CN115354491B - 一种纳米纤维素复合材料及其制备方法与应用 - Google Patents
一种纳米纤维素复合材料及其制备方法与应用 Download PDFInfo
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Abstract
本发明公开了一种纳米纤维素复合材料及其制备方法与应用。本发明将水溶性铈盐、水溶性碱和细菌纤维素膜于水中进行微波反应,得到负载氧化铈纳米颗粒的细菌纤维素膜,即得纳米纤维素复合材料。本发明制得的纳米纤维素复合材料不仅保证了CeO2NPs的分散性和稳定性,增强了其生物防护性能和机械强度,而且以纤维直径只有4nm左右和富含亲水基团的细菌纤维素作为载体,使其过滤性和透气性更好,易于回收、处理和实现重复利用,另外,原料成本低廉,合成方法简单,易于工业化生产,利用该纳米纤维素复合材料生产的纳米口罩具备表面过滤功能优异、阻隔效率高、抗菌效果好、使用材料薄、透气性能好、成本低廉、环保等特点。
Description
技术领域
本发明涉及一种纳米纤维素复合材料及其制备方法与应用。
背景技术
普通医用口罩的结构一般分为三层:外层S(防水)、中间层M(过滤)和内层S(吸水),中间层M是其起到防护作用的关键,该层为熔喷无纺布过滤层,一般是由许多丛横交错的聚丙烯纤维以随机方向层叠而成的膜。纤维尺寸对防止细菌、血液渗透起至关重要的作用,因为纤维的直径越小,比表面积就越大,孔隙结构越精细复杂,从而过滤性能就越好。目前熔喷层纤维直径的范围在0.5微米-10微米之间,极端条件下最好的也在0.2微米左右,这致使普通医用口罩仅能阻挡直径>3微米的细菌气溶胶颗粒。熔喷无纺布过滤层除通过纤维空隙起到“筛”的作用来实现对飞沫等的过滤外,还能利用静电吸引来实现对颗粒产生静电粘附。但是,静电并不是始终处于饱和的状态,口罩从生产再到消费者手中使用,每一个环节都会使熔喷无纺布过滤层中的静电含量逐步减少,静电的衰减导致了熔喷无纺布口罩防护效能的下降;而且随着人体呼吸和佩戴时间的增长,口罩逐渐受潮,其静电吸附能力减弱,隔离效果逐渐变差。目前绝大多数的口罩又不具有抗菌和抗病毒等特殊性能。这些导致口罩对小颗粒细菌、病毒等无法实现长久有效的隔离防护。
此外,口罩属于一次性消耗品,对熔喷无纺布的需求量大,导致其原材料价格一涨再涨;另外,无纺布的生产需要一套设备来完成,流程复杂、扩产难度大且耗时长,外加价格昂贵,一台进口的无纺布设备价格都是上亿元。
因此,研究开发一种纤维直径更小、抗菌效果好且成本低廉的纤维复合材料十分有意义。
发明内容
本发明的目的在于克服现有技术不足,提供一种纳米纤维素复合材料及其制备方法与应用,旨在使纳米纤维素复合材料的纤维直径更小,抗菌效果好,成本低廉,应用于替代传统的熔喷无纺布来制备口罩能获得更好的隔离效果。
为实现上述目的,第一方面,本发明提供了一种纳米纤维素复合材料的制备方法,包括以下步骤:将水溶性铈盐、水溶性碱和细菌纤维素膜于水中进行微波反应,得到负载氧化铈纳米颗粒(CeO2NPs)的细菌纤维素膜,即得所述纳米纤维素复合材料(BC@CeO2NPs)。
与植物纤维素相比,BC(细菌纤维素)是不含任何杂质的天然纤维素,没有半纤维素、木质素等杂质,以100%的纤维素形式存在。BC膜具有由直径4nm左右的纤维相互交织形成网状连通、孔镶套、孔道弯曲的超精细三维结构,相比传统的熔喷无纺布,孔隙率高、机械强度和过滤效果好。另外,BC分子内具有大量的亲水基团,因此具有非常好的透气和透水性能。
