CN110074136B - 一种铜铁氧化物及混合纳米颗粒的制备方法和抗菌应用 - Google Patents
一种铜铁氧化物及混合纳米颗粒的制备方法和抗菌应用 Download PDFInfo
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- CN110074136B CN110074136B CN201910204976.3A CN201910204976A CN110074136B CN 110074136 B CN110074136 B CN 110074136B CN 201910204976 A CN201910204976 A CN 201910204976A CN 110074136 B CN110074136 B CN 110074136B
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- copper
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Abstract
本发明属于纳米颗粒制备技术领域，公开了一种铜铁氧化物及混合纳米颗粒的制备方法和抗菌应用。一定比例的Cu(NO3)2·3H2O和Fe(NO3)3·9H2O溶解在去离子水中；在不断搅拌下将NaOH溶液滴加到混合物中；然后甲醛加入在混合物中，所得溶液转移到碳化硅(SiC)反应管中，并在微波室中进行反应，产生铜铁氧化物及混合纳米颗粒；冷却后，合成的样品离心并用去离子水洗涤；然后将收集的样品放置在烘箱中干燥过夜。本发明的实验表明它们至少对9种重要人体致病菌有高效抗菌性能，比如可以在15分钟内以109对数减少的速度杀死大肠杆菌；在孵育后4小时后，多药耐药性的肺炎克雷伯菌菌株约有108对数减少。
Description
技术领域
本发明属于纳米颗粒制备技术领域，尤其涉及一种铜铁氧化物及混合纳米颗粒的制备方法和抗菌应用。
背景技术
目前，业内现有技术是：传染病是世界上第二大死亡原因(在美国排名第三)，也是全球失能调整生命年的主要原因。细菌引起的感染，包括由沙门氏菌，大肠杆菌或志贺氏菌引起的感染，在传染病中占据很大一部分。例如，最近爆发的在火腿中的李斯特菌感染与牛肉馅中的沙门氏菌感染青霉素和其他抗生素对治疗由细菌引起的感染至关重要，但在很多病原体中已经观察到的抗生素耐药性增加已成为极为严重的公共卫生问题。即便是耐药性不是限制其使用的因素，抗生素的其他缺点，例如它们对宿主的毒性，使得人们需要探索其它新型抗菌试剂。随着纳米技术的进步，使用纳米级无机材料作为抗菌剂来控制微生物的感染，如表1所示，引起了越来越多的关注。纳米级无机材料具有很高表面积与体积比和独特的物理与化学特性。例如，已发现银纳米颗粒(Ag NP)是最有效的抗菌剂之一。据报道，只需50至60μg/mL的Ag NPs就能抑制培养基上生长的105CFU细菌。最近的研究发现，氧化锌纳米结构也可作为非常有希望的无机抗菌材料。具有聚乙烯吡咯烷酮(PVP)涂层的氧化锌量子点在孵育48小时后被证实具有针对单核细胞增生李斯特菌(5.3-log减少)和大肠杆菌(6-log减少)的有效抗菌活性。将氧化铜纳米颗粒(CuO NP)掺入纤维素和壳聚糖中以形成生物相容的抗菌复合材料。在孵育16小时后，加载298nmol/mg CuONP的复合物能有效减少耐药细菌的生长(例如，大肠杆菌的大约3-log生长减少和无乳链球菌的5-log生长减少)。然而，很多开发出来的无机抗菌材料对人体细胞有毒性。比如表1中的具有最佳抗菌性能的材料，银纳米颗粒或氧化铜纳米颗粒均对人体细胞有毒。它们的毒性主要来源于它们的离子，如银离子(Ag+)和铜离子(Cu+，Cu2+)。这些纳米颗粒的毒性极大地限制了它们的应用，尤其是有关食品和医疗上的应用。另外，文献中报道的大多数无机抗菌材料的研究仅关注有限的细菌种类，如大肠杆菌和金黄色葡萄球菌。因此，开发能够有效抑制多种细菌(菌株)的新材料仍然是重要的和迫切的。
