CN109414016B - 用于表面抗菌抗生物污损的胶体涂料 - Google Patents
用于表面抗菌抗生物污损的胶体涂料 Download PDFInfo
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- CN109414016B CN109414016B CN201780041112.3A CN201780041112A CN109414016B CN 109414016 B CN109414016 B CN 109414016B CN 201780041112 A CN201780041112 A CN 201780041112A CN 109414016 B CN109414016 B CN 109414016B
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Abstract
本发明涉及一种抗菌抗生物污损涂料的制剂和方法,所述涂料包含:中空圆形胶体结构,包括:活性聚合物壳;以及活性或惰性核芯;其中所述活性聚合物壳包含一种或多种具有抗菌和抗生物污损活性的聚合物,并且所述聚合物选自由聚乙烯亚胺(PEI)、官能化壳聚糖(CHI)、聚季铵盐、聚二烯丙基二甲基氯化铵(PDDA)和聚六亚甲基双胍(PHMB)组成的组;其中所述活性或惰性核芯含有一种或多种消毒剂、抗微生物剂、香料或惰性溶剂;并且其中所述中空圆形胶体结构在至少3个月内是稳定的。
Description
相关申请的交叉引用
本申请要求于2016年6月30日提交的美国临时专利申请No. 62/493,330的优先权。
背景技术
本发明主题涉及用于固体和多孔表面的表面涂料技术领域,特别是具有抗菌性能、触杀性能以及抗粘附性能的组合的涂料材料。此外还公开了该涂料的制备方法以及性质和性能的细节。
根据世界卫生组织的报告,在全球范围内,水传播疾病和与水有关的疾病是主要的杀手,其导致每年超过340万人死亡。水源和暴露于水中的表面即使在封闭***中也容易受到由生物膜导致的污染和污损,这些生物膜是细菌污染的关键因素。用于水净化和保护饮用水免受污染的水过滤膜容易受到影响,因为存在于水中的细菌可以在膜上繁殖,从而导致生物污损。生物污损会导致严重且明显的性能损伤并缩短膜的使用寿命,并且被污染的膜可能成为机会性病原体的储库。因此,已经广泛研究设计了具有抗污损性能的过滤膜。
美国公开专利申请No.2010/0133172描述了一种复合亲水性组合物,其主要由涂覆在选择性渗透膜上的亲水性聚合物、多酚化合物和表面活性剂制成,其设计用于抵抗水传播的污染物的污损。美国专利No.4,634,530描述了一种将预形成的聚苯并咪唑半透膜化学改性的方法,该方法基于膜的磺化从而增强了抗污损性能。美国专利 No.6,177,011描述了一种通过用聚乙烯醇涂覆芳香族聚酰胺涂覆从而提供的具有高耐污损性的反渗透复合膜。美国专利No.6,280,853 描述了一种具有多孔载体和交联的聚酰胺表面的复合膜,所述交联的聚酰胺表面具有接枝到其上的聚环氧烷基团,其表现出改善的抗污损性。美国公开专利申请No.2012/0048799描述了一种具有可交联聚合物的复合膜,所述可交联聚合物包含聚(甲基)丙烯酸酯和/或聚(甲基) 丙烯酰胺主链和具有抗污损性的多官能酰卤交联剂。美国公开专利申请No.2013/0240445描述了涂覆有聚合物的过滤膜,所述聚合物包含苯二醇或取代酚,其具有抗污损性能,并需要重复清洁和重复使用以长期使用。美国公开专利申请No.2012/0211414描述了一种具有高抗污损性的选择性膜,其在反渗透膜上使用亲水性涂料。
其它存在生物污损和细菌生长风险的表面包括市政饮用水分配管网和储罐。下水道和排水***、热交换器和冷却塔也提供有利于生物膜形成的环境。预计2mm厚的细菌表面层将导致冷却塔***中 80%的能量损失。因此,已经开发出用于这些固体表面的保护性涂料。
CN101143994B描述了一种主要由铜和锌离子组成的抗污损涂料。美国公开的专利申请No.2012/0135149描述了一种用于与水接触的抗生物污损涂料,其由含有能够进行迈克尔反应的反应性基团的大分子支架组成。美国专利No.8,080,285B2描述了一种抗生物污损涂料,其含有将颗粒释放到水中的聚硅氧烷类聚合物和圆柱形纳米填料。美国公开的专利申请No.2014/0148552A1描述了一种用于抗生物污损的仿生剂,其由允许表面粘附的锚定部分和表现出抗生物污损活性的两性离子部分组成。
目前,本领域仍需要具有长效活性的抗菌抗生物污损涂料,并且其能够应用于固体和非固体表面。本发明主题涉及用于固体和多孔表面的可逆和不可逆涂料的抗菌抗生物污损的胶体涂料,其提供广谱抗菌性能,阻止细菌生物膜形成并防止生物污损。本发明的涂料设计用于各种应用,特别适用于涂覆水过滤膜、导管、管道和其它与水接触的表面,以及纺织品和其它多孔介质,包括空气微粒过滤器。本发明的组合物作为用于暴露于空气的固体和多孔表面的抗菌抗生物污损涂料也是有效的。该抗菌抗生物污损胶体涂料能够储存和释放消毒剂、抗微生物剂和香料。
发明内容
本发明涉及一种抗菌抗生物污损涂料制剂,包含:
中空圆形胶体结构,包括:
a)活性聚合物壳;以及
b)活性或惰性核芯;
其中所述活性聚合物壳包含一种或多种聚合物,所述一种或多种聚合物具有抗菌和抗生物污损活性,并选自由聚乙烯亚胺(PEI)、官能化壳聚糖(CHI)、聚季铵盐、聚二烯丙基二甲基氯化铵(PDDA) 和聚六亚甲基双胍(PHMB)组成的组;
其中所述核芯具有活性并含有一种或多种消毒剂、抗微生物剂和香料;以及
其中所述核芯具有惰性并含有水或惰性溶剂;并且
其中所述中空圆形胶体结构在至少3个月内是稳定的。
在另一方面中,本发明主题涉及一种制造用于无孔表面、多孔膜或多孔材料的抗菌抗生物污损涂料的方法,包括:
-按以下步骤制备抗菌抗污损制剂:
(a)制备含有一种或多种活性聚合物的水溶液;
(b)将抗微生物剂或溶剂加入至所述活性聚合物的水溶液中;
(c)制备具有中空圆形胶体结构的乳液,包括:将含有一种或多种表面活性剂的稳定剂混合物加入至所述抗微生物剂或溶剂和活性聚合物的溶液中,以形成抗菌抗生物污损制剂;以及
(d)由抗菌和抗生物污损制剂制备所述抗菌抗生物污损涂料;以及
-将所述抗菌抗生物污损涂料涂覆在无孔表面、多孔膜或多孔材料上。
如下文中所详细描述的,本发明主题的组合物和方法解决了现有技术组合物和方法的困难和问题。
附图说明
图1:由分子量为1300至60000的PEI和聚乙烯醇(PVA)形成的胶体的光学显微镜图像。
图2:PEI聚合物在抗菌抗生物污损胶体涂料材料中的化学交联。
图3:由PEI-PHMB以比例(a)4:1、(b)2:1、(c)1:2以及 (d)1:4形成的胶体的光学显微镜图像。
图4:由(a)PHMB和(b)储存百里香油的PEI形成的胶体的光学显微镜图像。
图5:由储存百里香油的PEI-PHMB形成的胶体的光学显微镜图像。PEI-PHMB为不同的比例:(a)4:1,(b)1:1和(c)1:4。
图6:储存有(a)肉桂醛、(b)法呢醇和(c)混合抗微生物剂的PEI胶体乳液的照片。
图7:在106CFU/ml的金黄色葡萄球菌和铜绿假单胞菌下,PEI (实施例1)、PDDA和PEI-PDDA(实施例5)涂料的抗菌性能。