CeO2NPs具有多种优点,①CeO2NPs独特的抗菌机制具有可逆价态转化的优势,且无需外部激活或辅助工具。由于表面氧空位的存在以及Ce3+和Ce4+之间的可逆转换,因此CeO2NPs具有特殊的储放氧性质,可释放大量的ROS(活性氧物质,Reactive OxygenSpecies),如•OH、1O2和 O2 •−,极其活跃且具有强氧化能力的ROS能在短时间内破坏细胞和基因结构,降解微生物中的多种有机成分包括DNA、RNA和蛋白质,从而达到抗菌和抗病毒的目的,而其他纳米颗粒如ZnO、TiO2等只能产生一种ROS(O2 •−),且需要在紫外线辅助的条件下。另外,CeO2NPs可通过静电吸附的方式吸附在细菌膜表面,以与生物分子相互作用,干扰细胞呼吸、DNA复制、细胞分裂,增加细菌膜的比表面积等,从而将细菌杀死。②CeO2NPs使用寿命长,可以长时间保持高效率。除了可控产生的ROS能高效持久地杀菌外,CeO2NPs释放微量的金属离子穿透细胞壁进入细胞内,并与巯基(-SH)反应,使蛋白质凝固,破坏细胞合成酶的活性,细胞丧失分裂繁殖能力而死亡。金属离子还能破坏微生物电子传输系统、呼吸系统和物质传输系统。当菌体失去活性后,金属离子又会从菌体中游离出来,重复进行杀菌活动,因此其抗菌效果持久。③CeO2NPs的生物安全性高。纳米材料的生物安全性和其与生物体相互作用的机制是推动实际应用的关键。大量的研究表明CeO2NPs毒性相对较低。而其他纳米金属颗粒如纳米银,虽然具有广谱和高效抗菌性而备受关注,但是相对表现出来的高毒性(即使低剂量)限制了它们在保健领域的进一步应用。④CeO2NPs资源丰富,价格相对低廉。在所有17种稀土元素种,铈具有最高的自然丰度(66.5ppm),甚至高于铜(60ppm)和锡(2.33ppm)。
以上这些充分的证明了CeO2NPs在抗菌领域的巨大潜力,但在充分发挥其潜力之前还需要做更多的工作,首先保持CeO2NPs的稳定性是其有效应用于抗菌领域的最大挑战。这种稳定性至关重要因为它将决定这些纳米材料与生物实体的相互作用、抗菌活性、效果以及作用机理。发明人发现通过一步微波合成法能将具有高效抗菌性能的CeO2NPs稳定地在BC表面富集的-OH官能团上成核和生长,制备得到的纳米纤维素复合材料能够确保CeO2NPs高效性的同时维持其稳定性。该纳米纤维素复合材料不仅可以结合细菌纤维素和CeO2NPs的优势,保证CeO2NPs的分散性和稳定性,增强其生物防护性能和机械强度,而且可以通过纳米材料本身的自清洁性能使BC@CeO2NPs复合纳米膜易于回收和处理,实现重复利用。
另外,微波辅助溶液法去合成纳米材料可以提供额外的优势:①快速体积加热、缩短反应时间、提高合成效率;②微波合成中反应物的均匀加热,克服了水热容器加热不均匀的缺点,这使溶液中的热梯度最小化并提供均匀的成核和生长条件,纳米材料的形成一体化而具有均匀的尺寸分布;③通过不同的微波反应参数可调控合成材料的尺寸、形貌、结构等;④微波加热安全、卫生、对环境无污染,符合现代社会的绿色可持续发展。
优选地,所述微波反应的反应温度为60-150℃,反应时间为3-5min,升温时间为0.5~5min,所述水溶性铈盐在所述水中的摩尔浓度为0.013~0.041mol/L,所述水溶性铈盐与所述水溶性碱的摩尔比为0.6:1~40:1,所述水溶性铈盐与所述细菌纤维素膜的质量比为0.29:1~0.91:1。