表1.文献中报道的常见无机抗菌材料及其最佳抗微生物性能的总结
综上所述，现有技术存在的问题是：现有的银纳米颗粒或氧化铜纳米颗粒均对人体细胞有毒。
发明内容
针对现有技术存在的问题，本发明提供了一种铜铁氧化物及混合纳米颗粒的制备方法和抗菌应用。
本发明是这样实现的，一种铜铁氧化物及混合纳米颗粒的制备方法所述铜铁氧化物及混合纳米颗粒的制备方法包括：
第一步，0.242g Cu(NO3)2·3H2O和0.404g Fe(NO3)3·9H2O溶解在10ml去离子水中；在不断搅拌下将1～10ml 1M NaOH溶液滴加到混合物中；按照质量比0.242g Cu(NO3)2·3H2O：0.404g Fe(NO3)3·9H2O＝1～10:10～1；
第二步，100微升～1毫升37％甲醛加入混合物中，所得溶液转移到碳化硅SiC反应管中，并在200℃的微波室中保持并反应；
第三步，冷却后，合成的样品离心并用去离子水洗涤；然后将收集的样品放置在烘箱中干燥过夜。
进一步，所述第二步在200℃的微波室中保持2小时。
进一步，所述第三步将收集的样品放置在60℃烘箱中干燥过夜。
本发明的另一目的在于提供一种由所述铜铁氧化物及混合纳米颗粒的制备方法制备的铜铁氧化物及混合纳米颗粒。
本发明的另一目的在于提供一种包含所述铜铁氧化物及混合纳米颗粒的喷雾剂。纳米颗粒可以与稀释的酒精溶液或其他的溶剂形成胶体悬浮液的喷剂。
本发明的另一目的在于提供一种包含所述铜铁氧化物及混合纳米颗粒的用于伤口或手术的防菌、抗菌的绷带。
本发明的另一目的在于提供一种包含所述铜铁氧化物及混合纳米颗粒的医疗设备的表面涂层。纳米颗粒可以和药膏混合在一起，用于伤口涂抹。
本发明的另一目的在于提供一种包含所述铜铁氧化物及混合纳米颗粒的过滤器。
本发明的另一目的在于提供一种包含所述铜铁氧化物及混合纳米颗粒的食品加工设备、工具的涂料或混合食品包装膜。纳米颗粒可以与生物相容性的高分子材料混合、拉丝，可以纺成线或做成绷带，或者用于制作过滤器的过滤芯；或者与塑料混合造成薄膜，应于食品包装。纳米颗粒可以和油漆用的粘合剂混合，形成新的杀菌漆。
综上所述，本发明的优点及积极效果为：本发明采用一步水热法制备了不同形貌和不同成分的铜铁氧化物以及与氧化铁、氧化铜混合纳米颗粒。当这些铜铁氧化物纳米粒子在室温下与细菌悬浮液混合在一起时，展现出快速杀菌能力。本发明的实验表明它们可以在15分钟内以109对数减少的速度杀死大肠杆菌。据业内的技术人员所知，这是迄今为止现有文献中报导的最快的杀菌速度。
本发明制备的纳米颗粒可用在许多抗菌应用中。在医疗上，可以使将其制成喷雾剂或者混于绷带中用于伤口或手术的防菌、抗菌。也可以将它用作医疗设备的表面涂层。这些材料对革兰氏阳性菌和阴性菌的快速灭杀作用可确保特殊工具(医疗以及食品设备、工具)的无菌要求。在环境应用中，这些材料可以在水中或加水过滤器中，避免使用紫外光或其他化学制品。在食品工业应用中，它们可用作食品加工设备、工具的涂料，或混合到食品包装膜中，用作防菌包装。该材料的合成过程简单、可大规模生产，并且可以用于廉价的原材料生产。
