CN110028072B - 一种锰掺杂介孔二氧化硅纳米粒的制备方法 - Google Patents
一种锰掺杂介孔二氧化硅纳米粒的制备方法 Download PDFInfo
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Abstract
本发明公开一种锰掺杂介孔二氧化硅纳米粒的制备方法,所述的锰掺杂介孔二氧化硅纳米粒是以表面活性剂十六烷基三甲基溴化铵(CTAB)为模板剂,以四乙氧基硅烷(TEOS)作为硅烷,在TEOS水解的过程中掺入氯化锰(MnCl2·4H2O),使得在纳米粒内部形成‑O‑Mn‑O‑化学键。然后高温煅烧除去模板剂即得到锰掺杂介孔二氧化硅纳米粒。所制备的纳米粒具有规整的介孔结构,粒径均一,分散性较好,并且具有谷胱甘肽(GSH,5和10μM)触发降解的特征,弥补了普通二氧化硅纳米粒生理环境中降解缓慢的缺陷,有望成为一种新的生物可降解的药物递送载体。
Description
技术领域
本发明属于纳米材料的制备技术领域,具体涉及一种锰掺杂介孔二氧化硅纳米粒的制备方法。
背景技术
无机载体生物相容性好,化学/热稳定性好,药物包载能力强,易于尺寸调控以及结构修饰,在纳米医学领域引起广泛的关注。介孔二氧化硅纳米粒作为无机纳米载体的典型代表,其在药物输送、分子成像、生物传感以及癌症诊疗等方面的潜在应用得到了广泛研究。但是普通的介孔二氧化硅纳米粒中固有的-Si-O-Si-键化学性质稳定不易断裂,从而使得其很难在生理环境中降解,低的降解率有可能导致纳米载体在体内聚积,容易对机体造成急/慢性伤害。因此成为制约无机载体应用的瓶颈之一。因此,如何改善无机载体的生物可降性成为亟待解决的重要研究内容。
锰元素(Mn)是体内必须的金属元素,通过水热反应将Mn掺杂到-Si-O-Si-骨架中,制备锰掺杂介孔二氧化硅纳米粒,该纳米粒将保持较大的比表面积与孔容积,将有效负载药物,并且新形成的-O-Mn-O-键能够在肿瘤细胞内还原性环境([GSH]=2-10μM)断裂,导致锰离子从纳米骨架中溶出,导致整个结构坍塌破裂。
因此,设计一种生物可降解的锰参杂介孔二氧化硅纳米粒是十分有意义的,能够弥补二氧化硅纳米粒在生物医药领域应用时难以降解的缺陷。
发明内容
本发明的目的在于解决现有的介孔二氧化硅纳米粒在生理环境难以降解的特性,提供一种锰掺杂介孔二氧化硅纳米粒的制备方法,通过以下步骤实现:
(1)精密称取十六烷基三甲基溴化铵(CTAB)22.50mg,用22.5mL乙醇溶解以后,与150mL去离子水混合后磁力搅拌20min;然后用质量分数为25%的浓氨水将上述体系的pH调整至11.5;置入250mL圆底烧瓶以后水浴加热至75℃,磁力搅拌的状态下;磁力搅拌的状态下用2.5ml针筒滴加1.25mL正硅酸乙酯(TEOS);滴加完TEOS以后,立即加入0.1-1TEOS摩尔量的MnCl2·4H2O或MnCl2,并于75℃搅拌反应2h,反应结束后置室温熟化24h;其中正硅酸乙酯为逐滴加入,等待正硅酸乙酯加毕以后再加入锰源。其中MnCl2与正硅酸乙酯的摩尔比为1:1-1:10。
(2)将上述体系超速离心(12000r/min,30min),将离心后的纳米粒用100ml乙醇分散,室温水浴搅拌洗涤30分钟,然后再超速离心(12000r/min,30min),洗涤过程重复三次,得到白色固体物质,然后放入烘箱干燥。
(3)将干燥好的样品置于马弗炉中,550℃持续煅烧6h以除去模板剂,即得到锰掺杂介孔二氧化硅纳米粒。其中出去模板剂的方法为高温煅烧。本发明制备的锰掺杂介孔二氧化硅纳米粒的粒径约为100nm,介孔孔径3.4nm,Zeta电位约为-20mV。
本发明制备的锰掺杂介孔二氧化硅纳米粒是以表面活性剂十六烷基三甲基溴化铵(CTAB)为模板剂,以四乙氧基硅烷(TEOS)作为硅烷,在TEOS水解的过程中掺入氯化锰(MnCl2·4H2O),使得在纳米粒内部形成-O-Mn-O-化学键。然后高温煅烧除去模板剂即得到锰掺杂介孔二氧化硅纳米粒。所制备的纳米粒具有规整的介孔结构,粒径均一,分散性较好,并且具有谷胱甘肽(GSH,5和10μM)触发降解的特征,弥补了普通二氧化硅纳米粒生理环境中降解缓慢的缺陷,可成为一种新的生物可降解的药物递送载体。