更优选地,所述微波反应的反应温度为150℃,反应时间为3min,升温时间为1min,所述水溶性铈盐与所述水溶性碱的摩尔比为0.99:1。在此工艺条件下,所得CeO2NPs大小均匀、颗粒稳定,在细菌纤维素膜上的分散程度更好,而且能耗更低。
优选地,所述水溶性铈盐为硝酸铈,所述水溶性碱为一水合氨。本发明所用水溶性铈盐并不局限于为硝酸铈;本发明所用水溶性碱并不局限于为一水合氨,还可以为氢氧化钠、氢氧化钾等。
优选地,所述细菌纤维素膜的制备方法包括以下步骤:所述细菌纤维素膜的制备方法包括以下步骤:将木醋杆菌接种于液体培养基中静态培养,即得所述细菌纤维素膜。
优选地,所述液体培养基包括以下浓度的组分:葡萄糖20g/L、酵母浸粉5g/L、蛋白胨5g/L、无水柠檬酸1.15g/L、磷酸氢二钠十二水合物6.8g/L和余量的水;所述静态培养过程中,先以液体培养基初始体积1/7~1/5的接种量接种培养三天,再稀释11~14倍继续培养三天,然后稀释4~7倍继续培养三天,即得所述细菌纤维素膜;所述静态培养的温度为25~27℃。采用该特定工艺条件的静态培养,对BC的物化性质如形貌、内部结构、孔隙分布等进行高产高效和可控合成,确保所得BC的纤维直径在4nm左右。
优选地,所述木醋杆菌接种于液体培养基前,先在固体培养基中活化培养。
优选地,所述固体培养基包括以下浓度的组分:葡萄糖20g/L、酵母浸粉5g/L、蛋白胨5g/L、无水柠檬酸1.15g/L、磷酸氢二钠十二水合物6.8g/L、琼脂15g/L和余量的水。
第二方面,本发明提供了所述制备方法制得的纳米纤维素复合材料。
第三方面,本发明提供了一种口罩,包括所述纳米纤维素复合材料。所述口罩具备表面过滤功能优异、阻隔效率高、抗菌效果好、使用材料薄、透气性能好、成本低廉、环保等特点。
与现有技术相比,本发明的有益效果为:本发明通过一步微波合成法将CeO2NPs稳定地在细菌纤维素表面的-OH上成核和生长,制备得到的纳米纤维素复合材料不仅保证了CeO2NPs的分散性和稳定性,增强了其生物防护性能和机械强度,而且以纤维直径只有4nm左右和富含亲水基团的细菌纤维素作为载体,使其过滤性和透气性更好,易于回收、处理和实现重复利用,另外,原料成本低廉,合成方法简单,易于工业化生产,利用该纳米纤维素复合材料生产的纳米口罩具备表面过滤功能优异、阻隔效率高、抗菌效果好、使用材料薄、透气性能好、成本低廉、环保等特点。
附图说明
图1为本发明的设计方案简图;
图2为实施例1所得氧化铈纳米颗粒的TEM图;
图3为实施例1所得纳米纤维素复合材料的TEM图;
图4为实施例1所得纳米纤维素复合材料的SEM图;
图5为CeO2NPs和实施例1所得纳米纤维素复合材料的XRD图;
图6为实施例1所得纳米纤维素复合材料的TGA图;
图7为CeO2NPs粒径随微波反应温度变化的变化趋势图;
图8为CeO2NPs粒径随微波反应时间变化的变化趋势图;
图9为CeO2NPs粒径随氨水添加量变化的变化趋势图;
图10为CeO2NPs在BC膜上负载量变化的TGA图;
图11为根据实施例1中的最佳工艺条件制得的纳米纤维素复合材料的抗菌效果图。
具体实施方式
为更好地说明本发明的目的、技术方案和优点,下面将结合具体实施例对本发明进一步说明。本领域技术人员应当理解,此处所描述的具体实施例仅用以解释本发明,并不用于限定本发明。
实施例1
1、BC膜的制备
1.1、培养基的制备
