CN105565506B - 一种负载具有核‑壳结构的磁性纳米颗粒的生物复合材料及其制备方法和用途 - Google Patents
一种负载具有核‑壳结构的磁性纳米颗粒的生物复合材料及其制备方法和用途 Download PDFInfo
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Abstract
本发明公开了一种负载具有核‑壳结构的磁性纳米颗粒的生物复合材料及其制备方法和用途。本发明的复合材料通过包括下列步骤的制备方法制得:1)Fe3O4纳米颗粒的制备;2)Fe3O4@mSiO2纳米颗粒的制备;3)Fe3O4@mSiO2@MANHE纳米颗粒的制备;4)枯草杆菌@Fe3O4@mSiO2@MANHE复合材料的制备。本发明的制备方法中所采用的原材料成本低廉,容易获得;操作简单、方便,整个过程中没有使用昂贵的设备;本发明的复合材料对水体中的Cr(VI)具有很好的吸附降解效果,并且能够快速地从水体中分离出来,不会造成二次污染,具有广泛的应用前景。
Description
技术领域
本发明属于功能材料技术领域,具体涉及到一种负载具有核-壳结构的磁性纳米颗粒的生物复合材料,该复合材料的制备方法,以及利用该复合材料来处理含六价铬废水的用途。
背景技术
六价铬(简写为Cr(VI))为吞入性毒物/吸入性极毒物,具有致敏、致畸、致癌等严重不良后果,并且对环境具有持久危险性。六价铬化合物常用于电镀、电子元器件加工等工艺中,动物接触含有六价铬的水后,六价铬会被体内许多组织和器官的细胞吸收,引起胃肠道及肝、肾功能损害,还可能伤及眼部,出现视网膜出血、视神经萎缩等问题,因此针对含六价铬废水的处理亟需受到社会各界的广泛关注。
由于同时具备磁性颗粒和纳米颗粒的双重优势,Fe3O4磁性纳米颗粒已经广泛应用于靶向药物载体、细胞分离、核磁共振、免疫分析、核酸杂交等生物医学领域。同时,这种超顺磁性材料在环境保护监测领域也具有很好的应用前景,可以作为吸附材料来处理工业废水中存在的重金属。但是,Fe3O4磁性纳米颗粒易氧化,比表面积较高,具有强烈的聚集倾向,难以直接应用。
采用定型SiO2对Fe3O4磁性纳米颗粒进行表面包覆后,SiO2包覆层不但提高了Fe3O4磁性纳米颗粒的化学稳定性,而且由于SiO2包覆层的表面存在羟基,也提高了Fe3O4磁性纳米颗粒的生物相容性,拓宽了在生物、催化等领域的应用。另外,由于复合材料表面存在大量的硅醇基,因此可以根据不同的需要,在其表面修饰不同的功能型聚合物,以实现去除不同重金属的目的。然而,这种SiO2包覆Fe3O4磁性纳米颗粒后形成的复合材料在吸附处理重金时有其固有的不足之处,成本较高,并且会造成二次污染等问题。由于这些原因,直接阻碍了其在环境治理中的应用。
近年来,由于具有处理方法清洁、无二次污染和低成本等优势,生物法已经得到广泛关注,但是微生物处理污染物也有其自身的弊端,处理周期长、菌体难以从水中分离等因素制约了实际应用。
发明内容
针对上述情况,本发明利用吸附法和生物降解法各自的优点,将两者加以结合,通过将Fe3O4磁性纳米颗粒经由包覆该磁性纳米颗粒核芯的聚合物外壳修饰到枯草杆菌(Bacillus subtilis)表面,使其在利用Fe3O4磁性纳米颗粒来快速富集Cr(VI)的同时,又可以利用将其负载的微生物来快速降解Cr(VI),大大缩短了污染物的处理周期,同时还可以利用纳米颗粒本身的磁性来实现从水体中快速分离,很好地克服了阻碍其应用的瓶颈,使其在重金属污染治理方面得到广泛应用。
