CN115304977A - 控制、排斥和/或灭活病毒和细菌的pH/CO2响应性智能抗病原体涂层 - Google Patents
控制、排斥和/或灭活病毒和细菌的pH/CO2响应性智能抗病原体涂层 Download PDFInfo
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Abstract
本文公开了具有可逆润湿性的涂层,该涂层具有疏水状态,其中所述涂层具有排斥细菌、真菌和病毒中至少一种的疏水表面;和亲水状态,其中所述涂层具有使细菌、真菌和病毒中的至少一种灭活的亲水表面,其中所述疏水状态可通过暴露于第一转换刺激而转换为所述亲水状态,并且所述亲水状态可通过暴露于第二转换刺激而转换为所述疏水状态。这种在超疏水性和超亲水性之间的可逆润湿性转换可以重复至少三次,这表明细菌、真菌或病毒的受控排斥或灭活过程至少可以转换三次。
Description
技术领域
本文公开了抗病原体涂层和防止细菌、真菌和病毒中的至少一种传播的方法,以及制备抗病原体涂层的方法。
背景技术
由于其自清洁和防水特性,开发液体排斥表面是减少病毒/细菌污染的有效方法。然而,由于粘附,仍然存在病毒残留物,这有害地将表面转化为污染物。
发明内容
为了提供对本发明的一些方面的基本理解,以下给出了本发明的简化概述。该概述不是对本发明的广泛概述。它既不旨在识别本发明的关键或重要要素,也不旨在描绘本发明的范围。相反,该概述的唯一目的是以简化形式呈现本发明的一些概念,作为下文呈现的更详细描述的序言。
鉴于上述问题,设计新型智能抗病原体表面以可控方式排斥和灭活附着在表面上的任何病毒(特别是SARS-CoV-2)或细菌具有重要意义。
本文公开了具有可逆润湿性的涂层,该涂层具有疏水状态,其中该涂层具有排斥含有细菌、真菌和病毒中至少一种的流体的疏水表面;和亲水状态,其中涂层具有锚定流体并使细菌、真菌和病毒中的至少一种灭活的亲水表面,其中疏水状态可通过暴露于第一转换刺激而转换为亲水状态,并且该亲水状态可通过暴露于第二转换刺激而转换为疏水状态。
本文还公开了防止细菌、真菌和病毒中的至少一种传播的方法,其涉及将具有可逆润湿性的涂层应用到固体表面,所述涂层包含疏水表面;以及将包含疏水表面的涂层暴露于转换刺激以产生包含亲水表面的涂层,其中具有亲水表面的涂层使细菌、真菌和病毒中的至少一种灭活。
本文还公开了制备具有可逆润湿性的涂层的方法,其涉及聚合烷基磺酰基硫代羰基磺酰基-羧酸;以及将Ag颗粒、叔胺基、羧基和季铵化合物中的至少一种添加到聚合产物中。
为了实现上述和相关目的,本发明包括在下文中充分描述并且在权利要求中特别指出的特征。以下描述和附图详细阐述了本发明的某些说明性方面和实施方式。然而,这些仅表示可以采用本发明原理的各种方式中的几种。当结合附图考虑时,本发明的其他目的、优点和新颖特征将从本发明的以下详细描述中变得显而易见。
附图说明
图1(A)和(B)分别是1微米水平和10微米水平的pH/CO2响应性智能铜板表面的扫描电子显微镜图像。(C)和(D)分别是1微米水平和10微米水平裸铜板表面的扫描电子显微镜图像。
图2A以图形方式描绘了pH/CO2响应性智能铜板在三个循环后对水滴的可逆润湿性。
图2B以图形方式描绘了pH/CO2响应性智能铜板对空气中水滴的粘附力。
图3(图3a和图3b)描绘了润湿性和接触角。
图4描绘了润湿性和接触角θ。
具体实施方式
本文描述了具有可调润湿性的pH/CO2响应性智能抗病原体涂层的开发,该涂层至少具有以下之一:排斥一种可载有病毒/细菌的液滴(或流体)并灭活残留的病毒/细菌。表面润湿性可通过pH/CO2刺激在超疏水性和超亲水性之间切换。智能抗病原体涂层在超疏水状态中可有效排斥病毒/细菌液滴。在暴露于转换刺激(例如溶解CO2的酸性水溶液/碳酸氢钠溶液/水)后,抗病原体涂层的表面成功地将润湿性从超疏水性变为超亲水性。在超亲水状态中,表面可以锚定载有病毒/细菌的液滴,并通过疏水和静电相互作用与病毒/细菌牢固结合。由于这种相互作用,病毒的分解随后使其自身表现为RNA泄漏到溶液中并丧失传染性。