图8:在106CFU/ml的金黄色葡萄球菌和铜绿假单胞菌下, PHMB、PDDA和PHMB-PDDA(实施例6)涂料的抗菌性能。
图9:在106CFU/ml的金黄色葡萄球菌和铜绿假单胞菌下,PEI、 PHMB和PEI-PHMB(实施例7)涂料的抗菌性能。
图10:在106CFU/ml的金黄色葡萄球菌、枯草芽孢杆菌、大肠杆菌和铜绿假单胞菌下,PEI、PHMB和PEI-PHMB(实施例7-12) 涂料的抗菌性能。
图11:水过滤膜上的涂覆过程的示意图(实施例23-27)。该图是实验室规模的纳滤膜。
图12:两种市售锡类抗生物絮凝剂和两种PEI涂料在纳滤膜上的抗菌性能。测试生物:106CFU/ml的大肠杆菌。
图13:不同量的PEI-PHMB(实施例7)表面涂料在纳滤膜上的抗菌性能。测试生物:106CFU/ml的大肠杆菌。
图14:由未涂覆的纳滤膜、市售抗生物污损剂以及PEI涂料(实施例1)在纳滤膜上的细菌粘附示出的抗生物污损性能。测试生物: 106CFU/ml的大肠杆菌。
图15:由未涂覆的纳滤膜和PEI-PHMB(实施例8)涂料在纳滤膜上的细菌粘附示出的抗生物污损性能。测试生物:106CFU/ml 的大肠杆菌。
图16:穿过纳滤膜的水通量。
图17:(a)胶体PEGDA-X(其中X为CHIT、EGG、NR3、 NR4、SO3和LYN)的杀菌活性(实施例4),(b)不同量的 PEGDA-EGG、PEGDA-NR3、PEGDA-LYN和PEGDA-NR4的杀菌活性。
图18:涂覆的纳滤膜的飞行时间二次离子质谱(ToF-SIMS)图像。位于m/z为86和113的碎片属于NR3,m/z为84、126和213 的碎片属于NR4。
图19:与涂覆有PEGDA-NR3、PEGDA-NR4和PEGDA-NR3/NR4 的纳滤膜接触后活细菌减少百分比的图。测试生物:106CFU/ml的大肠杆菌。
图20:暴露于109CFU/ml的大肠杆菌48小时后,(a)未涂覆的纳滤膜以及涂覆有(b)PEGDA-NR3、(c)PEGDA-NR4和(d) PEGDA-NR3/NR4的纳滤膜的SEM图像。
图21:(a)来自于大学池塘表面的生水在7天内穿过未涂覆的纳滤膜以及涂覆有PEGDA-NR3/NR4的纳滤膜的水通量。(b)在7 天实验中,未涂覆的纳滤膜和涂覆有PEGDA-NR3/NR4的纳滤膜的染料截留实验结果。
图22:(a)以0.1L/min穿过未涂覆的微滤膜和涂覆有 PEGDA-NR3/NR4的微滤膜的水通量,以及(b)膜的细菌去除率。
图23:在表面上涂覆多巴胺和抗菌抗生物污损胶体涂料的方法的示意图。
图24:使用多巴胺粘附层涂覆的基材的照片,所述基材包括(a) 不锈钢、(b)塑料(PVC)和(c)玻璃。
图25:在具有多巴胺粘附层的基材上制备的不同量的 PEI-PHMB胶体涂料(实施例8)上存活的金黄色葡萄球菌和大肠杆菌细菌的减少百分比。
图26:涂料的加速老化效果以及PEI-PHMB胶体涂料(实施例 8)对(a)金黄色葡萄球菌和(b)大肠杆菌的杀菌活性的影响。
图27:在暴露于108CFU/ml的大肠杆菌培养物后,在未涂覆的不锈钢、以及涂覆有位于多巴胺粘附层上的PEI-PHMB胶体涂料(实施例8)的不锈钢上粘附的大肠杆菌的SEM图像。
图28:在暴露于108CFU/ml的大肠杆菌培养物后,在未涂覆的塑料PVC、以及涂覆有位于多巴胺粘附层上的PEI-PHMB胶体涂料 (实施例8)的塑料PVC上的大肠杆菌的SEM图像。
图29:示出在暴露于108CFU/ml的大肠杆菌培养物后,在未涂覆的不锈钢、以及涂覆有位于多巴胺粘附层上的PEI-PHMB胶体涂料(实施例8)的不锈钢上的生物污损程度的荧光显微镜图像。
图30:示出在暴露于108CFU/ml的大肠杆菌培养物后,在未涂覆的塑料PVC、以及涂覆有位于多巴胺粘附层上的PEI-PHMB胶体涂料(实施例7)的塑料PVC上的生物污损程度的荧光显微镜图像。
图31:在暴露于108CFU/ml的大肠杆菌培养物14天后,来自于未涂覆的和涂覆的(a)不锈钢和(b)塑料PVC的可回收的活细菌。
图32:在加速老化的条件下,对于105CFU/ml的MRSA、粪肠球菌、不动杆菌和铜绿假单胞菌,用抗菌抗生物污损胶体涂料(实施例8)涂覆的医院织物的长效杀菌活性。
图33:(a)在DDI水中浸泡和快速搅拌后,未涂覆的医院织物、经酒精处理的医院织物、经漂白处理的医院织物和涂覆(实施例 12)的医院织物的杀菌性能,(b)在加速老化的条件下,在DDI水中浸泡和快速搅拌后,对于105CFU/ml的MRSA、粪肠球菌、不动杆菌和铜绿假单胞菌,经过醇处理的医院织物和涂覆(实施例8)的医院织物的杀菌性能。
图34:喷涂有PEI-PHMB胶体涂料的HEPA过滤器的照片以及在医院环境中对天然空气传播细菌的性能的总结。
图35:涂覆有用于胶体抗菌抗生物污损的环氧类制剂(a)涂料 -1(实施例35)和(b)涂料-2(实施例36)的不锈钢的照片。
图36:在基材上制备的不同量的环氧涂料-1(实施例35)上存活的金黄色葡萄球菌和大肠杆菌细菌的减少百分比。
图37:在暴露于108CFU/ml的大肠杆菌培养物后,大肠杆菌粘附在未涂覆的不锈钢和涂覆有环氧涂料-1(实施例35)和涂料-2(实施例36)的不锈钢上的SEM图像。
图38:大肠杆菌在未涂覆的不锈钢和涂覆有环氧涂料-1(实施例35)和涂料-2(实施例36)的不锈钢上的粘附的图。
图39:涂料的加速老化效果以及环氧涂料(实施例35)对于106 CFU/ml的(a)金黄色葡萄球菌和(b)大肠杆菌的杀菌活性的效果。
具体实施方式
本发明的化学组合物是抗菌抗生物污损胶体涂料,其具有用于暴露在空气和水/液体环境中的固体和多孔表面的理想物理特性。生物污损或生物学污损通常定义为湿润表面上细菌、植物、藻类或动物的积累。
本发明的涂料是中空的圆形颗粒的胶体悬浮液,包含至少两种或更多种聚合物,例如官能化生物聚合物(壳聚糖)、磷脂酰胆碱以及含有伯胺、仲胺和/或叔胺和两性离子基团的聚合物链。通过在给定的浓度和pH下使聚合物自组装成中空圆形颗粒来制备涂料组合物。可以使用稳定剂和/或通过交联来控制粒径。该中空的圆形颗粒可含有惰性或活性成分的核芯。惰性(非抗菌)核芯可包含例如水或惰性溶剂。活性(抗菌)核芯可包含例如一种或多种消毒剂、抗微生物剂和香料。
稳定剂可选自聚乙烯醇(PVA)和/或聚乙二醇(PEG)衍生物,并且可应用具有PVA或PEG基团的聚合物。在一个具体实施方案中,稳定剂为约0.01-20%(w/v)的PVA,mw=31,000-186,000g/mol;为约0.01-20%(w/v)的PEGMA,Mn=200-1000,优选=500;为约 0.01-20%(w/v)的MPEGMA,Mn=200-5000,优选=950。
表面涂料可以通过喷涂、浸涂、洗涂和擦拭或通过使用化学连接剂来完成。可以使用逐层涂覆法组合复合涂料。此外,含有该胶体的油漆和环氧树脂涂料可以直接涂覆在表面上。在所有情况下,本发明的涂料在空气和水中是稳定的,并且可抵抗水流的侵蚀。该涂料被设计为在工业、商业、市政和家庭用途中是安全有效的。
抗菌抗生物污损胶体涂料包含聚合物,该聚合物包括但不限于活性聚合物,例如聚乙烯亚胺(PEI)、聚二烯丙基二甲基氯化铵 (PDDA)、聚六亚甲基双胍(PHMB)、壳聚糖(CHIT)、聚季铵 盐(PQAC)和聚乙烯醇(PVA)。将特定活性聚合物定义为具有低 粘附性和/或有益抗菌性的活性聚合物。
