CN113463373A - 一种用于抗菌的生物安全纳米纤维膜及其制备方法 - Google Patents
一种用于抗菌的生物安全纳米纤维膜及其制备方法 Download PDFInfo
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Abstract
本发明公开了一种用于抗菌的生物安全纳米纤维膜及其制备方法。该膜能实现高效抑菌,并能保障生物安全性。该膜的制备方法简易,将N,N‑二甲基甲酰胺(DMF)与聚丙烯腈(PAN)混合制得纺丝溶液,采用气体辅助法制得PAN纳米纤维膜,采用聚苯胺改性制得PANI/PAN纳米纤维膜,再经乙酸锌、氢氧化钠改性后与Zn(NO3)2·6H2O和C6H12N4制备的水热反应前驱液进行水热反应后制得PANI/PAN/ZnO纳米纤维膜。各种测试手段对材料的表征表明改性效果良好,可以验证抗菌性能的生物安全纳米纤维膜的功效。
Description
技术领域
本发明涉及抗菌膜制备技术领域,用于制备在废水污染环境下正常工作的抗菌效应的高效生物安全纳米纤维膜。
背景技术
近年来,由于废水污染事故频繁发生,含有细菌等微生物的废水引起的水污染严重危害生态环境以及人类的生命健康,因此,高效抗菌膜材料的制备已成为一项紧迫的任务。在过去的几十年中,研究人员探索了多种抗菌材料来抑制微生物生长,但是这些方法普遍存在抗菌效率低,操作过程繁琐,设备成本高以及存在二次污染等缺点,这些缺点严重限制了它们在实际中应用。目前,采用抗菌膜是处理含微生物废水的有效方法,因为其降解抑菌效率高、环境友好、操作简单可靠等优势,因此引起了研究人员的广泛关注。
纳米纤维膜因其具有发达孔隙结构、比表面积大、渗透性强以及可调控性的特点在膜制备领域受到广泛关注。纳米纤维膜表面负载抗菌活性物质发挥抑制微生物生长的核心作用。由于负载了抗菌活性物质,纳米纤维膜对微生物具有较高的抑制效率,近年来成为抗菌膜制备领域的研究热点。但目前报道的抗菌膜材料仍存在抗菌效率差、生物相容性弱、耐受性差、环保性低等问题,严重阻碍了其实际应用。因此,开发一种低成本、简易的方法来制备抗菌效率高、环保性强、稳定性好、生物安全性强的抗菌生物安全纳米纤维膜,用于在废水污染物中抑制微生物生长迫在眉睫。
发明内容
针对现有技术的不足,本发明提供一种用于抗菌的生物安全纳米纤维膜及其制备方法,有效提高纤维膜的抗菌性能,具备工业化生产可行性。
为解决上述技术问题,本发明提供了如下技术方案:一种用于抗菌的生物安全纳米纤维膜及其制备方法,包括如下步骤:
将有机溶剂N,N-二甲基甲酰胺(DMF)与聚丙烯腈(PAN)混合制备PAN溶液。用气体辅助法气纺1.5h后将PAN溶液制成纳米纤维膜,采用苯胺溶液和过硫酸铵溶液改性PAN纳米纤维膜,在氮气氛围下聚合1.5h得到PANI/PAN膜。经乙酸锌溶液和氢氧化钠溶液多次浸涂,得到改性后的PANI/PAN膜。最后,利用水热法将ZnO负载在PANI/PAN膜的表面,即得到可用于抗菌的生物安全ZnO/PANI/PAN纳米纤维膜。
上述步骤中,PAN溶液浓度为0.02mol/L。
上述苯胺溶液的浓度为0.02mol/L,过硫酸铵溶液浓度为0.03mol/L。
上述乙酸锌溶液浓度为20mg/mL,氢氧化钠溶液浓度为0.2mol/L。
上述浸涂次数为4次。
上述气体辅助法纺丝条件为:推进泵作用下针头注射速度为3.5mL/h,施加气流维持在12L/min,针与收集器之间的垂直距离保持在18cm。
本发明与现有技术相比,其显著优点是:
与现有技术相比,本发明在不影响纳米纤维膜其他性能的前提下,得到具有抗菌效应的生物安全纳米纤维膜。
附图说明
为了更清楚地说明本发明实施例的技术方案,下面将对实施例描述中所需要使用的附图作简单地介绍,显而易见地,下面描述中的附图仅仅是本发明的一些实施例,对于本领域普通技术人员来讲,在不付出创造性劳动性的前提下,还可以根据这些附图获得其它的附图。其中:
图1为ZnO/PANI/PAN纳米纤维膜抗菌机理示意图。
图2为原始PAN膜、PANI/PAN膜和ZnO/PANI/PAN膜的FT-IR谱图。
图3为原始PAN膜、PANI/PAN膜和ZnO/PANI/PAN膜的XRD图谱。
图4为原始PAN膜、PANI/PAN膜和ZnO/PANI/PAN膜的XPS谱。
图5为原始PAN膜、PANI/PAN膜和ZnO/PANI/PAN膜的TGA曲线。