本文所述的技术试图提高抗病原体涂层的超疏水性和超亲水性之间的可逆转换的响应率。在此,完成超疏水性和超亲水性之间的可逆循环通常需要至少20分钟但少于2小时。在另一个实施方案中,完成超疏水性和超亲水性之间的可逆循环通常需要至少30分钟但少于1小时。
开发了具有可逆润湿性的智能抗病原体涂层,以使表面排斥和灭活广谱的细菌、真菌和病毒,包括SARS-CoV-2。响应于转换刺激,例如pH/CO2刺激,表面润湿性可在超疏水性和超亲水性之间转换。载有病毒/细菌的液滴(或液体)在超疏水状态中被表面脱落,而在超亲水状态下锚定在表面上。浸渍有抗病毒和抗微生物剂(例如季铵化合物、质子化叔胺基、羧基和/或银)的超亲水涂层能够杀死与其接触的病毒或细菌。智能涂层可应用于固体表面,例如金属、塑料、玻璃、聚合物、纸张、纺织品、织物、纱布和其他纤维。
涂层的可转换润湿性行为源于,例如CO2响应性聚合物分子中的叔胺基团的可逆质子化/去质子化。疏水性聚合物链在中性水溶液中保持脱水和塌缩的形式。在暴露于dCO2(或NaHCO3)溶液时,CO2响应性聚合物中的叔胺基团被CO2与水反应产生的碳酸质子化为带正电荷的叔胺,其呈现出亲水性构型。随着聚合物链化学结构的可逆变化,表面润湿性可以反复转换。
智能抗病原体涂层的要素包括具有可逆润湿性的液体排斥表面,其对广泛范围的病毒和细菌,特别是SARS-CoV-2具有更强的功效。例如,智能抗病原体涂层可以在超疏水状态中以99.98%的比率有效排斥载有SARS-CoV-2病毒的液滴。在另一个实施方案中,智能抗病原体涂层可以在超疏水状态中以99.99%的比率有效排斥载有SARS-CoV-2病毒的液滴。智能抗病原体涂层的要素还包括一种pH/CO2响应性聚合物羧基封端的聚(甲基丙烯酸-2-(二乙氨基)乙酯),其是杀病毒的。该聚合物的杀病毒效率大于80%。在另一个实施方案中,该聚合物的杀病毒效率大于85%。
如图3所示,接触角值被用作衡量液体对固体的润湿性的标准。一般来说,当接触角大于90度时(见图3a),其被定义为“非润湿系统”或“疏水”,当接触角小于90度时(见图3b),其被定义为“润湿系统”或“亲水”。在另一个实施方案中,疏水涂层具有100度或更大的接触角值并且亲水涂层具有80度或更小的接触角值。在又一个实施方案中,疏水涂层具有120度或更大的接触角值并且亲水涂层具有60度或更小的接触角值。图4提供了另一个观察接触角(θ)的视图。
本文描述了提供可调润湿性和抗病原体特性的pH/CO2响应性智能抗病原体涂层的制造和使用。涂层包括pH/CO2响应性聚合物、低表面能材料和一金属Ag层。Ag层提供了表面的分级粗糙度。这种具有低表面能并包含具有分级纳米/微米结构的表面的涂层代表了超疏水性的基础。通过对pH/CO2响应性聚合物的修饰,改变外部刺激来控制表面的润湿性行为。例如,涂层在pH 7或更高的空气中是超疏水的,而在pH 5.5或更低的水性介质中是超亲水的。此外,本文所述的涂层表现出可调的抗病原体特性,该特性由表面的润湿性调节。载有病毒/细菌的水性液滴(流体)在超疏水状态中被表面脱落,而在超亲水状态中锚定在表面上。
本文还描述了以下发现:包含叔胺和羧基的pH/CO2响应性聚合物羧基封端的聚(甲基丙烯酸-2-(二乙氨基)乙酯)是杀病毒/杀菌的。在暴露于弱酸性溶液(例如,pH 5.5或更低)时,pH/CO2响应性聚合物分子中的叔胺基团被质子化为带正电荷的叔胺。当载有病毒/细菌的水性液滴(流体)粘附在超亲水涂层上时,病毒/细菌(尤其是SARS-CoV-2)可以被带正电荷的叔胺和带负电荷的羧基灭活。