化学交联可以将L-α-磷脂酰胆碱(EGG)、2-(二乙基氨基)乙基甲基丙烯酸酯(NR3)、[3-(甲基丙烯酰基氨基)丙基]二甲基-(3-磺丙基)氢氧化铵(NR4)以及3-磺丙基甲基丙烯酸酯(SO3)连接到主要的聚合物材料上。在关于附图的讨论之后所述的内容中,实施例 1-12描述了详细的制备方法。
附图的讨论
以下对附图的讨论参考下述部分中描述的实施例。参考了具体实施例。应当注意的是,所有附图和实施例并不意味着限制所附权利要求中要求保护的主题。
该涂料的胶体可以在一定尺寸范围内,以适应不同的涂料功能。例如,如图16所示,当涂料用于过滤应用时,增加胶体尺寸可以增加水通量。各种因素会影响胶体颗粒的尺寸。例如,可以通过调节组成聚合物的分子量来控制胶体颗粒的尺寸。图1示出了一系列PEI抗菌抗生物污损胶体涂料制剂的光学显微镜图像:10%PEI(Mn 60,000)、10%PEI(Mn=10,000)以及10%PEI(Mn=1,200)。具有较低分子量(约1,200g/mol)的PEI形成2微米的胶体,而具有较高分子量(约60,000g/mol)的PEI形成20微米的胶体。将图1中的组成聚合物的量增加至20%PEI(mw=10,000),也可改变胶体颗粒的尺寸。在聚合物的情况下,分子量(mw)表示平均分子量。改变活性聚合物的组成比例也可改变粒径。从左到右,粒径分别为2μm、 1μm、0.8μm和0.5μm。在图3中,以不同组成比例的PEI和PHMB ((a)4:1,(b)2:1,(c)1:2和(d)1:4)制备PEI-PHMB抗菌抗生物污损胶体涂料,从而使胶体粒径在5-20微米变化。具体地,在图3中,得到的粒径为(a)1μm,(b)0.5-2μm,(c)2-3μm和 (d)0.5μm。
也可以通过交联来控制粒径,这可以增加聚合物长度,且接枝不同的官能部分或聚合物可产生新的性能和功能。该方法可用于将两性离子分子、金属抗微生物剂和灭菌蛋白质和酶结合到主要聚合物中。例如,可以根据图2中所示的一般反应使PEI进行交联。
也可以通过使用稳定剂来控制胶体粒径,并且其受pH和浓度的影响较小。表1示出了包含不同浓度的PEI和PHMB的抗菌抗生物污损胶体涂料。
表1
样品No. | PHMB(20%)(μl) | PEI(20%)(μl) | DDI(μl) | PEI:PHMB |
1 | 50 | 50 | 0 | 1:1 |
2 | 50 | 25 | 25 | 2:1 |
3 | 50 | 12.5 | 37.5 | 4:1 |
4 | 25 | 50 | 25 | 1:2 |
5 | 12.5 | 50 | 37.5 | 1:4 |
C1 | 50 | 0 | 50 | N/A |
C2 | 0 | 50 | 50 | N/A |
可以进一步改变胶体粒径以适应活性核芯材料。显微镜图像(图 1和图3-5)证实该抗菌抗生物污损涂料的胶体颗粒是圆形且中空的,因此能够含有活性核芯材料。活性核芯材料可以是例如精油、香料、抗微生物剂和/或消毒剂。抗微生物剂包括多元醇,如法呢醇、肉桂醛和百里香油,以及混合抗微生物剂(百里香油、肉桂醛和法呢醇)。一些活性核芯可以是精油,其与香料、消毒剂和抗微生物剂具有相同的活性。制备包含、储存并释放配制涂料中的精油、香料、抗微生物剂和消毒剂的胶体颗粒的方法如实施例13-22所示。图4和5显示了含有百里香油的抗菌抗生物污损胶体涂料制剂。并成功配制了PEI、 PHMB和PEI-PHMB胶体和百里香油(实施例13-15)。图4中的粒径为(a)2-5μm和(b)1μm。在图5中,粒径为(a)0.5-2μm,(b) 1-2μm和(c)1-3μm。当使用活性核芯时,作为非限制性实施例,该涂料可以是PEI与肉桂醛、法呢醇和混合抗微生物剂(百里香油、肉桂醛和法尼醇)的稳定胶体悬浮液形式(图6)。根据本发明的可能的其它活性核芯组合利用胶体颗粒的中空区域来容纳、包封、储存和释放包含离子、分子和生物分子的活性物质,以用于消毒和抑制细菌污染。
一个示例性的涂料制剂,按重量计包含:
a.约0.01%-20%(w/v)的PVA,mw=31,000-186,000g/mol;
b.约0.01%-20%(w/v)的PEGMA,Mn=500;
c.约0.01%-20%(w/v)的MPEGMA,Mn=950;
d.0.0001%-5%(w/v)的聚乙烯亚胺,mw 1,200-60,000g/mol;购自SigmaAldrich;
e.0.05%-3%(w/v)的聚六亚甲基双胍,mw=2,000-2,600g/mol;
f.0.01%-20%(w/v)的聚二烯丙基二甲基氯化铵, mw=250,000-350,000g/mol;
g.0.01%-1.5%(w/v)的百里香油;
h.0.01%-1.5%(w/v)的法呢醇,mw=222g/mol;以及
i.0.05%-1.5%(w/v)的肉桂醛,mw=132g/mol。
因此,总活性聚合物的具体范围为0.0001%-30%(w/v)。理想地,活性聚合物的比例为1-4:4-1,含量为10w%-20w%。
图7示出了PEI(实施例1)、PDDA和PEI-PDDA(实施例5) 对于金黄色葡萄球菌和铜绿假单胞菌的杀菌性能。PEI-PDDA涂料 (PEI为97.339%,PDDA为91.457%)使活金黄色葡萄球菌减少 99.99%(4Log),使铜绿假单胞菌减少40%。图8描述了PHMB、 PDDA和PHMB-PDDA(实施例6)对于金黄色葡萄球菌和铜绿假单胞菌的类似的杀菌试验。PHMB-PDDA涂料(PHMB为99.990%, PDDA为91.457%)使活金黄色葡萄球菌减少99.99%(4Log),使铜绿假单胞菌(PHMB为51.389%,PDDA为31.433%)减少55%。图9示出了PEI、PHMB和PEI-PHMB(实施例7)对于金黄色葡萄球菌和铜绿假单胞菌的结果。PEI-PHMB涂料(PEI为97.339%,PHMB为99.990%)使活金黄色葡萄球菌减少99.99%(4Log),使铜绿假单胞菌生物膜形成减少99.99%(4Log)(PEI为39.912%,PHMB 为51.389%)。在后一种情况下,显示了PEI-PHMB组合的协同效应。图10描述了PEI、PHMB、PEI-PHMB涂料(实施例7-12)对于金黄色葡萄球菌、枯草芽孢杆菌、大肠杆菌和铜绿假单胞菌的杀菌活性。 PEI-PHMB涂料对于活细菌保持99.99%(4Log)的减少。
图11示出了一种用本发明的抗菌抗生物污损胶体涂料涂覆水过滤膜如反渗透膜(实施例24)、纳滤膜(实施例25)、超滤膜(实施例26)和微滤膜(实施例27)的方法。该方法包括:通过渗余物流将涂料引入膜,通过过滤使胶体颗粒沉积到膜表面上并随后粘附。该方法使涂覆的膜具有抗菌和抗生物污损性能。该方法的一个优点在于,即使在操作膜***中也可以简单地进行涂覆而不会中断。该涂料可以通过酸性反洗来移除。表2示出了抗菌抗生物污损胶体涂料在纳滤膜上的保留情况。
表2