本发明创新的抗菌材料对于阻止微生物引起的传染病非常重要，因为目前世界上抗药性病原体的数量和能力都在增加。采用微波辅助水热法合成了Fe2O3/Cu2O/CuFe2O复合材料的CuxFeyOz纳米粒子，并把该材料对9种重要人体致病菌的抗菌活性进行了评估。纳米粒子展现出非常有效的杀菌能力：例如，在孵育15分钟后，大肠杆菌B的生存力降低超过9-log；在孵育后4小时后，多药耐药性的肺炎克雷伯菌菌株约8-log降低。当这些纳米粒子与其他重要的人类病原体(包括革兰氏阳性和革兰氏阴性菌株)一起孵育时，获得了类似的结果。对哺乳动物细胞的细胞毒性试验表明，纳米粒子在1mg/ml浓度下毒性较小。结果显示了开发基于CuxFeyOz复合材料的新型抗菌剂的广阔前景。
本发明的铜铁氧化物及混合纳米颗粒杀菌效率高。与表1的其他纳米粒子比较，毒性小，与银或氧化铜粒子比较，制作过程简单，原材料便宜。
附图说明
图1是本发明实施例提供的铜铁氧化物及混合纳米颗粒的制备方法流程图。
图2是本发明实施例提供的(a)CuxFeyOz NPs的代表性SEM图像，插入的是放大的图像；(b)CuxFeyOzNP的EDS元素扫描图(O，Fe和Cu的元素)。(c)CuxFeyOz NP的XRD谱；(d)与CuxFeyOzNP混合后MO和MB的归一化特征吸收峰α(t)/α(0)和时间关系。
图3是本发明实施例提供的CuxFeyOz NPs(PBS中1mg/ml)对各种致病菌的抗菌试验(细菌数量随时间的变化情况)；每个试验点代表3次独立的实验(KP4/484为2次)。
图4是本发明实施例提供的细菌抑制测试：在相应的生长培养基中与1mg/mlCuxFeyOzNPs共培养细菌；结果代表3次独立的生长实验；BDL：低于检测限(<200CFU/mL)。
图5是本发明实施例提供的CuxFeyOz对小鼠成纤维细胞的细胞毒性：细胞暴露于0mg/ml(对照)，1mg/ml和10mg/ml的CuxFeyOz NPs24小时后的细胞活力；结果代表3次独立实验。
图6是本发明实施例提供的通过改变甲醛体积合成的不同CuxFeyOz NP的代表性SEM图像：A：S200；B：S250；C：S300；D：S350；E：S400；和F：S500。
图7是本发明实施例提供的不同CuxFeyOzNP样品的SEM和动态光散射之间的尺寸比较示意图。
图8是本发明实施例提供的不同CuxFeyOz NP样品XRD谱以及相对的CuFeO2，CuO，Cu2O和Fe2O3的峰的组分示意图。
图9是本发明实施例提供的不同CuxFeyOz NP样品的催化性能：A:暴露于CuxFeyOzNP中后剩余的甲基橙浓度；整个过程中都保持着黑暗的条件；B：不同CuxFeyOzNP样品中平衡的甲基橙浓度。
图10是本发明实施例提供的S200和S500样品对大肠杆菌B的抗菌活性测试示意图。
具体实施方式
为了使本发明的目的、技术方案及优点更加清楚明白，以下结合实施例，对本发明进行进一步详细说明。应当理解，此处所描述的具体实施例仅仅用以解释本发明，并不用于限定本发明。
本发明现通过微波辅助水热法合成的氧化亚铜(Cu2O)，氧化铁(Fe2O3)和氧化铜铁(CuFeO2)纳米颗粒(称为CuxFeyOz NPs)的混合物对很多革兰氏阳性和阴性细菌具有很高的抗菌活性。该材料还可以抑制在生长培养基中的细菌的生长。针对小鼠成纤维细胞的细胞毒性试验表明，这些纳米颗粒在低工作浓度(≤1mg/ml)下对哺乳动物细胞的毒性较小。
下面结合附图对本发明的应用原理做详细的描述。
如图1所示，本发明实施例提供的铜铁氧化物及混合纳米颗粒的制备方法包括以下步骤：
S101：0.242g Cu(NO3)2·3H2O(ACROS Organics)和0.404g Fe(NO3)3·9H2O彻底溶解在10ml去离子水中；在不断搅拌下将10ml 1M NaOH溶液滴加到混合物中；