①液体培养基的制备(以1000mL为例):在1000mL的超纯水中,依次加入葡萄糖20g、酵母浸粉5g、蛋白胨5g、无水柠檬酸1.15g和磷酸氢二钠十二水合物6.8g,高压灭菌120℃,30min后使用;
②固体培养基的制备(以1000mL为例):在1000mL的超纯水中,依次加入葡萄糖20g、酵母浸粉5g、蛋白胨5g、无水柠檬酸1.15g、磷酸氢二钠十二水合物6.8g和15g琼脂,高温灭菌120℃,30min后制备琼脂板。
1.2、BC膜的静态培养
从-80℃冰箱中取出一管冷冻保存的木醋杆菌的菌种,依次放入-20℃、-4℃冰箱中进行解冻,再采用一次性接种环将菌种从菌种管中取出在上述固体琼脂平板上划“Z”字,直至划满整个平板,然后在平板上做好标记,依旧将平板倒置放入培养箱中培养3天左右。三天后,取3mL前述液体培养基加入到15mL离心管中,以0.5mL添加到前述15ml离心管中,再转移到恒温培养箱中,26℃恒温静置培养3天。三天后,取40mL前述液体培养基加入到50mL离心管中,再将15mL离心管中的菌种液全部转移至该离心管中,转移至培养箱中,26℃培养3天。三天后,在1L的容器瓶中添加200mL前述液体培养基,随后将50mL离心管中的菌种液转移至该容器中,移至培养箱中26℃静置培养3天。三天后可以在气-液面观察到有白色乳状薄膜产生,即得BC膜。
培养完成后的BC薄膜取出浸泡在乙醇溶液中进行杀菌,然后用90℃的超纯水连续加热搅拌煮30min,再用0.5wt%NaOH溶液于90℃清洗20min,重复两~三次,以去除薄膜上的培养基和细菌,直至BC薄膜呈透明状即可,最后再用超纯水90℃清洗40min,以洗去薄膜中的碱液,使薄膜成中性即可,洗好的薄膜放在超纯水中保存。
2、BC@CeO2NPs的制备
2.1微波反应温度对CeO2NPs粒径的影响
取49.325mL超纯水,加入0.217g Ce(NO3)3,充分搅拌溶解后,在Ce(NO3)3溶液中加入0.675mL 1M的NH4OH溶液,快速摇匀,然后在每个微波管加入10mL该溶液,放入0.1467gBC膜进行微波反应,制得BC@CeO2NPs。其中,微波反应条件如下:升温时间1min,反应温度60~180℃,反应时间3min,搅拌转速200rpm。
图7显示,随着微波反应温度的变化,CeO2NPs粒径有着显著的变化,当微波反应温度为150℃时,CeO2NPs性能稳定,尺寸大小均匀,膜负载均匀可控。
2.2微波反应时间对CeO2NPs粒径的影响
取49.325mL超纯水,加入0.217g Ce(NO3)3,充分搅拌溶解后,在Ce(NO3)3溶液中加入0.675mL 1M的NH4OH溶液,快速摇匀,然后在每个微波管加入10mL该溶液,放入0.1467gBC膜进行微波反应,制得BC@CeO2NPs。其中,微波反应条件如下:升温时间1min,反应温度150℃,反应时间3~5min,搅拌转速200rpm。
图8显示,随着微波反应时间的变化,CeO2NPs粒径有着显著的变化,当微波反应时间为3min时,CeO2NPs性能稳定,尺寸大小均匀,膜负载均匀可控。
2.3 NH4OH用量对CeO2NPs粒径的影响
取49.325mL超纯水,加入0.217g Ce(NO3)3,充分搅拌溶解后,在Ce(NO3)3溶液中加入0.675~1.025mL 1M的NH4OH溶液,快速摇匀,然后在每个微波管加入10mL该溶液,放入0.1467g BC膜进行微波反应,制得BC@CeO2NPs。其中,微波反应条件如下:升温时间1min,反应温度150℃,反应时间3min,搅拌转速200rpm。