图12比较了纳滤膜上的两种市售的锡类抗生物污损剂(不同浓度的2,2-二溴-3-次氮基丙酰胺(DBNPA)水溶液,Dow)和两种PEI 涂料(实施例1)的抗菌性能。用市售的抗生物污损剂处理的膜具有较低的杀菌性能(活性降低3%和21%),而本发明的PEI胶体涂料可以实现活细菌减少超过97%。图13表明即使在非常低的涂覆量下,本发明的PEI-PHMB胶体涂料(实施例7和27)与未涂覆的纳滤膜相比也能保持高于99.99%的细菌减少。图14包括浸没在细菌培养物中的膜样品在14天期间拍摄的一系列SEM图像。与未涂覆的膜和用市售抗生物污损剂(DBPNA,Dow)处理的膜相比,涂覆有本发明的PEI胶体(实施例1)的纳滤膜上的细菌粘附可忽略不计。这些研究证实,所述胶体涂料既具有抗菌性能又具有抗生物污损性能。图 15示出了在预计的大肠杆菌浓度为2500CFU/cm2和0的情况下,未涂覆样品和涂覆了PEI-PHMB的样品中纳滤膜上的生物膜生长。涂覆的膜不存在大肠杆菌。图16示出了PEI-PHMB胶体涂料对水通量的影响。在所有三种制剂中保持了活大肠杆菌减少99.99%,但胶体颗粒的大小从1微米增加到2微米和10微米。在相同涂覆量下使用较大胶体可以改善涂料对水通量的影响。表3表明涂料改善了膜的截留率/保留率。使用甲基橙溶液制备表3中所示的未涂覆膜和涂覆膜的截留数据。
表3
图17(a)描述了与未改性的壳聚糖(CHIT)、L-α-磷脂酰胆碱 (EGG)、2-(二乙氨基)乙基甲基丙烯酸酯(NR3)、[3-(甲基丙烯酰基氨基)丙基]二甲基-(3-磺丙基)氢氧化铵(NR4)、甲基丙烯酸3-磺丙酯(SO3)和溶菌酶(LYN)(实施例4)交联的胶体PEGDA的杀菌性能。在这些样品中PEGDA用作惰性聚合物,不同的抗菌、抗粘附和抗生物污损分子可以交联到PEGDA上。图17b示出了在不同组合物中EGG、NR3、NR4和LYN的进一步杀菌研究的结果。与EGG和LYN相比,NR3表现最佳。NR4具有较低的杀菌活性,但表现出优异的抗粘附性能。如图18中的纳滤膜表面的ToF-SIMS映射图所示,通过简单地刷涂抗菌抗生物污损胶体涂料(实施例28)可以实现均匀的表面涂覆。
图19和20绘制了未涂覆的纳滤膜以及涂覆有胶体 PEGDA-NR3、PEGDA-NR4和PEGDA-NR3/NR4的纳滤膜的抗菌和抗生物污损结果。图19表明,即使在多次使用后,与比未涂覆的膜相比,涂覆有胶体PEGDA-NR3和PEGDA-NR3/NR4的纳滤膜保持了活细菌减少80%-99%。图20表明,虽然PEGDA-NR4具有显著较低的杀菌活性,但其阻止了细菌在膜表面上的粘附。胶体 PEGDA-NR3/NR4通过“触杀”和“抗粘附”提供双重抗菌活性。图21 绘制了涂覆有胶体PEGDA-NR3/NR4的纳滤膜和未涂覆的纳滤膜的水通量和染料截留。如图21(a)所示,与未涂布的膜相比,水通量得到改善(由于NR4使得具有更高的表面亲水性),并且如图21(b)的染料截留实验所示,并未影响膜的分离性能。膜的故意污损表明,涂有胶体PEGDA-NR3/NR4抗菌抗生物污损涂料的纳滤膜对生物污损具有更强的抵抗力。图22绘制了未涂覆的微滤膜和涂覆的微滤膜 (实施例29)的水通量和细菌过滤。从该研究中可以看出,涂料没有改变膜的过滤性能。类似地,涂有胶体PEGDA-NR3/NR4抗菌抗生物污损涂料的微滤膜对抗生物污损性更强。因此,本发明的涂料将这些以及类似的抗菌、抗粘附和抗生物污损分子和部分结合到活性聚合物如PEI、PHMB、PDDA、PQAC和类似的抗菌聚合物中,以构建用于表面的多重抗菌抗生物污损胶体涂料。
在实施例30中描述了将多巴胺和类似材料作为粘附层用于表面上的本发明涂料,并在图23中示出。多巴胺粘附层通过儿茶酚基团与聚合物的胺或硫醇基团之间的希夫反应与胶体涂料结合。其他分子连接剂如乙烯基砜可以通过“点击化学”将抗菌抗生物污损胶体涂料粘附于目标物。图24示出了具有多巴胺粘附层的基材上的抗菌抗生物污损胶体涂料,其中所述基材包括不锈钢、塑料PVC和玻璃(实施例31)。表4中的不锈钢和塑料PVC样品的X射线光电子能谱表明,通过胶体PEI-PHMB的更高的氮含量,涂料成功地粘附到表面上。具体地,表4(a)示出了在水中洗涤后,具有多巴胺粘附层的不锈钢上的胶体涂料的X射线光电子能谱的元素分析结果;表4(b) 示出了在水中洗涤后,具有多巴胺粘附层的塑料PVC上的胶体涂料的X射线光电子能谱的元素分析结果。
表4(a)
表4(b)
在水中浸泡7天后,表面上的氮含量无明显降低,在此期间将基材置于35℃的去离子蒸馏(DDI)水中,在快速搅拌下模拟流动环境。结果表明该涂料适用于水生环境,并且耐水腐蚀和侵蚀。
图25绘制了抗菌抗生物污损胶体涂料(实施例8)在具有多巴胺粘附层的基材上的杀菌性能。该图示出了每单位面积涂覆量的表面杀菌性能对革兰氏阳性和革兰氏阴性细菌的影响。在涂覆水平为24 mg/cm2(湿基)或0.2mg/cm2PEI和0.05mg/cm2PHMB(干基)时,涂料可实现活细菌减少超过90%。在30mg/cm2(湿基)或0.24mg/cm2 PEI和0.06mg/cm2PHMB(干基)下可以使活细菌减少99.99% (4Log)。图26(a)和26(b)分别绘制了涂料加速老化的结果和对金黄色葡萄球菌和大肠杆菌杀菌性能的结果。每个实验日相当于浸入水中25天。结果表明,杀菌活性可以长时间保持,例如3-14天,超过7天和/或7-14天。
粘附在位于不锈钢和塑料PVC表面上的多巴胺粘附层上的抗菌抗生物污损胶体涂料(实施例8)的抗生物污损性能通过以下方法进行评价:通过图27和28中的扫描电子显微技术、通过图29和30 中的荧光显微技术、以及通过图31中的标准细菌学方法直接计数活细菌。将涂覆样品和未涂覆的样品浸入108CFU/ml的大肠杆菌培养物中14天。结果一致表明,如图27和28所示,与未涂覆的基材相比,涂覆的不锈钢和塑料PVC表面上的细菌粘附较少,并且与健康的大肠杆菌相比,这些细菌在总体形态上表现出差异。图29和30 示出了细菌生物膜在不锈钢和塑料PVC的未涂覆表面上的显著繁殖。生物膜含有死细菌和活细菌细胞的有机基质。即使在细菌培养 14天后,涂覆的表面依然主要显示来自涂料材料的荧光。从表面回收活细菌,培养并计数。图31中示出的结果表明,与未涂覆的样品相比,来自涂覆的不锈钢和塑料PVC的细菌减少了90%。这些结果证实了在水环境中涂料的长期抗菌和抗生物污损性能。
将抗菌抗生物污损胶体涂料应用于包括纺织物和非织造织物的多孔介质。图32示出了在加速老化下,涂覆的织物针对医院环境中发现的常见环境病原体的性能。通过将织物暴露于高温(50℃)一段给定的时间,然后用105CFU/ml的细菌溶液直接进行1分钟的接触时间来进行老化。结果表明,经过30天的加速老化研究,涂覆的织物保持了高杀菌活性。图33(a)示出了涂有低浓度抗菌抗生物污损胶体涂料的织物与用醇和漂白溶液处理的织物的比较。在1分钟的接触时间内,涂覆的织物可以使活细菌减少超过98%。图33(b)表明涂覆的织物在快速搅拌并暴露于水后仍然具有杀菌作用。与用乙醇处理的织物相比,其保持了超过90%的细菌减少。
图34示出了在空气过滤研究中使用的HEPA过滤器,其中一半过滤器涂有抗菌抗生物污损胶体涂料,另一半未涂覆。表5(a)表面空气过滤器上的胶体涂料在14天的时间内通过触杀可以减少超过 78%的细菌。
表5(a)
持续时间 | 总减少率 |
2周操作 | 78.79% |
4周操作 | 58.75% |