这种pH/CO2响应性智能抗病原体涂层采用两步法构建,其能够被应用于各种尺寸、形状和几何结构的各种金属、塑料、玻璃、聚合物、纸张、纺织品、织物、纱布和其他纤维基材。这种涂层的应用可以是抗微生物、抗润湿、抗腐蚀、自清洁或除冰应用中的一种或多种形式。
作为一般示例,智能抗病原体涂层包含足量的pH/CO2响应性聚合物和抗病毒颗粒(和/或根据所需情况抗细菌、抗真菌,但为简洁仅描述抗病毒)以具有疏水性-亲水性转换和杀病毒/病毒复制抑制(和/或相应的抗细菌和/或抗真菌特性)两者的特性。在一个实施方案中,智能抗病原体涂层包含按重量计2%至20%的pH/CO2响应性聚合物,按重量计5%至40%的抗病毒颗粒,余量是其他涂层材料和/或添加剂,其促进涂层形成,但不抑制pH/CO2响应性聚合物和抗病毒颗粒的性能。在另一个实施方案中,智能抗病原体涂层包含按重量计3%至15%的pH/CO2响应性聚合物,按重量计10%至30%的抗病毒颗粒。在又一个实施方案中,智能抗病原体涂层包含按重量计4%至12%的pH/CO2响应性聚合物,按重量计15%至25%的抗病毒颗粒。
pH/CO2响应性智能涂层的制备
pH/CO2响应性共聚物羧基封端的聚(甲基丙烯酸-2-(二乙氨基)乙酯)(PDEM-CT)是通过可逆加成断裂转移(RAFT)聚合合成的。首先,合成了2-十二烷基磺酰基硫代羰基磺酰基-2-甲基丙酸(DMP)。DMP如下制备。通常,8.076g的1-十二硫醇、19.24g的丙酮和0.6g的三辛酰基甲基氯化铵在10℃于氩气气氛中搅拌。然后将1.6mL的NaOH水溶液(50wt%)、3.04g的CS2和4.04g的丙酮依次滴加到混合物中。搅拌15分钟后,将7.13g的CHCl3倒入上述混合物中。随后,向所得混合物中滴加1.6mL的NaOH水溶液(50wt%)。在室温搅拌8小时后,将60mL水和10mL浓HCl依次加入混合物中。最后通过减压蒸馏除去丙酮。得到的固体用2-丙醇洗涤并在室温干燥。
然后,将DEAEMA(364.64mg)、DMP(16.4mg)和AIBN(30mg)溶解在Schlenk烧瓶中的6mL的1,4-二噁烷中,并通过三个冷冻-真空-解冻循环小心地将上述混合物脱气。反应在真空下在70℃持续18小时。聚合后,产物用5mL的1,4-二噁烷稀释,并通过在蒸馏水(pH 4.5)中渗析72小时进行纯化。最后,收集固体产物并通过冻干法干燥。在示例性实施方案中,将一块铜板浸入1.0mg ml-1AgNO3水溶液中。该溶液用紫外线(UV,254nm,3W)灯照射20分钟以在铜板上沉积一层银纳米颗粒。用蒸馏水洗涤并在空气中干燥后,将得到的铜板在含有50mg mL-1的pH/CO2响应性共聚物和1μL mL-1的1H、1H、2H、2H-全氟癸硫醇的乙醇溶液中温育8小时。之后,用乙醇洗涤样品以去除吸附化学物质,然后在50℃真空干燥5小时。
所得铜板表现出超疏水性,水接触大于150°。使用定量RT-PCR(实时聚合酶链式反应)基于病毒基因组拷贝数确定超疏水铜板表面上的病毒残留物。研究发现,超疏水铜板可以99.98%的比率有效排斥载有SARS-CoV-2病毒的液滴。当所制备的铜板暴露于弱酸性溶液(pH 5.5)时,铜板表面的润湿性从超疏水性变为超亲水性,水接触为0°。将超亲水铜板放入24孔板中,并将杜氏改良Eagle培养基(Dulbecco’s Modified Eagle Medium,DMEM)中的SARS-CoV-2溶液的液滴沉积在铜板的中心。温育24小时后,去除所得铜板,将板中的SARS-CoV-2等分用于6孔板中的VeroE6细胞的噬菌斑测定,以确定病毒感染性。在感染后72小时对6孔板中的VeroE6细胞的噬菌斑进行染色和计数。结果表明,智能抗病原体涂层的杀病毒效率为85.3%。