S102：500μl37％甲醛:加入混合物中，4ml所得溶液转移到10ml SiC反应管中，并在200℃的微波室中保持2小时；
S103：冷却后，合成的样品离心并用去离子水洗涤5次；然后将收集的样品放置在60℃烘箱中干燥过夜。
本发明实施例提供的铜铁氧化物及混合纳米颗粒的制备方法具体包括以下步骤：
第一步，0.242g Cu(NO3)2·3H2O和0.404g Fe(NO3)3·9H2O溶解在10ml去离子水中；在不断搅拌下将1～10ml 1M NaOH溶液滴加到混合物中；按照质量比0.242g Cu(NO3)2·3H2O：0.404g Fe(NO3)3·9H2O＝1～10:10～1；
第二步，100微升～1毫升37％甲醛加入混合物中，所得溶液转移到碳化硅SiC反应管中，并在200℃的微波室中保持并反应；
第三步，冷却后，合成的样品离心并用去离子水洗涤；然后将收集的样品放置在烘箱中干燥过夜。
下面结合实验对本发明的应用原理作进一步的描述。
1、实验部分
1.1纳米颗粒合成和表征：CuxFeyOz NPs是通过微波辅助水热合成(Monowave 400，Anton Paar)制造的。在典型的合成中，将0.242g Cu(NO3)2·3H2O(ACROS Organics)和0.404g Fe(NO3)3·9H2O(Alfa Aesar)彻底溶解在10ml去离子水中。首先在不断搅拌下将10ml 1M NaOH溶液滴加到混合物中。然后还将500μl37％甲醛(J.T.Baker)加入混合物中。将4ml所得溶液转移到10ml SiC反应管中，并在200℃的微波室中保持2小时。冷却后，将合成的样品离心并用去离子水洗涤5次。然后将收集的样品放置在60℃烘箱中干燥过夜。样品的形貌用场发射扫描电子显微镜(FEI Inspect F)检测。扫描电子显微镜(HitachiSU9000STEM/SEM)进一步研究CuxFeyOz NP的形态和元素组成。X射线衍射仪(XRD；PANalytical X'Pert PRO MRD)用来表征所制备样品的晶体结构。CuxFeyOz NPs的Zeta电位是通过Malvern ZetasizerNano ZS系统在25℃下测量，被确定为28.3meV。使用甲基橙(MO)和亚甲基蓝(MB)水溶液在室温下浓度为30μM进行染料降解实验。所有实验均以浓度为0.5mg/ml的CuxFeyOzNPs和固定体积V＝20ml的染料溶液进行。反应体系保持在黑暗中并不断搅拌。在每个时间间隔(2,4,6,8,10和24小时)时，取出等分试样并以12000rpm离心以除去NP，并通过紫外可见光谱仪来研究剩余溶液中MO和MB的浓度变化。
1.2抗菌活性测试：在各种细菌菌株上测试样品的抗菌活性(参见支持信息表3)。通常情况下，大肠杆菌B和金黄色葡萄球菌生长在胰蛋白酶解酪蛋白大豆肉汤培养基(TSB)中，大肠杆菌O157：H7，肺炎克雷伯菌菌株4/484和ATCC-BAA-2472，单核细胞增生李斯特菌，鼠伤寒沙门氏菌ATCC-700408和弗氏志贺菌生长在Luria Bertani培养基(LB)中。细胞通常在37℃下振荡(250rpm)生长12至16小时。幽门螺杆菌细胞通常在微量厌氧条件下(5％O2,5％CO 2,90％N2)在血琼脂(BA)平板上生长。在培养基中生长好的细菌细胞通过以4,000rpm离心5分钟后，用磷酸盐缓冲盐水(PBS)洗涤两次，最后重悬于PBS中，并与CuxFeyOzNPs混合进行的抗菌活性测试。对于大肠杆菌B和金黄色葡萄球菌测试，将1mgCuxFeyOzNP直接悬浮于细菌悬浮液中。