抗菌性能在30天内减少至58.75%,这可能是由于涂料层被污垢覆盖。图34和表5(b)还报道了涂覆有被PEI-PHMB包封的百里香油的HEPA过滤器可以在14天的时间内通过触杀和释放杀使细菌减少超过96%。
表5(b)
与未涂覆的空气过滤器部分相比,在细菌与涂覆表面接触时,涂料层可使细菌不能存活。
在专利CN 1605607中描述的普通防腐涂料的基础上,制备环氧聚合物涂料材料。其符合国内和饮用水安全评价标准(2011年)的配电设备和保护材料中列出的相关规范,并可用于船舶水容器、配水管和食品接触容器。表6示出了环氧涂料的基本配方:
表6
不锈钢基材上的聚合物涂覆量为33mg/cm2(图35)。图36示出了涂覆量对涂料的杀菌性能的影响。当涂覆量超过21mg/cm2时,杀菌性能可达到大于80%。图37示出了与涂有环氧涂料-1(实施例 35)和涂料-2(实施例36)的不锈钢上没有细菌的情况相比,细菌在未涂覆的不锈钢上的粘附性。
图33证实两种涂料在14天的时间内可以使细菌粘附减少 99.9%。在将涂覆的不锈钢浸入水中后进行的加速老化研究表明,涂料缓慢侵蚀,并且可以长时间保持杀菌活性。
实施例
第1部分:胶体涂料配方
实施例1.聚乙烯亚胺(PEI)
将分子量为1,000g/mol至60000g/mol的聚乙烯亚胺(PEI)用于制备抗菌抗生物污损胶体涂料。简而言之,将聚合物溶解在蒸馏水中,以制备浓度为0.1重量%至40重量%的PEI溶液。然后将PEI 溶液以5:1至1:5的体积比加入到含有0.1重量%至10重量%聚合物的聚乙烯醇(PVA)溶液中。在快速搅拌下逐滴添加,然后超声处理 1分钟,产生图1中所示的胶体材料。
实施例2.官能化壳聚糖
使用分子量为5000g/mol至120000g/mol的生物聚合物壳聚糖和官能化壳聚糖来制备抗菌抗生物污损胶体涂料。简而言之,将聚合物溶解在蒸馏水中,以制备浓度为0.1重量%至40重量%的生物聚合物溶液。然后将生物聚合物溶液以5:1至1:5的体积比加入到含有0.1 重量%至10重量%聚合物的聚乙烯醇(PVA)溶液中。在快速搅拌下逐滴添加,然后超声处理1分钟,产生胶体材料。
实施例3.聚季铵盐
将分子量为5000g/mol至1000000g/mol的聚季铵盐用于制备抗菌抗生物污损胶体涂料,其中该聚季铵盐包括羟乙基纤维素乙氧基化物、聚[(2-乙基二甲基铵基甲基丙烯酸乙基硫酸乙酯)-共-(1-乙烯基吡咯烷酮)]以及聚[(3-甲基-1-乙烯基咪唑氯化物)-共-(1-乙烯基吡咯烷酮)]。简而言之,将聚合物溶解在蒸馏水中,以制备浓度为0.1重量%至40重量%的聚季铵盐溶液。然后将聚季铵盐溶液以5:1至1:5的体积比加入到含有0.1重量%至10重量%聚合物的聚乙烯醇(PVA) 溶液中。在快速搅拌下逐滴添加,然后超声处理1分钟,产生胶体材料。
实施例4.聚合物交联
通过使活性聚合物(图2)与分子量为500g/mol至950g/mol 的第三聚合物如聚(乙二醇)甲基丙烯酸酯或聚(乙二醇)甲基醚甲基丙烯酸酯交联,以调节胶体的形状和尺寸,以用于基于PEI的抗菌抗生物污损胶体涂料。
实施例5.PEI+PDDA(比例1:1)
将分子量为1000g/mol至60000g/mol的聚乙烯亚胺(PEI)溶解在蒸馏水中,以制备浓度为10重量%至20重量%的PEI溶液。将分子量为150000g/mol至230000g/mol的聚二烯丙基二甲基氯化铵 (PDDA)溶解在水中,以制备浓度为10重量%至20重量%的PDDA 溶液。将相同体积相同浓度的PEI和PDDA溶液快速混合在一起,然后超声处理1分钟,以制得比例为1:1的胶体PEI:PDDA。
实施例6.PHMB+PDDA(比例1:1)
将分子量为2000g/mol至2600g/mol的聚六亚甲基双胍 (PHMB)溶解在蒸馏水中,以制备浓度为10重量%至20重量%的 PHMB溶液。将分子量为150000g/mol至230000g/mol的聚二烯丙基二甲基氯化铵(PDDA)溶解在水中,以制备浓度为10重量%至 20重量%的PDDA溶液。将相同体积相同浓度的PHMB和PDDA溶液快速混合在一起,然后超声处理1分钟,以制得比例为1:1的胶体 PHMB:PDDA。
实施例7.PEI+PHMB(比率1:1)
将分子量为10000g/mol的聚乙烯亚胺(PEI)溶解在蒸馏水中,以制备浓度为10重量%至20重量%的PEI溶液。将分子量为2000 g/mol至2600g/mol的聚六亚甲基双胍(PHMB)溶解在蒸馏水中,以制备浓度为10重量%至20重量%的PHMB溶液。将相同体积相同浓度的PEI和PHMB溶液快速混合在一起,然后超声处理1分钟,以制得比例为1:1的胶体PEI:PHMB。将胶体稀释以获得最终浓度为 2重量%至12重量%的PEI(1重量%至6重量%)和PHMB(1重量%至6重量%)。
实施例8.PEI+PHMB(比例4:1)
将分子量为10000g/mol的聚乙烯亚胺(PEI)溶解在蒸馏水中,以制备浓度为10重量%至20重量%的PEI溶液。将分子量为2000 至2600g/mol的聚六亚甲基双胍(PHMB)溶解在蒸馏水中,以制备浓度为2.5重量%至5重量%的PHMB溶液。将相同体积的PEI和 PHMB溶液快速混合在一起,然后超声处理1分钟,以制得比例为 4:1的胶体PEI:PHMB,如图3a所示。将胶体稀释,以获得最终的1 重量%至6重量%的PEI和0.25重量%至1.5重量%的PHMB。
实施例9.PEI+PHMB(比例2:1)
将分子量为10000g/mol的聚乙烯亚胺(PEI)溶解在蒸馏水中,以制备浓度为10重量%至20重量%的PEI溶液。将分子量为2000 至2600g/mol的聚六亚甲基双胍(PHMB)溶解在蒸馏水中,以制备浓度为5重量%至10重量%的PHMB溶液。将相同体积的PEI和 PHMB溶液快速混合在一起,然后超声处理1分钟,以制得比例为 2:1的胶体PEI:PHMB,如图3b所示。将胶体稀释以获得最终的1重量%至6重量%的PEI和0.5重量%至3重量%的PHMB。
实施例10.PEI+PHMB(比率1:2)
将分子量为10000g/mol的聚乙烯亚胺(PEI)溶解在蒸馏水中,以制备浓度为5重量%至10重量%的PEI溶液。将分子量为2000 g/mol至2600g/mol的聚六亚甲基双胍(PHMB)溶解在蒸馏水中,以制备浓度为10重量%至20重量%的PHMB溶液。将相同体积的 PEI和PHMB溶液快速混合在一起,然后超声处理1分钟,以制得比例为1:2的胶体PEI:PHMB,如图3c所示。将胶体稀释,以获得最终的0.5重量%至3重量%的PEI和1重量%至6重量%的PHMB。
实施例11.PEI+PHMB(比率1:4)
将分子量为10000g/mol的聚乙烯亚胺(PEI)溶解在蒸馏水中,以制备浓度为5重量%至10重量%的PEI溶液。将分子量为2000 g/mol至2600g/mol的聚六亚甲基双胍(PHMB)溶解在蒸馏水中,以制备浓度为10重量%至20重量%的PHMB溶液。将相同体积的 PEI和PHMB溶液快速混合在一起,然后超声处理1分钟,以制得比例为1:2的胶体PEI:PHMB,如图3d所示。将胶体稀释,以获得最终的0.25重量%至1.5重量%的PEI和1重量%至6重量%的PHMB。
实施例12.PEI+PHMB(比率39:1)
