CN1970084B - 一种类水滑石-囊泡复合体及其制备方法 - Google Patents
一种类水滑石-囊泡复合体及其制备方法 Download PDFInfo
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Abstract
一种类水滑石-囊泡复合体及其制备方法，属于新材料技术领域。类水滑石包裹在囊泡内或类水滑石与囊泡共存。类水滑石具有水滑石的晶体结构，化学式为：[M(II)(1-x)M(III)x(OH)2]x-[An- x/n]x-.mH2O。囊泡可由阳离子表面活性剂、阴离子表面活性剂、两性表面活性剂和非离子表面活性剂形成。类水滑石-囊泡复合体为均一稳定的体系，类水滑石的含量范围为0.5～8g/L，表面活性剂的浓度为10～60mmol/L，粒径为40～400nm，常温下可稳定放置1年以上。本发明的类水滑石-囊泡复合体集类水滑石和囊泡两种物质于一体，可用于药物输送与控释、化妆品和油田开发。
Description
技术领域
本发明涉及一种类水滑石-囊泡复合体及其制备方法，属于新材料技术领域。
背景技术
类水滑石(Hydrotalcite-like compounds，简写为HTlc)又称为层状双金属氢氧化物(Layered double hydroxides，简写为LDHs)，其结构通式为[M(II)(1-x)M(III)x(OH)2]x+[An- x/n]x-.mH2O，式中M(II)和M(III)分别指二价和三价金属阳离子，An-为层间阴离子，x为每摩尔HTlc中M(III)的摩尔分数，m为每摩尔HTlc中层间结晶水的摩尔数。类水滑石具有水镁石片层结构，层板由于三价金属离子同晶置换二价金属离子而带结构正电荷，层间存在可交换的客体阴离子与层板正电荷相平衡。类水滑石的用途十分广泛，如阴离子交换剂、传感器、陶瓷前驱体、吸附剂、催化剂及催化剂载体、污水处理剂、农药载体、基因和药物分子的无机载体等，因而近几年来引起人们的关注。
囊泡(vesicle)是两亲分子有序组合体的一种形式，它是由密闭双分子层所形成的球形或者椭球形的单室或者多室类缔合结构。这种有序组合体具有独特的结构和性质，潜在应用价值很高，如它有一个水溶性的内核，非常类似于细胞膜，因而可用于细胞膜的生物模拟、药物的封装及输送等。囊泡的制备方法主要有两类：一是机械力诱导形成法，如超声波振荡法、干膜超声波法、乙醇注射法、氯仿注射法、挤压法以及逆相蒸发法等，这些方法操作起来麻烦，而且靠机械作用形成的囊泡都是亚稳定的，对其应用有所限制；二是自发形成法，即在适当条件下由两亲分子自组装形成囊泡，如通过pH值、温度、盐度的调控以及有机添加剂或重金属离子的加入等来诱导囊泡的自发形成。自发形成的囊泡制备简单，稳定性好，其尺寸、电荷密度和渗透性等容易通过改变两种表面活性剂的链长或相对量来调控。
本发明采用类水滑石诱导囊泡形成，制备出稳定的类水滑石-囊泡复合体，可用于药物载体、化妆品、油田开发等领域。
发明内容
本发明提供了一种类水滑石-囊泡复合体及其制备方法。
本发明同时还提供了一种囊泡制备新方法，即由类水滑石诱导自发形成囊泡。
本发明所述的类水滑石-囊泡复合体，是类水滑石包裹在囊泡内形成的复合体，和/或类水滑石和囊泡共存形成的复合体，是在类水滑石诱导下表面活性剂自发形成囊泡的同时而制成。
本发明的类水滑石-囊泡复合体中，类水滑石的含量范围为0.5～8g/L，表面活性剂的浓度为10～60mmol/L。
本发明的类水滑石-囊泡复合体为均一稳定的体系，在常温下能稳定放置1年以上。
所述的类水滑石，具有水滑石的晶体结构，化学组成通式为：
[M(II)(1-x)M(III)x(OH)2]x+[An- x/n]x-.mH2O
其中，M(II)可为Mg2+、Mn2+、Fe2+、Co2+、Ni2+、Cu2+、Zn2+或Ca2+等；M(III)可为Al3+、Cr3+、Mn3+、Fe3+、Co3+、Ni3+或La3+等；An-可为CO3 2-、SO4 2-、CI-、NO3 -、无机阴离子或有机阴离子等。
所述的囊泡由表面活性剂形成，可选自下列之一或组合：
阳离子表面活性剂，优选溴化十六碳烷基三甲铵(CTAB)，C12-C18链长的烷基三甲基溴化铵，双十二烷基二甲基溴化铵(DDAB)，十六烷基氯化吡啶，十二烷基三甲基羟基铵(DTOH)或双十二烷基羟基铵(DDAOH)；