首先,本发明提供了一种负载具有核-壳结构的Fe3O4磁性纳米颗粒的枯草杆菌生物复合材料的制备方法,其包括如下步骤:
(1)Fe3O4纳米颗粒的制备:
按照七水合硫酸亚铁:无水醋酸钠=1:5~8的摩尔比,将七水合硫酸亚铁(FeSO4·7H2O)和无水醋酸钠(NaOAc)加入到乙二醇中,搅拌至溶液呈透明状后转移至高压反应釜中,于150~200℃密闭反应5~8小时,反应结束后,经离心、洗涤、干燥,得到Fe3O4纳米颗粒;
(2)Fe3O4@mSiO2纳米颗粒的制备:
将步骤(1)中获得的Fe3O4纳米颗粒加入到乙醇和水的混合液中,超声分散,在搅拌条件下,按照Fe3O4纳米颗粒:十六烷基三甲基溴化铵:四乙氧基硅烷=1:3~5:2~3的质量比,依次向上述体系中加入十六烷基三甲基溴化铵(CATB)和四乙氧基硅烷(又称为原硅酸四乙酯,TEOS),室温反应6~10小时,反应完成后,经磁性分离、洗涤、干燥,得到Fe3O4@mSiO2纳米颗粒;
(3)Fe3O4@mSiO2@MANHE纳米颗粒的制备:
将步骤(2)中获得的Fe3O4@mSiO2纳米颗粒加入到N,N-二甲基甲酰胺中,超声分散,在搅拌条件下,按照Fe3O4@mSiO2纳米颗粒:γ-氨丙基三乙氧基硅烷=50~100mg:1mL的比例,向上述体系中加入γ-氨丙基三乙氧基硅烷(KH500),室温搅拌过夜,经磁性离心、洗涤、干燥,得到氨基修饰的Fe3O4@mSiO2纳米颗粒;
将上述氨基修饰的Fe3O4@mSiO2纳米颗粒加入到环己酮中,超声分散,在惰性气体保护及搅拌条件下,按照氨基修饰的Fe3O4@mSiO2纳米颗粒:4,4'-偶氮双(4-氰基戊酰氯)=1:20~30的质量比,向上述体系中加入4,4'-偶氮双(4-氰基戊酰氯)(ABCPA-Cl),室温搅拌过夜,经磁性离心、洗涤、干燥,得到ABCPA修饰的Fe3O4@mSiO2纳米颗粒;
将上述ABCPA修饰的Fe3O4@mSiO2纳米颗粒加入到环己酮中,超声分散,在惰性气体保护及搅拌条件下,按照ABCPA修饰的Fe3O4@mSiO2纳米颗粒:N-丙烯酰氧基琥珀酰亚胺=1:20~30的质量比以及N-丙烯酰氧基琥珀酰亚胺:4-乙烯基吡啶=1g:10~15mL的比例,向上述体系中加入N-丙烯酰氧基琥珀酰亚胺和4-乙烯基吡啶,于70~80℃反应0.5~1小时,反应完成后,经磁性离心、洗涤、干燥,得到Fe3O4@mSiO2@MANHE纳米颗粒;
(4)枯草杆菌@Fe3O4@mSiO2@MANHE复合材料的制备:
将枯草杆菌加入到PBS溶液中,分散均匀,按照枯草杆菌(湿重):Fe3O4@mSiO2@MANHE纳米颗粒=50~100:1的质量比,向上述体系中加入步骤(3)中获得的Fe3O4@mSiO2@MANHE纳米颗粒,并置于30℃/120rpm的恒温摇床上过夜,经磁性离心、洗涤、干燥,得到负载具有核-壳结构的Fe3O4磁性纳米颗粒的枯草杆菌生物复合材料。
优选的,在上述制备方法中,步骤(1)中所述七水合硫酸亚铁与无水醋酸钠之间的摩尔比为1:7。
优选的,在上述制备方法中,步骤(2)中所述乙醇和水的混合液中乙醇与水之间的体积比为4:1。
