，将步骤(2)处理后的铝片浸泡于硅化液中反应3h。然后取出样品用去离子水洗涤。
(4)氟化层：将全氟辛基三甲氧基硅烷和无水乙醇按体积比为1∶99的比例混合得到氟化液。将步骤(3)处理后的铝片浸入到氟化液中氟化处理9min，然后将样品取出用乙醇冲洗后，在140℃的真空干燥箱中干燥。
(5)润滑油层：将过量的机油滴加到步骤(4)处理后的铝片表面，再以15°的角度倾斜1h使多余的润滑油从样品表面流出。
经过上述步骤便得到以铝片为固体基底的液体灌注润滑涂层。其中，聚多巴胺活化层表面均匀；二氧化硅纳米粒子平均直径为20nm，使表面粗糙度Ra(轮廓算术平均偏差)增加59nm，占涂层总重量的58％；氟化层含氟量占该层元素总量的25％；润滑油层占涂层重量的24％。
制备出的以铝片为固体基底的液体灌注润滑涂层具有优异抗污染性和抗生物黏附性。当液体灌注润滑涂层接触各种与机油不互溶的污染液体时，如豆浆，咖啡，氯化钠和甲基橙混合水溶液，甘油，亚甲基蓝溶液和甲基橙溶液，污染液体的液滴(20μL)均能从倾斜角为15°的液体灌注润滑涂层表面上滑落，且其表面没有留下任何污染的痕迹。将带有液体灌注润滑涂层的铝片浸泡于荧光标记的牛血清蛋白溶液24h后，利用紫外可见分光光度计测量牛血清蛋白在278nm处的吸光度的变化，计算得到液体灌注润滑涂层表面对牛血清蛋白的黏附量为40μg/cm2。将带有液体灌注润滑涂层的铝片和表面经氟化处理的铝片浸泡于大肠杆菌培养液中培养24h后，通过扫描电子显微镜可以明显看出氟化处理后的铝片疏水性表面黏附较多大肠杆菌，而液体灌注润滑涂层表面没有明显黏附大肠杆菌，经对比计算菌落数，大肠细菌在液体灌注润滑涂层表面黏附量与氟化处理的疏水性表面相比减少98.2％。

Claims (3)

1.一种具有普适性的液体灌注润滑涂层，其特征是形成于固体基底表面，由聚多巴胺活化层、二氧化硅纳米粒子层、氟化层和润滑油层四部分组成，其中，聚多巴胺活化层为最内层，通过聚乙烯亚胺辅助下多巴胺氧化自聚形成；二氧化硅纳米粒子层通过硅酸四甲酯缩聚反应形成，占涂层总重量的56～65％，二氧化硅纳米粒子平均直径为20～35nm，该层使表面粗糙度Ra(轮廓算术平均偏差)增加50～80nm；氟化层通过含氟硅烷处理形成，含氟量占该层元素总量的18～39％；润滑油层为最外层，通过润滑油毛细作用稳定于二氧化硅纳米粒子的粗糙结构中形成，占涂层重量的23～30％；
所述的液体灌注润滑涂层具有优异的抗污染特性和抗生物黏附特性：倾斜角10～15°时，即可使污染液体的液滴(10～50μL)从其表面滑落，不留下污染的痕迹，与蛋白质溶液接触24h后，蛋白质在其表面黏附量小于50μg/cm2，与细菌培养液接触24h后，细菌在其表面黏附量与疏水性表面相比减少98％以上；
所述的液体灌注润滑涂层适用于多种固体基底，包括玻璃片、石英片、棉布、无纺布、滤纸、金属片、塑料片、木材，具有普适性；
所述的含氟硅烷为全氟辛基三甲氧基硅烷或全氟辛基三乙氧基硅烷；所述的润滑油包括乙基硅油、液体石蜡、Krytox GPL系列润滑油、机油、离子液体中的一种或多种。
2.如权利要求1所述的具有普适性的液体灌注润滑涂层，其制备方法包括以下内容：
(1)使用无水乙醇超声清洗固体基底30min后干燥备用；
(2)将(1)处理后的固体基底浸入多巴胺和聚乙烯亚胺的Tris缓冲溶液(pH＝8.5)中，多巴胺和聚乙烯亚胺浓度均为1mg/mL，接触空气反应4～6h，清洗并干燥后在固体表面得到聚多巴胺活化层；
(3)将硅酸四甲酯加入到盐酸(1mM)中，搅拌后与磷酸盐缓冲液(pH＝6.0)混合，硅酸四甲酯、盐酸和磷酸盐缓冲液的体积比为3∶200∶200，形成硅化液，将(2)处理后的固体基底放入到硅化液中反应3～6h，取出清洗后得到二氧化硅纳米粒子层；
(4)将(3)处理后的固体基底浸入到含氟硅烷的无水乙醇溶液中，含氟硅烷与无水乙醇体积比为1∶99，氟化处理8～15min，清洗后在100～140℃下干燥，得到氟化层；
(5)将润滑油滴加到(4)处理后的固体基底表面，再以15～20°的角度倾斜1h使多余的润滑油从样品表面流出，形成润滑油层，最终得到液体灌注润滑涂层。
3.如权利要求1所述的具有普适性的液体灌注润滑涂层，其特征在于，所述的污染液体为与润滑油层不互溶的液体，所述的蛋白质为牛血清蛋白，所述的细菌培养液包括大肠杆菌、金色葡萄球菌，所述的疏水性表面其水接触角大于90°。
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