图9显示,随着NH4OH用量的变化,CeO2NPs粒径有着显著的变化,当NH4OH用量为0.675mL时,CeO2NPs性能稳定,尺寸大小均匀,膜负载均匀可控。
确定最佳微波反应的工艺条件为:微波反应的反应温度为150℃,反应时间为3min,升温时间为1min,水溶性铈盐与水溶性碱的摩尔比为0.99:1。
取49.325mL超纯水,加入0.217g Ce(NO3)3,充分搅拌溶解后,在Ce(NO3)3溶液中加入0.675mL 1M的NH4OH溶液,快速摇匀,然后在每个微波管加入10mL该溶液,放入0.1467gBC膜进行微波反应,制得BC@CeO2NPs。其中,微波反应条件如下:升温时间1min,反应温度150℃,反应时间3min,搅拌转速200rpm。该工艺条件下制得的BC@CeO2NPs复合膜的表征见图2~6。图3和图4显示制得的CeO2NPs均匀分布在BC膜上,图5显示制得的BC@CeO2NPs有BC和CeO2NPs的特征峰(最上面的XRD曲线图对应BC@CeO2NPs,最下面的XRD曲线图对应CeO2NPs);图6显示BC@CeO2NPs约有17wt%的纳米颗粒。
2.4 CeO2NPs负载量的影响因素
取98.65mL超纯水,加入0.865g Ce(NO3)3,充分搅拌溶解后,在Ce(NO3)3溶液中加入1.35mL 1M的NH4OH溶液,快速摇匀,然后在每个微波管加入10mL该溶液,放入0.1467g BC膜进行微波反应,制得BC@CeO2NPs(对应图10中的A曲线);或者取99.9mL超纯水,加入1.080g Ce(NO3)3,充分搅拌溶解后,在Ce(NO3)3溶液中加入100μL 1M的NH4OH溶液,快速摇匀,然后在每个微波管加入10mL该溶液,放入0.1467g BC膜进行微波反应,制得BC@CeO2NPs(对应图10中的B曲线);取99.9mL超纯水,加入1.295g Ce(NO3)3,充分搅拌溶解后,在Ce(NO3)3溶液中加入100μL 1M的NH4OH溶液,快速摇匀,然后在每个微波管加入10mL该溶液,放入0.1467g BC膜进行微波反应,制得BC@CeO2NPs(对应图10中的C曲线),上述微波反应条件相同,均为升温时间1min,反应温度150℃,反应时间3min,搅拌转速200rpm。
由图10可知,通过调整不同的反应参数,如硝酸铈、氨水和BC膜的配比,可以可控的调整纳米颗粒在BC膜上的负载量。
效果例
采用如下方法研究BC@CeO2NPs样品的抗菌性能,具体为:
(1)从-80℃的冰箱中取出大肠杆菌、金黄色葡萄球菌和铜绿假单胞菌,置于冰中保存;
(2)准备三个液体培养基和6个固体培养基,放在超净工作台中紫外灭菌,将三种细菌分别放在三个液体培养基中,置于摇床中培养18-24小时。再将三种细菌放在6个固体培养基中(每种放两个)培养18-24小时。培养结束后,检测液体培养基中的细菌浓度,固体培养基保存起来(4℃),用液体培养基中的细菌涂板,进行下一步;
(3)用96孔板酶标仪(OD600)测浓度,得出OD值进行浓度换算(目标1.5×1011CFU/mL),将大肠杆菌稀释10倍,铜绿假单胞菌稀释10倍,金黄色葡萄球菌稀释15倍;
(4)将三十块板每十块板涂抹一种菌,在培养皿中心滴加BC@CeO2NPs样品或BC膜样品或BC膜冻干样品,或者不添加任何样品,放入培养箱中培养18-24h(注:同种菌在步骤(2)和(4)中的培养时间相同,BC@CeO2NPs样品、BC膜样品及BC膜冻干样品相应BC的量相同)。
