CN106256765B - 一种磁性羧甲基壳聚糖纳米材料及其制备方法 - Google Patents
一种磁性羧甲基壳聚糖纳米材料及其制备方法 Download PDFInfo
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- RUTXIHLAWFEWGM-UHFFFAOYSA-H iron(3+) sulfate Chemical compound [Fe+3].[Fe+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O RUTXIHLAWFEWGM-UHFFFAOYSA-H 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G49/00—Compounds of iron
- C01G49/02—Oxides; Hydroxides
- C01G49/08—Ferroso-ferric oxide [Fe3O4]
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
- C09C1/00—Treatment of specific inorganic materials other than fibrous fillers; Preparation of carbon black
- C09C1/22—Compounds of iron
- C09C1/24—Oxides of iron
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
- C09C3/00—Treatment in general of inorganic materials, other than fibrous fillers, to enhance their pigmenting or filling properties
- C09C3/10—Treatment with macromolecular organic compounds
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Abstract
本发明公开了一种磁性羧甲基壳聚糖纳米材料及其制备方法,包括如下步骤:(1)将三价铁盐与二价铁盐混合,其中Fe3+与Fe2+的摩尔比为1.5~2:1,加水配成溶液;(2)将羧甲基壳聚糖溶于水配成溶液,与步骤(1)的溶液混合并搅拌均匀,将混合液在微波条件下反应,微波的功率为700~900W,温度设为70~85℃,在反应过程中逐滴加入氨水,使溶液的pH稳定在8~9,反应30min;(3)反应结束后冷却到室温,用磁铁分离固液两相,倒去上层液体,将颗粒用去离子水洗涤至中性,再用无水乙醇洗涤,最后将固体颗粒冷冻干燥,得到磁性羧甲基壳聚糖纳米材料。该制备方法工艺简便,产品粒径均一,且具备较好的超顺磁性。
Description
技术领域
本发明涉及一种用微波法快速制备水溶性的羧甲基壳聚糖包裹的纳米四氧化三铁材料的绿色方法,属于材料科学领域。
背景技术
纳米磁性材料作为一种新材料,由于其独特的物理化学性质,使其在物理化学等方面表现出与常规磁性材料不同的特殊性质。而且,当纳米磁性材料的尺寸小于一临界值时,则会表现出超顺磁性,即当外界施予磁场时,磁畴中的原子以及晶体的磁矩会按照同一方向排列;不存在磁场时,净磁矩为零,使磁性消失。在众多超顺磁性材料中,由于超顺磁性氧化铁粒子具有很好的安全性,血液循环时间长,组织特异性高,故其被广泛用于磁流体、靶向给药、传感器和磁共振造影剂等领域。但是,单纯的纳米四氧化三铁具有较高的表面能,极易团聚,进入人体后容易聚集,引起血栓,没有生物活性基团,这极大地限制了其在生物医药和磁共振造影剂方面的应用。利用亲水基团来修饰四氧化三铁是一种增加其水溶性的有效方法。
壳聚糖由于具有无毒副作用、可经微生物降解、良好的生物可容性和成膜性等优良特性,在轻工业、食品、医药卫生、环保、生物工程、农业等诸多领域得到了应用。壳聚糖的来源极其丰富,广泛存在于植物细胞壁、甲壳类动物和昆虫的外壳中,其中海洋生物的生成量在10亿吨以上。目前,利用壳聚糖包裹的四氧化三铁纳米粒子已被成功制备,但是,壳聚糖的水溶性也不好。
发明内容