将分子量为1200至10000g/mol的聚乙烯亚胺(PEI)溶解在蒸馏水中,以制备浓度为5重量%至10重量%的PEI溶液。将分子量为2000至2600g/mol的聚六亚甲基双胍(PHMB)溶解在蒸馏水中,以制备浓度为10重量%至20重量%的PHMB溶液。将相同体积的 PEI和PHMB溶液快速混合在一起,然后超声处理1分钟,以制得比例为39:1的胶体PEI:PHMB。将胶体稀释,以获得最终的1重量%至 6重量%的PEI和0.025重量%至0.15重量%的PHMB。
实施例13.PHMB+百里香油(1:5)
将分子量为2000g/mol至2600g/mol的聚六亚甲基双胍 (PHMB)溶解在蒸馏水中,以制备浓度为5重量%至20重量%的 PHMB溶液。将测量量的百里香油加入至0.1重量%至10重量%的 PVA溶液中并乳化。将相同体积的PHMB和百里香油/PVA溶液快速混合在一起,然后超声处理1分钟以制得PHMB包封的百里香油。加入吐温80以稳定所得的胶体,如图4a所示。
实施例14.PEI+百里香油(1:5)
将分子量为1200g/mol至10000g/mol的聚乙烯亚胺(PEI)溶解在蒸馏水中,以制备浓度为5重量%至10重量%的PEI溶液。将测量量的百里香油加入至0.1重量%至10重量%的PVA溶液中并乳化。将相同体积的PEI和百里香油/PVA溶液快速混合在一起,然后超声处理1分钟,以制得PEI包封的百里香油。加入吐温80以稳定所得的胶体,如图4b所示。
实施例15.PEI+PHMB+百里香油
将分子量为10000g/mol的聚乙烯亚胺(PEI)溶解在蒸馏水中,以制备浓度为10重量%至20重量%的PEI溶液。将分子量为2000 g/mol至2600g/mol的聚六亚甲基双胍(PHMB)溶解在蒸馏水中,以制备浓度为10重量%至20重量%的PHMB溶液。将测量量的百里香油加入至0.1重量%至10重量%的PVA溶液中并乳化。加入给定量的PEI溶液,然后超声处理1分钟,然后加入适当体积的PHMB 溶液,接着再超声处理1分钟以制得胶体PEI:PHMB:百里香油材料,如图5所示。加入吐温80以稳定所得的胶体。
实施例16.PEI+肉桂醛
将分子量为1200g/mol至10000g/mol的聚乙烯亚胺(PEI)溶解在蒸馏水中,以制备浓度为5重量%至10重量%的PEI溶液。将测量量的肉桂醛加入至0.1重量%至10重量%的PVA溶液中并乳化。将相同体积的PEI和肉桂醛/PVA溶液快速混合在一起,然后超声处理1分钟以制得PEI包封的肉桂醛。加入吐温80以稳定所得的胶体,如图6a所示。
实施例17.PHMB+肉桂醛
将分子量为2000g/mol至2600g/mol的聚六亚甲基双胍 (PHMB)溶解在蒸馏水中,以制备浓度为5重量%至20重量%的 PHMB溶液。将测量量的肉桂醛加入至0.1重量%至10重量%P的 PVA溶液中并乳化。将相同体积的PHMB和肉桂醛/PVA溶液快速混合在一起,然后超声处理1分钟以制得PHMB包封的肉桂醛。加入吐温80以稳定所得的胶体。
实施例18.PEI+PHMB+肉桂醛
将分子量为10000g/mol的聚乙烯亚胺(PEI)溶解在蒸馏水中,以制备浓度为10重量%至20重量%的PEI溶液。将分子量为2000 g/mol至2,600g/mol的聚六亚甲基双胍(PHMB)溶解在蒸馏水中,以制备浓度为10重量%至20重量%的PHMB溶液。将测量量的肉桂醛加入至0.1重量%至10重量%的PVA溶液中并乳化。加入给定量的PEI溶液,然后超声处理1分钟,然后加入适当体积的PHMB溶液,接着再超声处理1分钟以制得胶体PEI:PHMB:肉桂醛材料。加入吐温80以稳定所得的胶体。
实施例19.PEI+法呢醇
将分子量为1200g/mol至10000g/mol的聚乙烯亚胺(PEI)溶解在蒸馏水中,以制备浓度为5重量%至10重量%的PEI溶液。将测量量的法呢醇溶解在DMSO/水溶液中,以获得浓度为10重量%至 50重量%的溶液。将法尼醇溶液加入至0.1重量%至10重量%的PVA 溶液中并乳化。将相同体积的PEI和法呢醇/PVA溶液快速混合在一起,然后超声处理1分钟以制得PEI包封的法呢醇。加入吐温80以稳定所得的胶体,如图6b所示。
实施例20.PHMB+法呢醇
将分子量为2000g/mol至2600g/mol的聚六亚甲基双胍 (PHMB)溶解在蒸馏水中,以制备浓度为5重量%至20重量%的 PHMB溶液。将测量量的法呢醇溶解在DMSO/水溶液中,以获得浓度为10重量%至50重量%的溶液。将法尼醇溶液加入至0.1重量%至10重量%的PVA溶液中并乳化。将相同体积的PHMB和法尼醇 /PVA溶液快速混合在一起,然后超声处理1分钟以制得PHMB包封的法呢醇。加入吐温80以稳定所得的胶体。
实施例21.PEI+PHMB+法呢醇
将分子量为10000g/mol的聚乙烯亚胺(PEI)溶解在蒸馏水中,以制备浓度为10重量%至20重量%的PEI溶液。将分子量为2000 至2600g/mol的聚六亚甲基双胍(PHMB)溶解在蒸馏水中,以制备浓度为10重量%至20重量%的PHMB溶液。将测量量的法呢醇溶解在DMSO/水溶液中,以获得浓度为10重量%至50重量%的溶液。将法尼醇溶液加入至0.1重量%至10重量%的PVA溶液中并乳化。加入给定量的PEI溶液,然后超声处理1分钟,然后加入适当体积的 PHMB溶液,接着再超声处理1分钟以制得胶体PEI:PHMB:法呢醇材料。加入吐温80以稳定所得的胶体。
实施例22.PEI+PHMB+混合抗微生物剂
将分子量为10000g/mol的聚乙烯亚胺(PEI)溶解在蒸馏水中,以制备浓度为10重量%至20重量%的PEI溶液。将分子量为2000 g/mol至2600g/mol的聚六亚甲基双胍(PHMB)溶解在蒸馏水中,以制备浓度为10重量%至20重量%的PHMB溶液。制备含有百里香油、肉桂粉和法尼醇的混合抗微生物剂。将混合抗微生物剂溶液加入至0.1重量%至10重量%的PVA溶液中并乳化。加入给定量的PEI 溶液,然后超声处理1分钟,然后加入适当体积的PHMB溶液,接着再超声处理1分钟以产生胶体PEI:PHMB:混合抗微生物剂,如图 6c所示。加入吐温80以稳定所得的胶体。
第2部分:选择应用
实施例23.用于水过滤膜的抗生物污损涂料
通过过滤将抗菌抗生物污损胶体涂料涂覆在水过滤膜上。该方法在0.01MPa的跨膜压力下进行,涂料可以在0.1重量%至10重量%的范围内调节。涂覆也可以通过喷涂、洗涂和浸涂的方法进行。
实施例24.用于反渗透(RO)膜的抗生物污损涂料
通过死端式过滤将抗菌抗生物污损胶体涂料涂覆在RO膜上。该方法在0.1MPa的跨膜压力下进行,涂料可以在0.1重量%至10 重量%的范围内调节。涂覆也可以通过喷涂、洗涂和浸涂的方法进行。
实施例25.用于纳滤(NF)膜的抗生物污损涂料
通过死端式过滤将抗菌抗生物污损胶体涂料涂覆在纳滤膜上。该方法在0.1MPa的跨膜压力下进行,涂料可以在0.1重量%至10 重量%的范围内调节。涂覆也可以通过喷涂、洗涂和浸涂的方法进行。
实施例26.用于超滤(UF)膜的抗生物污损涂料
通过死端式过滤将抗菌抗生物污损胶体涂料涂覆在超滤膜上。该方法在0.05MPa的跨膜压力下进行,涂料可以在0.1重量%至10 重量%的范围内调节。涂覆也可以通过喷涂、洗涂和浸涂的方法进行。