其中,BC@CeO2NPs样品的制备方法为:取49.325mL超纯水,加入0.217g Ce(NO3)3,充分搅拌溶解后,在Ce(NO3)3溶液中加入0.675mL 1M的NH4OH溶液,快速摇匀,然后在每个微波管加入10mL该溶液,放入0.1467g 实施例1所得BC膜进行微波反应,制得BC@CeO2NPs。其中,微波反应条件如下:升温时间1min,反应温度150℃,反应时间3min,搅拌转速200rpm;
BC膜样品:实施例1所得BC膜;
BC膜冻干样品:由实施例1所得BC膜冷冻干燥制得。
由图11可知,本发明制得的BC@CeO2NPs具有非常明显的抑菌圈(最上面两个图为BC@CeO2NPs的抑菌效果图;每组柱状图从左至右依次为大肠杆菌、金黄色葡萄球菌、铜绿假单胞菌)。
最后所应当说明的是,以上实施例仅用以说明本发明的技术方案而非对本发明保护范围的限制,尽管参照较佳实施例对本发明作了详细说明,本领域的普通技术人员应当理解,可以对本发明的技术方案进行修改或者等同替换,而不脱离本发明技术方案的实质和范围。
Claims (9)
1.一种纳米纤维素复合材料的制备方法,其特征在于,包括以下步骤:将水溶性铈盐、水溶性碱和细菌纤维素膜于水中进行微波反应,得到负载氧化铈纳米颗粒的细菌纤维素膜,即得所述纳米纤维素复合材料;所述微波反应的反应温度为60-150℃,反应时间为3-5min;所述水溶性铈盐与所述水溶性碱的摩尔比为0.6:1~40:1;所述水溶性铈盐为硝酸铈,所述水溶性碱为一水合氨。
2.如权利要求1所述的纳米纤维素复合材料的制备方法,其特征在于,升温时间为0.5~5min,所述水溶性铈盐在所述水中的摩尔浓度为0.013~0.041mol/L,所述水溶性铈盐与所述细菌纤维素膜的质量比为0.29:1~0.91:1。
3.如权利要求2所述的纳米纤维素复合材料的制备方法,其特征在于,所述微波反应的反应温度为150℃,反应时间为3min,升温时间为1min,所述水溶性铈盐与所述水溶性碱的摩尔比为0.99:1。
4.如权利要求1所述的纳米纤维素复合材料的制备方法,其特征在于,所述细菌纤维素膜的制备方法包括以下步骤:将木醋杆菌接种于液体培养基中静态培养,即得所述细菌纤维素膜。
5.如权利要求4所述的纳米纤维素复合材料的制备方法,其特征在于,所述液体培养基包括以下浓度的组分:葡萄糖20g/L、酵母浸粉5g/L、蛋白胨5g/L、无水柠檬酸1.15g/L、磷酸氢二钠十二水合物6.8g/L和余量的水;所述静态培养过程中,先以液体培养基初始体积1/7~1/5的接种量接种培养三天,再稀释11~14倍继续培养三天,然后稀释4~7倍继续培养三天,即得所述细菌纤维素膜;所述静态培养的温度为25~27℃。
6.如权利要求4所述的纳米纤维素复合材料的制备方法,其特征在于,所述木醋杆菌接种于液体培养基前,先在固体培养基中活化培养。
7.如权利要求6所述的纳米纤维素复合材料的制备方法,其特征在于,所述固体培养基包括以下浓度的组分:葡萄糖20g/L、酵母浸粉5g/L、蛋白胨5g/L、无水柠檬酸1.15g/L、磷酸氢二钠十二水合物6.8g/L、琼脂15g/L和余量的水。
8.如权利要求1~7任一项所述的制备方法制得的纳米纤维素复合材料。
9.一种口罩,其特征在于,包括如权利要求8所述的纳米纤维素复合材料。
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