优选的,在上述制备方法中,步骤(2)中所述乙醇和水的混合液中使用的水为去离子水。
优选的,在上述制备方法中,步骤(2)中所述Fe3O4纳米颗粒、十六烷基三甲基溴化铵、四乙氧基硅烷之间的质量比为1:3:2.3。
优选的,在上述制备方法中,步骤(3)中所述Fe3O4@mSiO2纳米颗粒与γ-氨丙基三乙氧基硅烷之间的比例为200mg:3mL。
优选的,在上述制备方法中,步骤(3)中所述氨基修饰的Fe3O4@mSiO2纳米颗粒与4,4'-偶氮双(4-氰基戊酰氯)之间的质量比为1:20。
优选的,在上述制备方法中,步骤(3)中所述ABCPA修饰的Fe3O4@mSiO2纳米颗粒与N-丙烯酰氧基琥珀酰亚胺之间的质量比1:20。
优选的,在上述制备方法中,步骤(3)中所述N-丙烯酰氧基琥珀酰亚胺与4-乙烯基吡啶之间的比例为1g:10mL。
优选的,在上述制备方法中,步骤(3)中所述惰性气体选自氮气、氦气、氩气中的任意一种,优选氮气。
优选的,在上述制备方法中,步骤(4)中所述枯草杆菌(湿重)与Fe3O4@mSiO2@MANHE纳米颗粒之间的质量比为100:1。
优选的,在上述制备方法中,步骤(4)中所述PBS溶液的pH值为7。
其次,本发明提供了通过上述制备方法制备的负载具有核-壳结构的Fe3O4磁性纳米颗粒的枯草杆菌生物复合材料。
最后,本发明提供了上述负载具有核-壳结构的Fe3O4磁性纳米颗粒的枯草杆菌生物复合材料在处理含六价铬废水中的用途。
与现有技术相比,利用上述技术方案的本发明具有如下优点:
(1)制备过程中所采用的原材料成本低廉,容易获得;
(2)操作简单、方便,整个过程中没有使用昂贵的设备;
(3)本发明的复合材料对水体中的Cr(VI)具有很好的吸附降解效果,并且能够快速地从水体中分离出来,不会造成二次污染,具有广泛的应用前景。
附图说明
图1为Fe3O4纳米颗粒的透射电镜图(TEM)。
图2为Fe3O4@mSiO2纳米颗粒的透射电镜图(TEM)。
图3为Fe3O4@mSiO2@MANHE纳米颗粒的透射电镜图(TEM)。
图4为处理Cr(VI)前后枯草杆菌的扫描电镜图(SEM)。
图5为枯草杆菌@Fe3O4@mSiO2@MANHE复合材料的透射电镜图(TEM)。
图6为枯草杆菌对Cr(VI)的降解曲线和OD600曲线图。
图7为枯草杆菌处理Cr(VI)的过程中在不同时段下的紫外可见吸收光谱图。
图8为枯草杆菌、Fe3O4@mSiO2@MANHE纳米颗粒、枯草杆菌@Fe3O4@mSiO2@MANHE复合材料对Cr(VI) 的降解效果对比图。
具体实施方式
以下将结合附图和具体的实施例对本发明做出进一步的说明。除非特意指出,下列实施例中所使用的药剂、实验材料及仪器等均可通过商业手段获得。
实施例1:Fe3O4纳米颗粒的制备。
将FeSO4·7H2O(2.02g,7.2mmol)和无水NaOAc(4.1g,50mmol)加入到乙二醇(50mL)中,搅拌0.5h,溶液透明时转移至高压反应釜中,于180℃反应6h,反应完成后冷却至室温,离心,得到黑色固体,用水和乙醇清洗3次,于60℃真空干燥5h,得到Fe3O4纳米颗粒(0.5g)。
图1为Fe3O4纳米颗粒的TEM。从中可以看出,Fe3O4纳米颗粒分散均匀且直径约为30nm。
实施例2:Fe3O4@mSiO2纳米颗粒的制备。