实施例27.用于微滤(MF)膜的抗生物污损涂料
通过死端式过滤将抗菌抗生物污损胶体涂料涂覆在微滤膜上。该方法在0.05MPa的跨膜压力下进行,涂料可以在0.1重量%至10 重量%的范围内调节。涂覆也可以通过喷涂、洗涂和浸涂的方法进行。
实施例28.用于NF膜的抗生物污损涂料(交联分子部分)
由PEGDA聚合物与L-α-磷脂酰胆碱(EGG)、2-(二乙氨基)乙基甲基丙烯酸酯(NR3)、[3-(甲基丙烯酰基氨基)丙基]二甲基(3-磺丙基)氢氧化铵(NR4)、3-磺丙基甲基丙烯酸酯(SO3)和溶菌酶(LYN) 交联来制备抗菌抗生物污损胶体涂料。胶体PEGDA-EGG、 PEGDA-NR3、PEGDA-NR4、PEGDA-SO3、PEGDA-LYN以及与未修饰的壳聚糖交联的PEGDA-CHI的杀菌活性如图17所示。将胶体涂料刷涂在纳米过滤膜上,但也可以使用其他涂覆的方法,包括过滤、喷涂、洗涂和浸涂技术。涂覆在纳米过滤膜上的PEGDA-NR3、 PEGDA-NR4和PEGDA-NR3/NR4的性能绘制于图18-20。
实施例29.用于MF膜的抗生物污损涂料(交联分子部分)
由PEGDA聚合物与L-α-磷脂酰胆碱(EGG)、2-(二乙基氨基) 乙基甲基丙烯酸酯(NR3)、[3-(甲基丙烯酰基氨基)丙基]二甲基(3- 磺丙基)氢氧化铵(NR4)、3-磺丙基甲基丙烯酸酯(SO3)和溶菌酶 (LYN)交联来制备抗菌抗生物污损胶体涂料。将胶体涂料喷涂到微滤膜上,但也可以使用其他涂覆方法,包括过滤、刷涂、洗涂和浸涂技术。涂覆在MF膜上的PEGDA-NR3/NR4的性能如在图21所示。
实施例30.使用多巴胺作为粘附层的抗菌抗生物污损涂料
将抗菌抗生物污损胶体涂料涂覆在具有多巴胺或类似分子粘附层的表面上。由tris-HCl缓冲液(pH8.5)溶液制备2mg/ml多巴胺溶液。通过喷涂、刷涂、洗涂和浸涂或类似的方法将粘合层涂覆在表面上。通过漂洗除去过量的多巴胺,并在涂覆抗菌抗生物污损胶体涂料之前干燥样品,如图23所示。
实施例31.使用多巴胺作为粘附层的高抗性涂料
将抗菌抗生物污损胶体涂料涂覆在沉积于不锈钢、塑料PVC和玻璃上的多巴胺粘附层的表面上(图24)。如图26中的加速研究所示,即使在搅拌下,表面上的涂料也是耐水的。如图26-31所示,即使在高细菌污染下其也能保持抗菌和抗生物污损性能。
实施例32.织物和非织造织物上的抗菌抗生物污损涂料
将抗菌抗生物污损胶体涂料稀释2倍和4倍,并通过湿涂法涂覆到纺织材料上。也可以使用喷涂、浸涂和相关的涂覆方法。此外,可以在织物的机洗中在漂洗循环期间添加涂料。
实施例33.织造织物和非织造织物上的高抗性涂料
将抗菌抗生物污损胶体涂料涂覆在医院床隔板织物上。图32和 33总结了涂覆的织物对一系列革兰氏阳性和革兰氏阴性细菌(包括病原体和耐药微生物)的杀菌性能。图32中加速老化的结果表明涂覆的织物长时间保持杀菌效果。在快速搅拌下反复浸入水中不会影响涂覆的织物的杀菌性能(参见图33)。
实施例34.微粒空气过滤器上的抗菌涂料
将实施例1-12和实施例13-22中给出的抗菌抗生物污损胶体涂料通过喷涂的方法涂覆在包括HEPA的微粒空气过滤器上。也可用电喷雾法、浸涂法、洗涂法和相关的方法作为替代方法。图34是喷涂有1PEI:1PHMB胶体涂料的HEPA过滤器及其对空气传播细菌的抗菌性能的图片。
实施例35.用于抗菌抗生物污损胶体涂料的环氧基制剂-1
通过将100体积份的环氧树脂与30至70体积份的固化剂和100 至200体积份的实施例8中的抗菌抗生物污损胶体涂料混合,从而制备典型的制剂。加入20至60体积份的溶剂,然后快速混合。
实施例36.用于抗菌抗生物污损胶体涂料的环氧类制剂-2
通过将100体积份的环氧树脂与30至70体积份的固化剂和100 至200体积份的实施例11中的抗菌抗生物污损胶体涂料混合,从而制备典型的制剂。加入20至60体积份的溶剂,然后快速混合。
实施例37.抗菌环氧树脂表面涂料
将实施例35和36中所述的环氧树脂涂料涂覆到不锈钢卡盘上,如图35所示,并用于抗菌研究(图37-39)。
第3部分:方法
表征
使用配备有能量色散X射线检测器的JEOL JSM-6300和 JEM-6300F扫描电子显微镜拍摄初始膜、具有抗菌制剂的膜、初始基材和涂覆有抗菌制剂的基材的SEM图像。
X射线光电子能谱
使用配备有多技术***(AES、SAM、XPS)的Model PHI 5600 (物理电子学)对初始基材和涂覆有抗菌制剂的基材上的元素组成进行分析。
荧光显微镜
使用Nikon TE2000E-PFS·双视图微型成像仪分析初始基材和涂覆有抗菌制剂的基材上生物污损的分布。
测试研究方案
抗菌活性
将通过再培养制备的细菌稀释至106CFU/mL。将100μL稀释剂滴在每个载体上。使用计时器监测载体与细菌的接触时间。然后,将载体转移到含有10mL中和剂溶液的无菌瓶中;所述中和剂溶液为 0.9%(w/v)NaCl、0.2%w/v吐温80和0.001M硫代硫酸钠。进行温育30分钟。
如果需要,用无菌盐水溶液连续稀释细菌。将100μL溶液接种到TSA琼脂中并培养24小时。取出平板并通过计数菌落形成单位 (CFU)计数。
抗粘附测试
在抗粘附测试中,在静态分批条件下将涂覆和未涂覆的膜暴露于108CFU/ml的大肠杆菌的营养肉汤培养基中,以模拟在14天期间最差的情况。培育后,用无菌DDI水轻轻洗涤膜以除去悬浮的微生物。然后在扫描电子显微镜(SEM)下观察洗涤的膜,以搜索和估计膜表面上粘附的细菌的密度。所使用的SEM是JEOLJSM 6300F型号。
膜渗透性
通过死端式过滤单元中的膜测量水渗透。在300kPa的压力和 25℃的进料温度下,通过60分钟内渗透的水的体积获得去离子水的流量。使用相同的装置在膜上进行吖啶橙筛分试验。制备浓度为0.1 g/L的进料溶液。在300kPa的压力和25℃的进料温度下,在30分钟内收集渗透液。通过UV-vis测量进料和渗透液中吖啶橙的浓度。根据方程式R=1-Cp/Cf计算修饰前后的截留量(R),其中Cp和Cf分别是渗透液和进料中的UV-vis浓度。
生物膜染色
用于染色生物膜的染色剂为FilmtracerTM 生物膜耐久性试剂盒。染色方案遵循制造商的说明。简而言之,将聚合物胶束溶液涂覆的不锈钢和PVC样品放入培养皿中,所述培养皿含有10 ml营养肉汤,其中大肠杆菌为108CFU/ml。培养后,使用PBS将未粘附的细菌从基材表面洗掉,并将漂洗后的基材转移到6孔板中。通过将3μl SYTO9和3μl碘化丙啶染色剂加入1ml过滤的无菌水中来制备染色剂的工作溶液。然后加入200μl根据制造商混合的染色剂。将染色皿在黑暗中温育20至30分钟。染色后,将样品用过滤的无菌水漂洗三次,以除去所有过量的染色剂。
膜上的胶束溶液的稳定性
进行测试以研究处理过的膜的稳定性。将处理过的膜安装在图6 所示的错流膜过滤单元中,并保持3巴的渗余物流。收集渗余物并使用UV-Vis光谱仪通过比色法分析洗脱的抗生物污损剂。结果表明,膜保留了超过85%的过滤抗生物污损剂。
多个表面上的胶束溶液的稳定性
将涂覆的样品暴露于50ml去离子蒸馏水中,并以100至200rpm 摇动14天。通过UV-vis分光光度计测量溶液中的浸出聚合物。测试样品上剩余涂料的抗菌活性。
Claims (23)