对于其他细菌菌株，首先将细菌悬浮液浓度标准化为PBS中OD600为2(～109至2×109CFU/ml，取决于菌株)，然后取0.25ml细菌悬浮液，用0.25mlPBS(作为对照)或0.25ml 2mg/ml CuxFeyOzNP悬浮液进行稀释。将细菌和CuxFeyOz NPs的混合物在37℃下振荡(200rpm)温育。在不同的时间间隔(分别为15,30,60,120和240分钟)取出等分试样，并在PBS中连续稀释10倍。将稀释液涂布在培养基平板上，并在37℃下孵育12至16小时。幽门螺杆菌细胞稀释液在微需氧条件下在BA平板上孵育3至5天。
1.3细菌生长抑制试验：对于细菌生长抑制试验，将细菌细胞直接与具有CuxFeyOzNPs的新鲜培养基溶液混合。简而言之，对于大肠杆菌B和金黄色葡萄球菌，首先将10mgCuxFeyOz NPs悬浮于0.1ml PBS中，然后加入9.9ml TSB(最终CuxFeyOz NPs浓度为1mg/ml)。然后将10μl细菌悬浮液混合到培养基-NPs混合物中，并在37℃下振荡(250rpm)保持12-16小时。对于肺炎克雷伯氏菌BAA-2472，鼠伤寒沙门氏菌700408和弗氏志贺菌，将2μl细菌悬浮液(对应于约2×106个细胞)混合到含有1mg/ml CuxFeyOz NPs的500μlTSB中。对于幽门螺旋杆菌，细胞在BA平板上生长，收获并重新悬浮于100μl脑心浸液中，用0.4％β-环糊精(BHI-βc)稀释直至最终浓度约为107个细胞，并混合到补充有2ml BHI-βc的0.1ml 20mg/mlCuxFeyOz NPs-PBS混合物中(最终CuxFeyOzNPs浓度为1mg/ml)。然后将这些细菌-培养基-CuxFeyOzNPs混合物在需氧(除幽门螺杆菌外的所有菌株)或微氧(幽门螺杆菌)条件下在37℃振荡孵育18小时。在培养完成后，从每个样品中取出等分试样量的混合物，并在PBS中稀释10倍。然后将稀释液涂在琼脂平板上，并如上所述在37℃温育。对照组的试验用等体积的PBS代替CuxFeyOzNPs悬浮液。
1.4细胞毒活性测试：使用制造商推荐(Sigma-Aldrich)的标准WST-8染料测定法进行CuxFeyOz NPs的细胞相容性测试。在实验期间，小鼠成纤维细胞在75-cm2T型烧瓶中生长，并在37℃下于潮湿的CO2培养箱中温育6-7天，直至80-90％细胞生长融合。此后，使用0.5％胰蛋白酶EDTA分离细胞，通过台盼蓝试验(0.4％)(EVE自动细胞计数器)计数，并将100μl5000cell/ml接种在96孔板中。将板在37℃下于CO2培养箱中保持24小时，以使细胞完全生长在孔板表面。同时，在Dulbecco改良的Eagle培养基(DMEM)中制备1mg/ml或10mg/mlCuxFeyOz NPs溶液。使细胞在孔板中于37℃生长24小时。24小时后，用含有1mg/ml或10mg/mlCuxFeyOzNPs培养基替换原来的培养基。用在不存有CuxFeyOzNPs的情况下孔板中生长的细胞作为对照(每种条件n＝8)。在24小时后，将10μlWST-8染料加入到每个含有细胞的孔中。活细胞将WST-8染料转化为黄色的formazan产物。纯DMEM培养基的试验结果用作基线背景。使用BioTek分光光度计在450nm处测量formazan的吸光度，用作细胞活力的量度。假设对照试验的活力为100％，计算细胞活力的相对变化。
2、结果