称取实施例1中制备的Fe3O4纳米颗粒(100mg),加入到乙醇(80mL)和去离子水(20mL)的混合液中,超声分散30min,在机械搅拌下,向上述混合物中加入CATB(300mg),然后通过微量注射器缓慢加入TEOS(0.25mL,234mg),室温反应6h,反应完成后,磁性分离,用去离子水洗涤3次,于60℃干燥24h,得到Fe3O4@mSiO2纳米颗粒(260mg)。
图2为Fe3O4@mSiO2纳米颗粒的TEM。从中可以看出,Fe3O4表面包覆了一层介孔二氧化硅(mesoporous silicon dioxide,简写为mSiO2),并且具有良好的分散性,纳米颗粒的直径增加至50nm。
实施例3:Fe3O4@mSiO2@MANHE纳米颗粒的制备。
称取实施例2中制备的Fe3O4@mSiO2纳米颗粒(200mg),加入到DMF(150mL)中,超声分散30min,在机械搅拌下,向上述混合物中加入KH550(3mL),搅拌过夜,磁性分离,用乙醇和去离子洗涤3次,烘干,得到氨基修饰的Fe3O4@mSiO2纳米颗粒(210mg),备用。
称取上述产品(10mg),加入到环己酮(9mL)中,超声分散30min,在氮气保护及机械搅拌下,向上述混合物中加入ABCPA-Cl(0.2g),搅拌过夜,磁性分离,用乙醇和去离子洗涤3次,烘干,得到ABCPA修饰的Fe3O4@mSiO2纳米颗粒(16mg),备用。
称取上述产品(10mg),加入到环己酮(9mL)中,超声分散30min,在氮气保护及机械搅拌下,向上述混合物中加入N-丙烯酰氧基琥珀酰亚胺(0.2g)和4-乙烯基吡啶(2mL),于70℃反应0.5h,反应完成后,磁性分离,用乙醇和去离子洗涤3次,烘干,得到Fe3O4@mSiO2@MANHE纳米颗粒(18mg),其中MANHE是指在纳米颗粒表面自由基引发剂(ABCPA片段)的引发下N-丙烯酰氧基琥珀酰亚胺和4-乙烯基吡啶发生聚合所产生的聚合物。
图3为Fe3O4@mSiO2@MANHE纳米颗粒的TEM。从图上可以看出,Fe3O4@mSiO2纳米颗粒包覆上一层聚合物(MANHE),分散性有所下降,纳米颗粒的直径进一步增加至100nm。
实施例4:枯草杆菌的培养以及对Cr(VI)的降解。
将枯草杆菌(购买自福建微生物学研究所,型号ATCC-6633)菌种接种到LB培养基中,并置于30℃/120rpm恒温摇床上培养48h,离心并收集菌体,随后用于处理Cr(VI)。
图4a为降解Cr(VI)前枯草杆菌的SEM,图4b为降解Cr(VI)后枯草杆菌的SEM。从图中可以明显看出,处理Cr(VI)之前的菌体表面光滑,而处理Cr(VI)之后的菌体表面凹凸不平。
实施例5:枯草杆菌@Fe3O4@mSiO2@MANHE复合材料的制备。
将实施例4中培养的细菌离心收集,称取湿重为1g的细菌加入到PBS溶液(20mL,pH=7)当中,分散均匀;称取实施例3中制备的Fe3O4@mSiO2@MANHE纳米颗粒(10mg),分散于上述混合液中,并置于30℃/120rpm的恒温摇床上过夜,磁性分离,得到枯草杆菌@Fe3O4@mSiO2@MANHE复合材料(1g ,湿重)。
图5为枯草杆菌@Fe3O4@mSiO2@MANHE复合材料的TEM。从图可以清晰地看出,Fe3O4@mSiO2@MANHE纳米颗粒被修饰到菌体表面上。