现有的锰元素掺杂的介孔二氧化硅纳米粒制备一般通过两个步骤:包括普通介孔二氧化硅纳米粒的制备以及将锰元素掺入普通介孔二氧化硅纳米粒的框架中。即先通过溶胶凝胶法制备普通介孔二氧化硅纳米粒,然后通过水合硫酸锰与普通介孔二氧化硅纳米粒高温(大于100℃)水热处理,将锰元素掺入二氧化硅纳米粒框架中。本专利是通过一锅法,即在TEOS水解的过程中掺入氯化锰(MnCl2·4H2O),使得在纳米粒内部形成-O-Mn-O-化学键,这样的制备方法使得锰元素在纳米粒中掺杂更加均匀,同时也提高了纳米粒在相同GSH环境中的降解效率。更重要的是:本专利所叙述的制备方法更加简单与省时。
附图说明
图1为本发明中实施方案1中锰掺杂介孔二氧化硅纳米粒的粒径与电位图。
图2为本发明中实施方案1中锰掺杂介孔二氧化硅纳米粒的透射电子显微镜图。
图3为本发明中实施方案1中锰掺杂介孔二氧化硅纳米粒的扫描电子显微镜图。
图4为本发明中实施方案1中锰掺杂介孔二氧化硅纳米粒的能谱扫描图。
图5为本发明中实施方案1中锰掺杂介孔二氧化硅纳米粒的元素分析图。
图6为本发明中实施方案1中锰掺杂介孔二氧化硅纳米粒氮气脱吸附与孔径分布曲线。
图7为本发明中实施方案1中锰掺杂介孔二氧化硅纳米粒的体外降解图谱。
图8为本发明中实施方案1中锰掺杂介孔二氧化硅纳米粒的体外降解透射电子显微镜图([GSH]=10mM)。
具体实施方式
本发明结合附图和实施例进一步说明本发明的内容,但是不应理解为对本发明的限制。在不背离本发明实质的情况下,对本发明方法、步骤或条件所作的修改和替换,都属于本发明的范畴。
实施例1
(1)精密称取十六烷基三甲基溴化铵(CTAB)22.50mg,用22.5mL乙醇溶解以后,与150mL去离子水混合后磁力搅拌20min;然后用质量分数为25%的浓氨水将上述体系的pH调整至11.5;置入250mL圆底烧瓶以后水浴加热至75℃,磁力搅拌的状态下;磁力搅拌的状态下用2.5ml针筒滴加1.25mL正硅酸乙酯(TEOS);滴加完TEOS以后,立即加入1/5TEOS摩尔量的MnCl2·4H2O,并于75℃搅拌反应2h。反应结束后置室温熟化24h;
(2)将上述体系超速离心(12000r/min,30min),将离心后的纳米粒用100ml乙醇分散,室温水浴搅拌洗涤30分钟,然后再超速离心(12000r/min,30min),洗涤过程重复三次,得到白色固体物质,然后放入烘箱干燥。
(3)将干燥好的样品置于马弗炉中,550℃持续煅烧6h以除去模板剂,即得到锰掺杂介孔二氧化硅纳米粒。
对上述制备的锰掺杂介孔二氧化硅纳米粒进行表征,如图1所示:纳米粒的水合粒径为100nm,电位为-20mV左右;透射电镜和扫描电镜(图2-3)所示,纳米粒圆整,粒径均一,分散性较好;由能谱扫描和元素分析图(图4-5)可见,纳米粒含有三种元素,氧、硅、锰的含量分别为:55.13%,42.41%和2.46%。由氮气吸脱附曲线(图6)可以看出Mn-Si NPs具有IV型吸附曲线,说明介孔结构均一,介孔的平均孔径为3.4nm。由体外降解实验(图7)可知:在没有GSH存在的情况下,锰掺杂介孔二氧化硅纳米粒中锰离子溶出率很低;而在GSH浓度为5mM或者10mM的环境中,锰离子能够迅速溶出,24h时分别溶出约60%与88%。以上结果说明Mn-Si NPs能够在肿瘤GSH环境中迅速降解。在透射电镜图中可以看出(图8)在GSH=10mM环境中,4h后锰掺杂介孔二氧化硅纳米粒边缘出现显著的降解现象,变得模糊;24h后,纳米粒出现显著的崩塌;48h时纳米粒基本降解为更小的颗粒,72h后,纳米粒基本全部降解。
实施例2
(1)精密称取十六烷基三甲基溴化铵(CTAB)22.50mg,用22.5mL乙醇溶解以后,与150mL去离子水混合后磁力搅拌20min;然后用质量分数为25%的浓氨水将上述体系的pH调整至11.5;置入250mL圆底烧瓶以后水浴加热至75℃,磁力搅拌的状态下;磁力搅拌的状态下用2.5ml针筒滴加1.25mL正硅酸乙酯(TEOS);滴加完TEOS以后,立即加入1/10TEOS摩尔量的MnCl2·4H2O,并于75℃搅拌反应2h。反应结束后置室温熟化24h;