如图2(a)所示，合成后的CuxFeyOzNPs有各种形状的颗粒，如立方体、薄片和不规则形状，平均直径为100±20nm(这里本发明只报告具有最好抗菌活性的混合物，本发明还合成了其他CuxFeyOz NPs，它们的特征可以在支持信息的表3部分找到)。高倍放大扫描电子显微镜(SEM)和能量色散X射线光谱(EDS)(图2(b))显示氧均匀分布在所有结构上，但Fe和Cu原子的分布不均匀。立方体形状的颗粒上有更多的Fe含量，而带状结构主要金属成分是Cu。图2(c)中的X射线衍射(XRD)图显示样品是Cu2O，Fe2O3和CuFeO2三种晶体颗粒的混合物，这与EDS的结果一致。事实上，图2(b)中的条带结构可能主要是Cu2O，而其他形状的颗粒是Fe2O3或CuFeO2。如图2(d)所示，CuxFeyOz NPs对阳离子染料，即甲基橙(MO)(～90％的降解)，显现出强烈的染料降解活性，但对阴离子染料，即甲基蓝(MB)，其降解的效果较差(
在24小时后，在黑暗下用0.5mg/ml NP悬浮液测试时，只减少8％)。这可归因于MB的分解主要通过还原反应，20而MO的分解主要是由于氧化反应。21即，本发明的结果表明合成后的CuxFeyOzNPs是有效的氧化剂。
CuxFeyOz NPs的优异的MO氧化活性表明它们应具有良好的抗菌活性。为了验证这一假设，本发明使用了9种重要的致病菌株进行抗菌试验，包括革兰氏阳性菌种，如金黄色葡萄球菌的罗森巴赫菌株ATCC-6538和单核细胞增生李斯特菌，以及革兰氏阴性菌种，如肠道寄生虫大肠杆菌(EHEC)菌株O157：H7，肺炎克雷伯菌菌株4/484和ATCC-BAA-1472，鼠伤寒沙门氏菌鼠伤寒沙门氏菌ATCC-700408，幽门螺杆菌X47和福氏志贺菌菌株2457T。其中，肺炎克雷伯菌菌株4/484和BAA-2472，以及鼠伤寒沙门氏菌菌株700408是多药耐药(MDR)菌株。非致病性大肠杆菌菌株B用作参考。在所有实验中，最终的CuxFeyOzNPs浓度为1mg/ml。图3显示了细菌存活的时间曲线，而表2总结了对不同细菌菌株观察到的细菌杀灭效率。CuxFeyOz NPs对几乎所有测试的细菌菌株均显示出高效的抗菌活性：首先，CuxFeyOz NPs可以非常有效地杀死革兰氏阴性菌和革兰氏阳性菌。结果显示大肠杆菌B在0.25小时(15分钟)内的减少量超过9-log，金黄色葡萄球菌在1小时内减少10-log。对于其他细菌，例如大肠杆菌O157：H7和单核细胞增生李斯特菌，在暴露在CuxFeyOz NPs中4小时后，观察到超过7-log的减少。本发明的结果表明，这些纳米粒子可以在非常短的暴露期内有效杀死细菌细胞。与表1中所示的其他无机纳米结构的最佳抗菌性能相比，仅有银纳米颗粒或氧化铜纳米颗粒可以获得类似或更好的结果。然而，银纳米颗粒或氧化铜纳米颗粒对宿主细胞都是具有高毒性的，而CuxFeyOz NPs则不是(参见下面的毒性试验)。此外，CuxFeyOz NPs还具有快速有效的针对高感染性耐药菌株的抗菌活性：多药耐药肺炎克雷伯菌菌株4/484，4小时后8.4-log减少；多药耐药肺炎克雷伯菌菌株BAA-2472，4小时后6.9-log减少；以及多药耐药鼠伤寒沙门氏菌菌株700408，2小时后，7.2-log减少。
CuxFeyOz NPs的高效抗菌活性也在细菌生长抑制试验得到证实，即有利的细菌生长条件下进行细菌培养时，将CuxFeyOz NPs作为细胞生长抑制剂与细胞一起孵育(图4)。将CuxFeyOz NPs和细菌混合，均在适当的新的培养基中培养，并在连续稀释后通过CFU计数细菌生长的数目(12至24小时后，取决于菌株)。本发明的结果表明CuxFeyOz NPs在有利的生长条件下对细菌的生长具有抑菌作用，例如，t＝24小时的最终细菌浓度(CFU/mL)与初始细菌浓度(t＝0小时的CFU/mL)相似。对于所有测试的细菌都观察到这种情况，包括肺炎克雷伯氏菌和鼠伤寒沙门氏菌的多药耐药菌株。此外，在BHI-βc培养基中共培养24小时后，幽门螺杆菌生长被完全抑制；相反，幽门螺旋杆菌在对照组中达到高达108CFU/ml的浓度(图4)。因此，结果进一步表明CuxFeyOz NPs是非常有前途的抗菌剂。