实施例6:枯草杆菌降解Cr(VI)(浓度为40ppm)及测试结果。
取100mL菌液,离心收集菌体,菌体重新分散在含有40ppm Cr(VI)的废水(100mL)中,并在不同时段取样,通过显色法测定各时段下的溶液浓度并绘制紫外可见吸收光谱图。
图6为枯草杆菌处理Cr(VI)的降解曲线和OD600曲线,从中可知,在Cr(VI)浓度下降的同时,细菌的OD600在原有的基础上有所增加,表明枯草杆菌能够耐受Cr(VI)的毒害作用,可以有效地存活于含Cr(VI)水体中。图7为枯草杆菌处理Cr(VI)的过程中在不同时段下的紫外可见吸收光谱图,从中可知,在364nm处,最大吸收波长随时间增加明显降低,说明Cr(VI)浓度在不断降低,120h后在364nm处已无吸收峰,表明溶液中的Cr(VI)浓度已基本趋近于0。
实施例7:枯草杆菌、Fe3O4@mSiO2@MANHE纳米颗粒、枯草杆菌@Fe3O4@mSiO2@MANHE复合材料处理Cr(VI)(浓度为40ppm)的效果对比。
称取相同质量的枯草杆菌、Fe3O4@mSiO2@MANHE纳米颗粒、枯草杆菌@Fe3O4@mSiO2@MANHE复合材料,分别分散在含有40ppm Cr(VI)的溶液中,在不同时段下取样,测定所取样品的浓度,并相应绘制紫外可见吸收光谱图。
图8为枯草杆菌、Fe3O4@mSiO2@MANHE纳米颗粒、枯草杆菌@Fe3O4@mSiO2@MANHE复合材料对Cr(VI)的降解效果对比图。通过对比可以明显发现,枯草杆菌@Fe3O4@mSiO2@MANHE复合材料去除六价铬的速率最快,并且效果最好。
综上所述,本发明通过将Fe3O4@mSiO2@MANHE纳米颗粒修饰到枯草杆菌B. subtilis上,实现了“边吸附边降解Cr(VI)”,降解速度快、去除效率高。更为重要的是,实现了菌体的磁性分离,解决了阻碍微生物处理重金属污染的应用问题。另外,本发明中公开的制备方法易于操作,并且所使用的原料廉价易得。因此,本发明的磁性纳米生物复合材料在未来的污水处理中将具有良好的应用前景。
Claims (10)
1.一种负载具有核-壳结构的Fe3O4磁性纳米颗粒的枯草杆菌生物复合材料的制备方法,其包括如下步骤:
1)Fe3O4纳米颗粒的制备:
按照七水合硫酸亚铁:无水醋酸钠=1:5~8的摩尔比,将七水合硫酸亚铁和无水醋酸钠加入到乙二醇中,搅拌至溶液呈透明状后转移至高压反应釜中,于150~200℃密闭反应5~8小时,反应结束后,经离心、洗涤、干燥,得到Fe3O4纳米颗粒;
2)Fe3O4@mSiO2纳米颗粒的制备:
将步骤1)中获得的Fe3O4纳米颗粒加入到乙醇和水的混合液中,超声分散,在搅拌条件下,按照Fe3O4纳米颗粒:十六烷基三甲基溴化铵:四乙氧基硅烷=1:3~5:2~3的质量比,依次向上述体系中加入十六烷基三甲基溴化铵和四乙氧基硅烷,室温反应6~10小时,反应完成后,经磁性分离、洗涤、干燥,得到Fe3O4@mSiO2纳米颗粒;
3)Fe3O4@mSiO2@MANHE纳米颗粒的制备:
将步骤2)中获得的Fe3O4@mSiO2纳米颗粒加入到N,N-二甲基甲酰胺中,超声分散,在搅拌条件下,按照Fe3O4@mSiO2纳米颗粒:γ-氨丙基三乙氧基硅烷=50~100mg:1mL的比例,向上述体系中加入γ-氨丙基三乙氧基硅烷,室温搅拌过夜,经磁性离心、洗涤、干燥,得到氨基修饰的Fe3O4@mSiO2纳米颗粒;