(2)将上述体系超速离心(12000r/min,30min),将离心后的纳米粒用100ml乙醇分散,室温水浴搅拌洗涤30分钟,然后再超速离心(12000r/min,30min),洗涤过程重复三次,得到白色固体物质,然后放入烘箱干燥。
(3)将干燥好的样品置于马弗炉中,550℃持续煅烧6h以除去模板剂,即得到锰掺杂介孔二氧化硅纳米粒。
实施例3
(1)精密称取十六烷基三甲基溴化铵(CTAB)22.50mg,用22.5mL乙醇溶解以后,与150mL去离子水混合后磁力搅拌20min;然后用质量分数为25%的浓氨水将上述体系的pH调整至11.5;置入250mL圆底烧瓶以后水浴加热至75℃,磁力搅拌的状态下;磁力搅拌的状态下用2.5ml针筒滴加1.25mL正硅酸乙酯(TEOS);滴加完TEOS以后,立即加入与TEOS相同摩尔量的MnCl2·4H2O,并于75℃搅拌反应2h。反应结束后置室温熟化24h;
(2)将上述体系超速离心(12000r/min,30min),将离心后的纳米粒用100ml乙醇分散,室温水浴搅拌洗涤30分钟,然后再超速离心(12000r/min,30min),洗涤过程重复三次,得到白色固体物质,然后放入烘箱干燥。
(3)将干燥好的样品置马弗炉550℃持续煅烧6h去以除去模板剂,即得到锰掺杂介孔二氧化硅纳米粒。
实施例4
(1)精密称取十六烷基三甲基溴化铵(CTAB)22.50mg,用22.5mL乙醇溶解以后,与150mL去离子水混合后磁力搅拌20min;然后用质量分数为25%的浓氨水将上述体系的pH调整至11.5;置入250mL圆底烧瓶以后水浴加热至75℃,磁力搅拌的状态下;磁力搅拌的状态下用2.5ml针筒滴加1.25mL正硅酸乙酯(TEOS);滴加完TEOS以后,立即加入1/10TEOS摩尔量的MnCl2,并于75℃搅拌反应2h。反应结束后置室温熟化24h;
(2)将上述体系超速离心(12000r/min,30min),将离心后的纳米粒用100ml乙醇分散,室温水浴搅拌洗涤30分钟,然后再超速离心(12000r/min,30min),洗涤过程重复三次,得到白色固体物质,然后放入烘箱干燥。
(3)将干燥好的样品置于马弗炉中,550℃持续煅烧6h以除去模板剂,即得到锰掺杂介孔二氧化硅纳米粒。
Claims (3)
1.一种锰掺杂介孔二氧化硅纳米粒的制备方法,其特征在于,通过以下步骤实现:
(1)称取十六烷基三甲基溴化铵22.50 mg,用22.5 mL乙醇溶解以后,与150 mL去离子水混合后磁力搅拌20 min;然后用质量分数为25%的浓氨水将上述体系的pH调整至11.5;置入250 mL圆底烧瓶以后水浴加热至75℃,磁力搅拌的状态下用2.5 mL 针筒滴加1.25mL 正硅酸乙酯;滴加完正硅酸乙酯以后,立即加入0.1-1倍正硅酸乙酯摩尔量的锰源,并于75℃搅拌反应2 h;锰源选用MnCl2·4H2O或MnCl2;MnCl2与正硅酸乙酯的摩尔比为1:1-1:10,反应结束后置室温熟化24 h,正硅酸乙酯为逐滴加入,等待正硅酸乙酯加毕以后再加入锰源;
(2)将上述体系超速离心,将离心后的纳米粒用100 mL 乙醇分散,室温水浴搅拌洗涤30分钟,然后再超速离心,洗涤过程重复三次,得到白色固体物质,然后放入烘箱干燥;超速离心条件为12000 r/min,30 min;
(3)将干燥好的样品置于马弗炉中,550℃持续煅烧6 h以除去模板剂,即得到锰掺杂介孔二氧化硅纳米粒。
2.根据权利要求1所述的制备方法,其特征在于:所述步骤(3)中除去 模板剂的方法为高温煅烧。
3.根据权利要求1所述的制备方法,其特征在于,制备的锰掺杂介孔二氧化硅纳米粒的粒径约为100 nm,介孔孔径3.4 nm,Zeta电位约为-20 mV。
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