除非在实施例和说明书和权利要求的其他地方另有说明,所有份数和百分比均以重量计,所有温度均以摄氏度为单位,并且压力处于或接近大气压。
对于给定特征的任何数字或数值范围,来自一个范围的数字或参数可以与来自用于相同特征的不同范围的另一数字或参数组合以产生数值范围。
除了在操作实施例中或另有说明的情况下,在说明书和权利要求书中使用的涉及成分的量、反应条件等的所有数字、值和/或表达应理解为在所有情况下通过术语“约”修饰。
虽然结合某些实施方案解释了本发明,但应理解,在阅读本说明书后,其各种修改将对本领域技术人员变得显而易见。因此,应该理解,本文公开的发明旨在覆盖落入所附权利要求范围内的这些修改。
Claims (22)
1.具有可逆润湿性的涂层,其包含:
疏水状态,其中所述涂层具有排斥含有细菌、真菌和病毒中至少一种的流体的疏水表面;和
亲水状态,其中所述涂层具有锚定流体并使细菌、真菌和病毒中的至少一种灭活的亲水表面,
其中所述疏水状态可通过暴露于第一转换刺激而转换为所述亲水状态,并且所述亲水状态可通过暴露于第二转换刺激而转换为所述疏水状态。
2.根据权利要求1所述的涂层,其中所述涂层包含质子化叔胺、羧基、季铵化合物和银颗粒中的至少一种。
3.根据权利要求1所述的涂层,其中所述涂层包含具有叔胺和羧基的羧基封端的聚(甲基丙烯酸-2-(二乙氨基)乙酯)。
4.根据权利要求1所述的涂层,其中所述第一转换刺激是溶解CO2的酸性水溶液/碳酸氢钠溶液/水。
5.根据权利要求1所述的涂层,其中所述细菌、真菌和病毒中的至少一种是SARS-CoV-2病毒。
6.根据权利要求1所述的涂层,其中所述涂层的所述亲水状态具有80%或更高的杀病毒效率。
7.根据权利要求1所述的涂层,其中所述涂层的所述亲水状态具有85%或更高的杀病毒效率。
8.根据权利要求1所述的涂层,其中所述涂层的所述疏水状态可以99.98%的比率有效排斥载有病毒的液滴。
9.根据权利要求1所述的涂层,其中所述涂层的所述疏水状态具有水接触大于150°的疏水性。
10.根据权利要求1所述的涂层,其中所述涂层的所述亲水状态具有水接触为0°的亲水性。
11.根据权利要求1所述的涂层,其中所述第二转换刺激为用N2吹扫然后在空气中用N2干燥的水。
12.根据权利要求1所述的涂层,其中所述疏水状态可转换为所述亲水状态且所述亲水状态可转换为所述疏水状态至少三个循环。
13.根据权利要求1-12中任一项所述的涂层,其中所述涂层为抗病原体涂层。
14.防止细菌、真菌和病毒中的至少一种传播的方法,其包括:
将具有可逆润湿性的涂层应用到固体表面,所述涂层包含疏水表面;以及
将包含疏水表面的涂层暴露于转换刺激以产生包含亲水表面的涂层,其中具有亲水表面的涂层使细菌、真菌和病毒中的至少一种灭活。
15.根据权利要求14所述的方法,其中所述固体表面是金属、塑料、玻璃、聚合物、纸张、纺织品、织物和纱布中的一种或多种。
16.根据权利要求14所述的方法,其中所述涂层包含质子化叔胺、羧基、季铵化合物和银颗粒中的至少一种。
17.根据权利要求14所述的方法,其中所述涂层包含具有叔胺和羧基的羧基封端的聚(甲基丙烯酸-2-(二乙氨基)乙酯)。
18.根据权利要求14所述的方法,其中所述转换刺激为溶解CO2的酸性水溶液/碳酸氢钠溶液/水。
19.根据权利要求14所述的方法,其中所述细菌、真菌和病毒中的至少一种是SARS-CoV-2病毒。
20.根据权利要求14-19中任一项所述的方法,其中所述涂层为抗病原体涂层。
21.制备具有可逆润湿性的涂层的方法,其包括:
聚合烷基磺酰基硫代羰基磺酰基-羧酸;以及
将Ag颗粒、叔胺基、羧基和季铵化合物中的至少一种添加到聚合产物中。
22.根据权利要求21所述的方法,其中所述涂层为抗病原体涂层。
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