1.一种抗菌抗生物污损涂料制剂,包含:
中空圆形胶体结构,包括:
a)活性聚合物壳;以及
b)活性或惰性核芯;
其中所述活性聚合物壳包含具有抗菌和抗生物污损活性的聚合物,并且所述聚合物选自由聚乙烯亚胺(PEI)、聚二烯丙基二甲基氯化铵(PDDA)和聚六亚甲基双胍(PHMB)组成的组中的两种或三种;
其中所述核芯具有活性并含有一种或多种消毒剂、抗微生物剂和香料;以及
其中所述核芯具有惰性并含有水或惰性溶剂;并且
其中所述中空圆形胶体结构在至少3个月内是稳定的。
2.根据权利要求1所述的涂料制剂,其中所述聚合物为PEI和PHMB。
3.根据权利要求1所述的涂料制剂,其中所述聚合物为PEI和PDDA。
4.根据权利要求1所述的涂料制剂,其中所述聚合物为PHMB和PDDA。
5.根据权利要求1所述的涂料制剂,其中所述聚合物为PEI、PHMB和PDDA。
6.根据权利要求1所述的涂料制剂,其中所述聚合物的浓度为所述聚合物壳的0.5重量%至100重量%。
7.根据权利要求6所述的涂料制剂,其中所述聚合物的浓度为所述聚合物壳的10重量%至20重量%。
8.根据权利要求1所述的涂料制剂,其中所述核芯为活性核芯,其包含一种或多种抗微生物剂,所述抗微生物剂选自由精油、多元醇和醛组成的组。
9.根据权利要求8所述的涂料制剂,其中所述抗微生物剂为精油,并且所述精油为百里香油。
10.根据权利要求8所述的涂料制剂,其中所述抗微生物剂为多元醇,并且所述多元醇为法呢醇。
11.根据权利要求8所述的涂料制剂,其中所述抗微生物剂为醛,并且所述醛为肉桂醛。
12.根据权利要求8所述的涂料制剂,其中所述一种或多种抗微生物剂包含精油、多元醇以及醛,所述精油为百里香油,所述多元醇为法呢醇,所述醛为肉桂醛。
13.根据权利要求1所述的涂料制剂,其中所述活性聚合物壳包含:0.0001%至5%(w/v)的PEI,该PEI的mw为1,200g/mol至60,000g/mol;0.05%至3%(w/v)的PHMB,该PHMB的mw为2,000g/mol至2,600g/mol;以及0.01%至20%(w/v)的PDDA,该PDDA的mw为250,000g/mol至350,000g/mol;并且其中所述活性核芯含有0.01%至1.5%(w/v)的百里香油、0.01%至1.5%(w/v)的法呢醇、以及0.05%至1.5%(w/v)的肉桂醛。
14.根据权利要求1所述的涂料制剂,其中所述涂料制剂还包含稳定剂。
15.根据权利要求13所述的涂料制剂,其中所述涂料制剂还包含:0.01%至20%(w/v)的聚乙烯醇,该聚乙烯醇的mw为31,000g/mol至186,000g/mol;0.01%至20%(w/v)的PEGMA,该PEGMA的Mn为500;以及0.01%至20%(w/v)的MPEGMA,该MPEGMA的Mn为950。
16.一种制造用于无孔表面、多孔膜或多孔材料的抗菌抗生物污损涂料的方法,包括:
-按以下步骤制备抗菌抗污损制剂:
(a)制备含有活性聚合物的水溶液,其中所述活性聚合物选自由聚乙烯亚胺(PEI)、聚二烯丙基二甲基氯化铵(PDDA)和聚六亚甲基双胍(PHMB)组成的组中的两种或三种;
(b)将抗微生物剂或溶剂加入至所述活性聚合物的水溶液中;
(c)制备具有中空圆形胶体结构的乳液,包括:将含有一种或多种表面活性剂的稳定剂混合物加入至所述抗微生物剂或溶剂和活性聚合物的溶液中,以形成抗菌抗生物污损制剂;以及
(d)由抗菌和抗生物污损制剂制备所述抗菌抗生物污损涂料;以及
-将所述抗菌抗生物污损涂料涂覆在无孔表面、多孔膜或多孔材料上。
17.根据权利要求16所述的方法,其中所述无孔表面为不锈钢表面、玻璃表面以及聚氯乙烯表面。
18.根据权利要求16所述的方法,其中所述多孔膜选自由反渗透膜、纳滤膜、超滤膜、微滤膜和高效微粒空气过滤器构成的组。
19.根据权利要求16所述的方法,其中所述多孔材料为非织造织物材料以及纺织材料。
20.根据权利要求16所述的方法,其中所述表面活性剂为聚乙烯醇以及聚乙二醇。
21.根据权利要求16所述的方法,其中涂覆抗菌抗生物污损涂料包括通过使用擦拭、刷涂、流延、浸涂、洗涂、旋涂、喷涂以及逐层涂覆中的至少一种方式,将所述抗菌抗生物污损涂料涂覆在无孔表面、多孔膜或多孔材料上。
22.根据权利要求16所述的方法,其中涂覆所述抗菌抗生物污损涂料包括:将所述抗菌抗生物污损制剂加入至油漆或环氧树脂中,从而直接涂覆在无孔表面、多孔膜或多孔材料上。
23.根据权利要求16所述的方法,其中将所述抗菌抗生物污损涂料涂覆在多孔膜上还包括:进一步通过过滤方法将圆形胶体截留于所述多孔膜表面上,从而形成可逆涂料。
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EP2898774A1 (en) * | 2014-01-28 | 2015-07-29 | Archroma IP GmbH | Composition for the treatment of textile materials |
JP2019528245A (ja) * | 2016-06-30 | 2019-10-10 | ザ ホン コン ユニバーシティ オブ サイエンス アンド テクノロジイ | 表面に使用するコロイド状抗菌および抗生物付着コーティング |
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2017
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- 2017-06-30 KR KR1020197000658A patent/KR102195307B1/ko active IP Right Grant
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- 2017-06-30 CN CN201780041112.3A patent/CN109414016B/zh active Active
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2021
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JP2023153927A (ja) | 2023-10-18 |
WO2018001359A1 (en) | 2018-01-04 |
US20190174749A1 (en) | 2019-06-13 |
JP2021169494A (ja) | 2021-10-28 |
EP3478064A4 (en) | 2020-01-15 |
KR20190017024A (ko) | 2019-02-19 |
JP2019528245A (ja) | 2019-10-10 |
KR102195307B1 (ko) | 2020-12-28 |
US10842148B2 (en) | 2020-11-24 |
EP3478064A1 (en) | 2019-05-08 |
CN109414016A (zh) | 2019-03-01 |
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