将上述氨基修饰的Fe3O4@mSiO2纳米颗粒加入到环己酮中,超声分散,在惰性气体保护及搅拌条件下,按照氨基修饰的Fe3O4@mSiO2纳米颗粒:4,4'-偶氮双(4-氰基戊酰氯)=1:20~30的质量比,向上述体系中加入4,4'-偶氮双(4-氰基戊酰氯),室温搅拌过夜,经磁性离心、洗涤、干燥,得到ABCPA修饰的Fe3O4@mSiO2纳米颗粒;
将上述ABCPA修饰的Fe3O4@mSiO2纳米颗粒加入到环己酮中,超声分散,在惰性气体保护及搅拌条件下,按照ABCPA修饰的Fe3O4@mSiO2纳米颗粒:N-丙烯酰氧基琥珀酰亚胺=1:20~30的质量比以及N-丙烯酰氧基琥珀酰亚胺:4-乙烯基吡啶=1g:10~15mL的比例,向上述体系中加入N-丙烯酰氧基琥珀酰亚胺和4-乙烯基吡啶,于70~80℃反应0.5~1小时,反应完成后,经磁性离心、洗涤、干燥,得到Fe3O4@mSiO2@MANHE纳米颗粒;
4)枯草杆菌@Fe3O4@mSiO2@MANHE复合材料的制备:
将枯草杆菌加入到PBS溶液中,分散均匀,按照枯草杆菌湿重:Fe3O4@mSiO2@MANHE纳米颗粒=50~100:1的质量比,向上述体系中加入步骤3)中获得的Fe3O4@mSiO2@MANHE纳米颗粒,并置于30℃/120rpm的恒温摇床上过夜,经磁性离心、洗涤、干燥,得到负载具有核-壳结构的Fe3O4磁性纳米颗粒的枯草杆菌生物复合材料。
2.根据权利要求1所述的制备方法,其特征在于:
步骤1)中所述七水合硫酸亚铁与无水醋酸钠之间的摩尔比为1:7。
3.根据权利要求1所述的制备方法,其特征在于:
步骤2)中所述乙醇和水的混合液中乙醇与水之间的体积比为4:1;
步骤2)中所述Fe3O4纳米颗粒、十六烷基三甲基溴化铵、四乙氧基硅烷之间的质量比为1:3:2.3。
4.根据权利要求1所述的制备方法,其特征在于:
步骤3)中所述Fe3O4@mSiO2纳米颗粒与γ-氨丙基三乙氧基硅烷之间的比例为200mg:3mL;
步骤3)中所述氨基修饰的Fe3O4@mSiO2纳米颗粒与4,4'-偶氮双(4-氰基戊酰氯)之间的质量比为1:20;
步骤3)中所述ABCPA修饰的Fe3O4@mSiO2纳米颗粒与N-丙烯酰氧基琥珀酰亚胺之间的质量比1:20;
步骤3)中所述N-丙烯酰氧基琥珀酰亚胺与4-乙烯基吡啶之间的比例为1g:10mL。
5.根据权利要求1所述的制备方法,其特征在于:
步骤3)中所述惰性气体选自氮气、氦气、氩气中的任意一种。
6.根据权利要求5所述的制备方法,其特征在于:
步骤3)中所述惰性气体为氮气。
7.根据权利要求1所述的制备方法,其特征在于:
步骤4)中所述枯草杆菌湿重与Fe3O4@mSiO2@MANHE纳米颗粒之间的质量比为100:1。
8.根据权利要求1所述的制备方法,其特征在于:
步骤4)中所述PBS溶液的pH值为7。
9.通过根据权利要求1至8中任一项所述的制备方法制备的负载具有核-壳结构的Fe3O4磁性纳米颗粒的枯草杆菌生物复合材料。
10.根据权利要求9所述的负载具有核-壳结构的Fe3O4磁性纳米颗粒的枯草杆菌生物复合材料在处理含六价铬废水中的用途。
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