图6为原始PAN膜、PANI/PAN膜、ZnO/PAN膜和ZnO/PANI/PAN膜对大肠杆菌和枯草芽孢杆菌的抑菌试验数字照片。M1,原始PAN膜;M2,ZnO/PAN膜;M3,PANI/PAN膜;M4,ZnO/PANI/PAN膜。
图7为原始PAN膜、PANI/PAN膜、ZnO/PAN膜和ZnO/PANI/PAN膜抑菌区的平均直径图。
图8为斑马鱼在ZnO/PANI/PAN膜环境下的生物安全检测图。
具体实施方式
为使本发明的上述目的、特征和优点能够更加明显易懂,下面结合实施例对本发明的具体实施方式作出详细的说明。
在下面的描述中阐述了很多具体细节以便充分理解本发明,但是本发明还可以采用其他不同于在此描述的其他方式来实施,本领域技术人员可以在不违背本发明内涵的情况下做类似推广,因此本发明不受下面公开的具体实施例的限制。
其次,此处所称的“一个实施例”或“实施例”是指可包含于本发明至少一个实现方式中的特定特征、结构或特性。在本说明中不同地方出现的“在一个实施例中”并非均指同一个实施例,也不是单独的或选择性的与其他实施例相互排斥的实施例。
实施例1
在干燥四口烧瓶(主要包括磁力搅拌器、温度计)中添加0.025mol PAN和0.025molDMF,充分混合后,在室温下用磁力搅拌器搅拌10~11h后得到均匀的浓度为0.02mol/L的PAN纺丝溶液。在组装的纺丝系统中纺丝,针头注射速度为3.5mL/h,施加气流维持在12L/min,针与收集器之间的水平距离保持在18cm。从气纺制备的PAN纤维膜从收集器上剥离后,放置在70℃的真空烘箱中干燥7h,完全除去表面的小分子量残留物(包括水,有机溶剂)。
实施例2
(1)用移液枪吸取60μL苯胺单体溶于50mL盐酸(1mol/L)中,充分搅拌后得到5wt%的苯胺溶液。
(2)准确称取0.15g过硫酸铵溶于50mL盐酸(1mol/L)中,充分搅拌后得到5wt%的过硫酸铵溶液。
(3)将PAN膜(3cm×3cm)浸入苯胺溶液中,将过硫酸铵溶液缓慢滴入含有PAN纳米纤维膜的苯胺溶液中。在氮气氛围下聚合2.5h后,得到了深绿色的PANI/PAN纳米纤维膜。最后,用去离子水冲洗膜后,放置于真空烘箱中80℃干燥3h。
(4)将PANI/PAN纳米纤维膜浸入乙酸锌溶液3min,然后在115℃下真空烘箱中热处理12min。随后将烘干的PANI/PAN膜在1mol/L NaOH水溶液中浸泡3min,然后在115℃下热处理12min,重复该步骤4次以确保PANI/PAN纳米纤维膜表面均匀负载ZnO晶种。
(5)准确称取4.0g C6H12N4和2g Zn(NO3)2·6H2O,加入150mL去离子水溶解得到水热反应前驱液。
(6)将表面负载ZnO种子的PANI/PAN纳米纤维膜和水热反应前驱液置于水热反应釜中,在100℃下反应7h后,用去离子水和乙醇清洗多次。最后,得到可用于抗菌的生物安全ZnO/PANI/PAN纳米纤维膜,抗菌机理如图1所示。
实施例3
采用Nicolet 7000 FT-IR光谱仪检测了分别鉴定实施例2制备的PAN膜,PANI/PAN膜,ZnO/PANI/PAN膜官能团和膜结构性质,如图2所示。可以看出,在2250cm-1处的吸收振动峰属于氰基(-CN)的伸缩振动/弯曲振动峰。在1643cm-1和1488cm-1处的振动峰是PANI中醌结构和苯结构的伸缩振动/弯曲振动峰。1247cm-1处的振动峰是芳族胺中C-N的拉伸振动峰。C-H的弯曲振动峰位于1138cm-1和776cm-1,这是PANI电导率和电子离域的特征峰。由于PANI的特征峰的存在,进一步证明了PAN纳米纤维膜上已经包覆了聚苯胺。
采用X射线粉末衍射(XRD)(Ultima IV,Rigaku,日本)对实施例2所制膜的纤维形态进行了研究,如图3所示。通过与标准光谱(JCPDS36-1451)的对比,证明样品的衍射主要来自ZnO的纤锌矿结构,这表明ZnO已成功沉积在纤维表面。
采用AXIS Ultra DLD x射线光电子能谱(XPS)分别检测实施例2所制膜的表面不同元素,如图4所示。XPS测量光谱表明纯PAN样品由元素C和N组成。强Zn 2p和O 1s峰的存在以及N 1s峰的衰减进一步证实了ZnO已经成功地改性PANI/PAN膜。