目前CuxFeyOzNPs的抗菌机制还不是很清楚。根据图2所示的成分分析，混合物中有三种不同的纳米颗粒，Cu2O，CuFeO2和Fe2O3。Cu2O纳米颗粒是众所周知的抗菌纳米材料22，最近的报道显示CuFeO2纳米颗粒可以杀死病毒23和真菌24。Fe2O3纳米颗粒是光催化材料，只有在能量高于能带隙的光照射下才能显示出抗菌活性25。因此，本发明假设CuxFeyOz NPs的抗菌性能主要来自Cu2O和CuFeO2。对于这两种材料，抗菌性质归因于化合物中的Cu+离子。23-24众所周知，铜离子能够通过与酶，蛋白质等反应后产生的变性或氧化机制有效地杀死微生物。26-27据报道，Cu2O纳米晶体可通过生化过程产生活性氧(ROS)28。通常，在生化过程中，作为氧化还原活性过渡金属，Cu可以在两种氧化还原状态，即氧化铜和还原亚铜，之间循环。Cu与H2O2反应与Fenton反应类似，其过程中可以产生羟基自由基，并且它还可以催化电子从供体生物分子转移到受体分子，例如与O2反应产生O2-。或羟基自由基(·OH)28-29。这些ROS对细菌细胞有毒，可破坏特定的微生物过程。ROS对细菌细胞的直接作用在于ROS可导致细胞化合物的氧化损伤30。研究表明，ROS可以破坏细胞膜，随后引起细胞质代谢物泄漏，离子梯度崩溃，导致细胞死亡。31-32此外，ROS可以破坏关键的大分子，铁-硫簇成分解酶，氧化蛋白质内的氨基酸残基，产生脂质过氧化物，并破坏DNA.32-33。
众所周知，高浓度的ROS也会引发哺乳动物细胞的损伤。因此，本发明有必要探索CuxFeyOz NPs对哺乳动物细胞的细胞毒性。本发明通过将小鼠成纤维细胞于37℃下暴露在不同浓度的CuxFeyOz NPs 24小时，进行CuxFeyOz NPs的细胞毒性试验。如图5所示，用10mg/ml CuxFeyOzNPs处理的成纤维细胞仅能保持低于10％的细胞活力。然而，当用1mg/mlCuxFeyOz NPs(其为用于抗菌活性测试的浓度，参见图3和4以及表2)处理时，超过70％的成纤维细胞保持存活。与其他高效抗菌无机材料(例如CuO纳米颗粒)相比，据报道，浓度为80μg/ml时，CuO纳米颗粒对肺细胞有毒，并且还可能对细胞造成DNA损伤。34因此，人们花费很多努力试图来用聚合物或配体来包覆CuO或Cu2O纳米颗粒以降低毒性。但是这种包覆同时也会降低其抗菌活性。本发明的结果表明，在用非常高浓度的CuxFeyOz NPs(10mg/ml)，其对小鼠成纤维细胞是有毒的。高浓度CuxFeyOz NPs的细胞毒性也间接地指证混合物中的Cu+离子在抗菌活性中起到了很重要作用。然而，在较低浓度下(1mg/ml)，它们的毒性要低得多，亦即它们是和细胞相容的。在该浓度(1mg/ml)下，本发明发现CuxFeyOz NPs对多种细菌具有快速、高效的抗菌活性。因此，对哺乳动物细胞的低毒性以及对多种细菌的高效抗菌活性表明，CuxFeyOz NPs抗菌剂可以具有广泛应用，例如用于水处理，伤口处理或用作医用设备涂层，等等。