本发明的目的在于提供一种温和快速地制备水溶的羧甲基壳聚糖/纳米四氧化三铁复合粒子的方法,采用高分子羧甲基壳聚糖为模板,在羧甲基壳聚糖原位生长纳米四氧化三铁粒子,利用羧甲基壳聚糖高分子和纳米颗粒之间的相互作用,有效的解决了一般化学制备方法粒径分布宽、易团聚的缺陷,获得了分散均匀,水溶性良好的纳米颗粒。本发明实现了在温和条件下快速制备水溶性羧甲基壳聚糖修饰的纳米氧化铁,该方法工艺简单,条件温和,所需设备少,可实现批量生产。
本发明目的通过以下技术方案实现:
一种磁性羧甲基壳聚糖纳米材料的制备方法,包括如下步骤:
(1)将三价铁盐与二价铁盐混合,其中Fe3+与Fe2+的摩尔比为1.5~2:1,加水配成溶液;
(2)将羧甲基壳聚糖溶于水配成溶液,与步骤(1)的溶液混合并搅拌均匀,将混合液在微波条件下反应,微波的功率为700~900W,温度设为70~85℃,在反应过程中逐滴加入氨水,使溶液的pH稳定在8~9,反应25~35min;
(3)反应结束后冷却到室温,用磁铁分离固液两相,倒去上层液体,将颗粒用去离子水洗涤至中性,再用无水乙醇洗涤,最后将固体颗粒冷冻干燥,得到磁性羧甲基壳聚糖纳米材料。
步骤(1)所述混合液中Fe3+的浓度为0.1~0.4mol/L,羧甲基壳聚糖的浓度为5~15g/L。
所述微波的条件为功率为800W,温度为80℃。
所述羧甲基壳聚糖的制备方法:
将纯化的壳聚糖粉末加入氢氧化钠溶液,搅拌3h,冷冻过夜,加水溶胀后缓慢加入异丙醇搅拌均匀,取氯乙酸分数次加入,加入后搅拌12h,滤出异丙醇,加水溶解,用稀醋酸调节pH为中性,依次用75%甲醇,无水乙醇洗涤,冷冻干燥得到羧甲基壳聚糖。
所述氯乙酸与壳聚糖粉末的质量比为1:(1~3),优选1:2。
所述纯化的壳聚糖粉末的制备方法为:将壳聚糖粉末加入醋酸水溶液中,在磁力搅拌下浸泡5h,然后将沉淀物固液分离,用去离子水洗涤2~3次,放入烘箱在温度为60~80℃下烘干,粉碎后即可。
所述三价铁盐是三氯化铁或硫酸铁的一种,所述二价铁盐是氯化亚铁和/或硫酸亚铁中的一种。
该方法包括以下工艺步骤:
与现有技术相比,本发明具有如下优点和有益效果:
(1)本发明在微波的条件下,在羧甲基壳聚糖中原位合成纳米四氧化三铁,从而使纳米四氧化三铁被羧甲基壳聚糖所包裹,所得到的羧甲基壳聚糖/四氧化三铁纳米粒子由于表面被羧甲基壳聚糖包裹,使得其表面带有大量亲水的羧基和氨基,有效增加了四氧化三铁的水溶性。
(2)同时,由于四氧化三铁被羧甲基壳聚糖包裹,增加了其表面电荷,有效地避免了自聚集与分布不均的问题,极大地提高了磁性纳米四氧化三铁在水中的稳定性。
(3)本发明羧甲基壳聚糖纳米材料尺寸较小,粒径均一,分散均匀,水溶性良好,在其表面修饰羧甲基壳聚糖,具有很好的生物相容性和可生物降解性,为实现纳米四氧化三铁在生物医药和生物成像等领域的应用提供了优良的载体。
(4)整个制备工艺清洁、条件温和、简单、无污染,适合大规模生产。
附图说明
图1为本发明制备的羧甲基壳聚糖(a)、羧甲基壳聚糖包裹纳米四氧化三铁(b)和四氧化三铁(c)粒子的红外(FT-IR)光谱。
图2(a)(b)分别为实施例3的纳米四氧化三铁粒子和实施例2的羧甲基壳聚糖包裹的纳米四氧化三铁粒子的X射线衍射(XRD)光谱。
图3(a)(b)分别为实施例3的纳米四氧化三铁粒子和实施例2的羧甲基壳聚糖包裹的纳米四氧化三铁粒子的粒径及粒径分布。
图4为本发明制备的羧甲基壳聚糖包裹纳米四氧化三铁粒子的透射电镜(TEM)。
具体实施方式
下面结合具体实施例对本发明作进一步具体详细描述,但本发明的实施方式不限于此,对于未特别注明的工艺参数,可参照常规技术进行。实施例1所用壳聚糖分子量为5万,脱乙酰度为90%。
实施例1
(1)纯化壳聚糖,将5g壳聚糖粉末加入1%的醋酸溶液中淹没,在磁力搅拌下浸泡5h,将溶液进行固液分离,用去离子水洗涤固体2次,再将块状壳聚糖放在70℃下烘干,粉碎后即为纯化的壳聚糖粉末。
(2)制备羧甲基壳聚糖,称取50g氢氧化钠固体,加100mL超纯水配成溶液,取2g纯化的壳聚糖粉末加入上述溶液,磁力搅拌3h,放入冰箱冷冻过夜,将溶胀后的样品转入200mL三口烧瓶,缓慢加入20mL异丙醇搅拌均匀,取1g氯乙酸分4次加入烧瓶,每次间隔20min,全部加入后机械搅拌12h,滤出异丙醇,加适量超纯水溶解,用稀醋酸调节pH为中性,依次用75%甲醇,无水乙醇洗涤2次,将样品冷冻干燥得到所需的羧甲基壳聚糖。
(3)制备羧甲基壳聚糖修饰的纳米四氧化三铁,采用微波法,在烧杯中加入5.14gFeCl3.6H2O和1.99g FeCl2.4H2O,加去离子水配成50mL溶液,取1g实施例1所制备的羧甲基壳聚糖溶于水配成50mL溶液并搅拌均匀,两者混合转入250mL的三口烧瓶,将盛混合液的烧瓶放在微波催化合成仪中,频率设为800W,温度设为80℃,在反应过程中逐滴加入25%的氨水,使溶液的pH稳定在8~9,反应30min。反应结束后将混合液冷却到室温,用磁铁分离固液两相,倒去上层液体,将颗粒用去离子水洗涤至中性,再用无水乙醇洗涤2~3次,最后将固体颗粒冷冻干燥2天,得到羧甲基壳聚糖包裹的氧化铁。