采用热重分析仪(TGA Q5000-IR),美国TA公司,对膜的每种组分的比例进行定量研究。升温速度为10℃/min,从室温升至800℃截止,得到了PAN,PANI/PAN和ZnO/PANI/PAN复合纤维膜的热分解图,如图5所示。从图中可以看出,有机聚合物在高温加热后分解,仅残留ZnO,表明样品中ZnO的负载量为44.2%。
实施例4
采用枯草芽孢杆菌和大肠杆菌菌株对PAN膜、PANI/PAN膜、ZnO/PAN膜和ZnO/PANI/PAN膜的抑菌活性进行测试,结果如图6所示。结果表明,纯PAN膜M1明显被细菌侵蚀,说明纯PAN膜不能解决生物污染问题。而ZnO/PAN和ZnO/PANI/PAN膜对枯草芽孢杆菌和大肠杆菌均有显著的抑菌效果(图7)。
实施例5
采用斑马鱼为实验对象,在可见光下测试ZnO/PANI/PAN膜的生物安全性。将5条斑马鱼(2条蓝色幼鱼和3条红色成鱼)在含有1.5g ZnO/PANI/PAN纳米纤维膜的培养皿中培养15天。如图8所示,在培养15天后,斑马鱼仍然保持着较高的生命力,说明ZnO/PANI/PAN纳米纤维膜具有良好的生物安全性。
本发明提供了一种用于抗菌的生物安全纳米纤维膜及其制备方法的思路及方法,具体实现该技术方案的方法和途径很多,以上所述仅是本发明的优选实施方式,应当指出,对于本技术领域的普通技术人员来说,在不脱离本发明原理的前提下,还可以做出若干改进和润饰,这些改进和润饰也应视为本发明的保护范围。本实施例中未明确的各组成部分均可用现有技术加以实现。
Claims (8)
1.一种用于抗菌的生物安全纳米纤维膜及其制备方法,其特征在于:包括,
将有机溶剂N,N-二甲基甲酰胺(DMF)与聚丙烯腈(PAN)混合制备PAN溶液。用气体辅助法将PAN溶液制成纳米纤维膜。
采用苯胺溶液和过硫酸铵溶液改性PAN纳米纤维膜,在氮气氛围下聚合1.5h得到PANI/PAN膜。
经乙酸锌溶液和氢氧化钠溶液多次浸涂,得到改性后的PANI/PAN膜。
利用水热法将ZnO负载在PANI/PAN膜的表面,即得到可用于抗菌的生物安全ZnO/PANI/PAN纳米纤维膜。
2.权利要求1所述的生物安全纳米纤维膜及其制备方法,其特征在于,所述通过气体辅助纺丝法将PAN溶液制成PAN纳米纤维膜,包括,气纺1.5h后得到PAN纳米纤维膜,然后从收集器上剥离纤维膜,并在70℃的真空烘箱中干燥7h,以去除残留的溶剂,整个气纺过程的环境温度和湿度分别保持在30±5℃和45±5%,其中气体辅助纺丝条件包括:推进泵作用下针头注射速度为3.5mL/h,施加气流维持在12L/min。针与收集器之间的水平距离保持在18cm。
3.权利要求1所述的生物安全纳米纤维膜及其制备方法,其特征在于,所述采用原位合成法制备PANI/PAN膜,包括将所述PAN膜浸入聚苯胺溶液中。将过硫酸铵/盐酸溶液缓慢滴入含有PAN纳米纤维膜的苯胺溶液中。在氮气氛围下聚合2.5h后,用去离子水除去膜上残余杂质,在真空烘箱中80℃烘干3h。
4.权利要求1所述的生物安全纳米纤维膜及其制备方法,其特征在于,所述聚苯胺溶液,包括将苯胺单体溶解于盐酸中,在室温下搅拌均匀得到。
5.权利要求1所述的生物安全纳米纤维膜及其制备方法,其特征在于,所述过硫酸铵/盐酸溶液,包括将过硫酸铵溶解于盐酸中,在室温下搅拌均匀得到。
6.权利要求1所述的生物安全纳米纤维膜及其制备方法,其特征在于,所述采用交替浸涂法制备ZnO/PANI/PAN膜,包括将所述PANI/PAN膜浸入乙酸锌溶液3min,然后在115℃下真空烘箱中热处理12min。后将烘干的PANI/PAN膜在NaOH溶液中浸泡3min,然后在115℃下热处理12min,重复上述步骤4次。然后将浸涂后的PANI/PAN膜和水热反应前驱液混合加入聚四氟乙烯反应釜中,通过水热法在100℃下反应7h后,用去离子水和乙醇清洗多次。
7.权利要求1~6任一所述的生物安全纳米纤维膜及其制备方法制得的纳米纤维膜,其特征在于:将枯草芽孢杆菌和大肠杆菌菌株置于膜表面培养,两种菌落在一段时间内均会受到显著的抑菌效果。
8.权利要求1~6任一所述的生物安全纳米纤维膜及其制备方法制得的纳米纤维膜,其特征在于:将斑马鱼在含有该纳米纤维膜的培养皿中培养。15天后,斑马鱼仍然保持着较高的生命力,说明该纳米纤维膜具有良好的生物安全性。
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