总之，本发明利用简单的微波辅助水热合成合成了CuxFeyOz混合纳米颗粒。EDS和XRD结果证实这些纳米颗粒由Cu2O，Fe2O3和CuFeO2组成。染料降解试验表明，这些纳米颗粒在黑暗条件下，经过24小时后可以降解90％的MO，证明它们是强氧化剂。CuxFeyOz NPs具有针对革兰氏阳性和革兰氏阴性细菌的高效抗菌活性，其中包括三种多药耐药菌株。本发明测试的9种细菌中，有两种菌株属于高度顽固的ESKAPE致病菌群，这些菌群曾在全世界大多数医院引起过感染。35此外，金黄色葡萄球菌，肺炎克雷伯菌和大肠杆菌菌株所引起感染在美国所有传染病中占近30％。36当CuxFeyOzNPs与生长培养基中的细菌共培养时，CuxFeyOzNPs也可以抑制细菌生长(抑菌效应)。毒性试验表明，抗菌应用1mg/ml CuxFeyOzNPs的浓度对哺乳动物细胞的毒性较小。因此，与其他无机抗菌材料相比，CuxFeyOz NPs可以有选择性地灭杀细菌。这是CuxFeyOz NPs一个非常有利和诱人的优点。此外，与银纳米颗粒相比，CuxFeyOz纳米颗粒制作价格低廉且化学性质稳定。显然，这些优点使得CuxFeyOz NPs成为许多商业产品的潜在候选者，例如抗菌霜，喷雾剂，涂料，以及消毒或水处理。
用于光催化表征的MO和MB的原始时间依赖性UV-Vis光谱和表总结了用于抗微生物测试的九种细菌。
表2 CuxFeyOzNP的抗微生物活性(细菌细胞悬浮于1X PBS中)。
(GP)：革兰氏阳性细菌(GN)：革兰氏阴性细菌
不同条件合成的CuxFeyOz NPs，在微波水热合成过程中，本发明保持反应物Cu(NO3)2·3H2O,Fe(NO3)3·9H2O和NaOH的量相同，系统地将37％甲醛的体积从200μl增加为500μl，从而获得了不同的CuxFeyOz NPs。本发明将样品的名称表示为S200，S250，......，S500，其对应于甲醛体积为200μl，250μl，...和500μl。
表3不同CuxFeyOzNP样品属性的总结
表4本发明中使用的细菌菌株，本发明用的菌种都是在乔治亚大学微生物实验室和食品安全中心，以及埃莫里大学公共卫生学院的。
ATCC:AmericanTypeCulture Collectio
以上所述仅为本发明的较佳实施例而已，并不用以限制本发明，凡在本发明的精神和原则之内所作的任何修改、等同替换和改进等，均应包含在本发明的保护范围之内。
Claims (7)
1.一种铜铁氧化物及混合纳米颗粒的制备方法，其特征在于，所述铜铁氧化物及混合纳米颗粒的制备方法包括：
第一步，0.242g Cu(NO3)2 •3H2O和0.404g Fe(NO3)3 •9H2O溶解在10ml去离子水中；在不断搅拌下将1~10ml 1M NaOH溶液滴加到混合物中；
第二步，100微升~1毫升37％甲醛加入混合物中，所得溶液转移到碳化硅SiC反应管中，并在200℃的微波室中保持并反应；
第三步，冷却后，合成的样品离心并用去离子水洗涤；然后将收集的样品放置在烘箱中干燥过夜；
所述第二步在200℃的微波室中保持2小时；
所述第三步将收集的样品放置在60℃烘箱中干燥过夜。
2.一种由权利要求1所述铜铁氧化物及混合纳米颗粒的制备方法制备的铜铁氧化物及混合纳米颗粒。
3.一种包含权利要求2所述铜铁氧化物及混合纳米颗粒的喷雾剂。
4.一种包含权利要求2所述铜铁氧化物及混合纳米颗粒的用于伤口或手术的防菌、抗菌的绷带。
5.一种包含权利要求2所述铜铁氧化物及混合纳米颗粒的医疗设备的表面涂层。
6.一种包含权利要求2所述铜铁氧化物及混合纳米颗粒的过滤器。
7.一种包含权利要求2所述铜铁氧化物及混合纳米颗粒的食品加工设备的涂料、食品加工工具的涂料或混合食品包装膜。
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