(4)羧甲基壳聚糖修饰的纳米四氧化三铁的结构表征
使用FT-IR、XRD、动态光散射(DLS)和TEM测定获得的羧甲基壳聚糖包覆型纳米四氧化三铁进行分析。
如图1所示,a、b分别为所制备的羧甲基壳聚糖和羧甲基壳聚糖纳米磁性材料。在羧甲基壳聚糖谱图中,1589cm-1和1406cm-1处为-COOH的不对称和对称的拉伸振动峰,2916cm-1处为C-H伸缩振动峰,1067cm-1处为C-O伸缩振动峰,3420cm-1处为O-H的伸缩振动。图b中为本发明所制的羧甲基壳聚糖包裹四氧化三铁颗粒,出现了羧甲基壳聚糖的位于2916cm-1处为C-H伸缩振动峰,1067cm-1处为C-O伸缩振动峰,且壳聚糖1589处的-COOH的不对称拉伸振动峰红移到了1626cm-1处,这可能是因为羧甲基壳聚糖通过-COOH与四氧化三铁结合,C=O不再受氢键影响而发生红移。587cm-1处的吸收峰是Fe-O的振动峰,证明产物主要是氧化铁。XRD测试结果分别见图2(a)衍射谱峰出现在2θ=30.24°、35.40°、43.48°、53.64°、57.04°、62.68°处,分别对应立方相Fe3O4的(220),(311),(400),(422),(511)和(440)晶面,这证明所制备的晶体主要为Fe3O4。如图3(a)所示,用羧甲基壳聚糖包裹的四氧化三铁纳米颗粒的粒径约为11nm,PDI=0.229。TEM照片如图4所示,羧甲基壳聚糖包覆纳米四氧化三铁呈现出的球形分布。
实施例2
将实施例1中的步骤(1)和(2)舍去,步骤(3)中不加入羧甲基壳聚糖,其余步骤与实施例1完全相同,制得被包裹的纳米四氧化三铁纳米材料。
如图1所示,在红外光谱中并没有出现羧甲基壳聚糖的特征峰,在587cm-1处的吸收峰是Fe-O的振动峰。XRD测试结果分别见图2(b),衍射谱峰出现在2θ=30.24°、35.40°、43.48°、53.64°、57.04°、62.68°处,分别对应立方相Fe3O4的(220),(311),(400),(422),(511)和(440)晶面,这证明所制备的晶体主要为Fe3O4。该纳米颗粒的粒径及粒径分布如图3(b)所示,粒径约为9nm,PDI=0.242。
Claims (8)
1.一种磁性羧甲基壳聚糖纳米材料的制备方法,其特征在于,包括如下步骤:
(1)将三价铁盐与二价铁盐混合,其中Fe3+与Fe2+的摩尔比为1.5~2:1,加水配成溶液;
(2)将羧甲基壳聚糖溶于水配成溶液,与步骤(1)的溶液混合并搅拌均匀,将混合液在微波条件下反应,微波的功率为700~900W,温度设为70~85℃,在反应过程中逐滴加入氨水,使溶液的pH稳定在8~9,反应25~35min;
(3)反应结束后冷却到室温,用磁铁分离固液两相,倒去上层液体,将颗粒用去离子水洗涤至中性,再用无水乙醇洗涤,最后将固体颗粒冷冻干燥,得到磁性羧甲基壳聚糖纳米材料。
2.根据权利要求1所述的制备方法,其特征在于,步骤(1)所述混合液中Fe3+的浓度为0.1~0.4mol/L,羧甲基壳聚糖的浓度为5~15g/L。
3.根据权利要求2所述的制备方法,其特征在于,所述微波的条件为功率为800W,温度为80℃。
4.根据权利要求1或2或3所述的制备方法,其特征在于,所述羧甲基壳聚糖的制备方法:
将纯化的壳聚糖粉末加入氢氧化钠溶液,搅拌3h,冷冻过夜,加水溶胀后缓慢加入异丙醇搅拌均匀,取氯乙酸分数次加入,加入后搅拌12h,滤出异丙醇,加水溶解,用稀醋酸调节pH为中性,依次用75%甲醇,无水乙醇洗涤,冷冻干燥得到羧甲基壳聚糖。
5.根据权利要求4所述的制备方法,其特征在于,所述氯乙酸与壳聚糖粉末的质量比为1:(1~3)。
6.根据权利要求5所述的制备方法,其特征在于,所述纯化的壳聚糖粉末的制备方法为:将壳聚糖粉末加入醋酸水溶液中,在磁力搅拌下浸泡5h,然后将沉淀物固液分离,用去离子水洗涤2~3次,放入烘箱在温度为60~80℃下烘干,粉碎后即可。
7.根据权利要求1或2或3所述的制备方法,其特征在于,所述三价铁盐是三氯化铁或硫酸铁的一种,所述二价铁盐是氯化亚铁和/或硫酸亚铁中的一种。
8.权利要求1~7任一项所述方法制备的磁性羧甲基壳聚糖纳米材料。
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