阴离子表面活性剂，优选十二烷基苯磺酸钠(SDBS)，双(2-乙基己基)琥珀酸磺酸钠(AOT)，十二烷基硫酸钠(SDS)，十六烷基三甲基苯磺酸钠(CTAT)，C8-C18链长的烷基硫酸盐或烷基磺酸盐；
两性表面活性剂，优选十二烷基丙基磺基甜菜碱(DSB)或十二烷基羧基甜菜碱(C12BE)等；
非离子表面活性剂，如聚氧乙烯类化合物(RO(C2H4O)nH)，多元醇类化合物或氧化胺。
本发明的类水滑石-囊泡复合体，其粒径介于40～400nm，优选的粒径介于80～150nm之间。
本发明所述的类水滑石-囊泡复合体的制备方法如下：
室温下在合适的容器中将类水滑石与表面活性剂溶液混合，振荡均匀即可。该制备方法简单、成本低。
本发明的技术特点如下：
1、发明了一类新型类水滑石-囊泡复合体，类水滑石包覆于囊泡的水核中，或类水滑石与囊泡共存。
2、本发明的类水滑石-囊泡复合体是在类水滑石诱导下自发形成囊泡的同时而制成，方法简单，反应温和。
3、本发明的类水滑石-囊泡复合体为均一稳定体系，类水滑石的含量范围为0.5～8g/L，表面活性剂的浓度为10～60mmol/L，粒径约为80～150nm，在常温下可稳定放置1年以上。
4、本发明的类水滑石-囊泡复合体集类水滑石和囊泡两种物质于一体，可拓宽和改进其用途，在药物输送与控释、化妆品和油田开发等领域有重要的应用前景。
附图说明
图1是实施例1类水滑石-囊泡复合体的透射电子显微镜(TEM)照片，a-d分别对应实施例1中类水滑石vol％分别为10％、40％、60％、100％的样品。
图2是实施例1类水滑石-囊泡复合体的高分辨透射电子显微镜(HR-TEM)照片，a，b和c，d分别对应实施例1中类水滑石vol％分别为10％和100％的样品。
图3是动态激光光散射测得的粒径分布图，a-d分别对应实施例1中类水滑石vol％分别为10％、40％、60％、100％的样品。
具体实施方式
下面结合实施例对本发明做进一步说明，但不限于此。
实施例1：
类水滑石采用10g/L的镁铝类水滑石溶胶；表面活性剂采用阴离子表面活性剂双(2-乙基己基)琥珀酸磺酸钠(AOT)与两性表面活性剂十二烷基羧基甜菜碱(C12BE)的复配溶液，AOT/C12BE摩尔比为2∶3，表面活性剂的总浓度为20mmol/L。将类水滑石溶胶和AOT/C12BE复配溶液在体积比为10％～60％的范围内混合，摇匀，可得到一系列类水滑石-囊泡复合体样品。
复合体样品的TEM照片见图1，可见在类水滑石诱导下形成了囊泡，且其双层膜清晰可见；其粒径介于80～150nm之间，少量囊泡的粒径可达到300～400nm。
图2是样品的HR-TEM照片，可见许多类水滑石片包覆于囊泡水核之中；将包覆的类水滑石片高倍放大可清晰地看到晶格条纹，且其晶格间距为0.926nm，与包覆前的纯类水滑石的晶格间距0.927nm一致。
由DLS分析结果(见图3)表明，复合体的流体动力学半径约为45-75nm，且随着类水滑石体积比的增加而增大。
实施例2：
类水滑石采用10g/L的锌铝类水滑石溶胶；表面活性剂采用阴离子表面活性剂十二烷基苯磺酸钠(SDBS)与阳离子表面活性剂磷酸三酯(PTA)的复配溶液，PTA/SDBS摩尔比为9∶1，表面活性剂的总浓度为30mmol/L。将类水滑石溶胶和PTA/SDBS复配溶液在体积比为10％～80％的范围内混合，摇匀，可得到一系列类水滑石-囊泡复合体样品。粒径介于90～200nm之间。
实施例3：
类水滑石采用10g/L的镁铁类水滑石溶胶；表面活性剂采用阴离子表面活性剂十二烷基苯磺酸钠(SDBS)与两性表面活性剂十二烷基丙基磺基甜菜碱(DSB)的复配溶液，DSB/SDBS摩尔比为2∶3，表面活性剂的总浓度为25mmol/L。将类水滑石溶胶和DSB/SDBS复配溶液在体积比为10％～70％的范围内混合，摇匀，可得到一系列类水滑石-囊泡复合体样品。粒径介于100～250nm之间。
Claims (2)
1.一种类水滑石-囊泡复合体，其特征在于，类水滑石包裹在囊泡内，是在类水滑石诱导下表面活性剂自发形成囊泡的同时而制成，类水滑石的含量范围为0.5～8 g/L，表面活性剂的浓度为10～60mmol/L；
所述的类水滑石具有水滑石的晶体结构，化学组成通式为：[M(II)(1-x)M(III)x(OH)2]x+[An- x/n]x-.mH2O，其中，M(II)为Mg2+、Mn2+、Fe2+、Co2+、Ni2+、Cu2+、Zn2+或Ca2+；M(III)为Al3+、Cr3+、Mn3+、Fe3+、Co3+、Ni3+或La3+；An-为CO3 2-、SO4 2-、Cl-、NO3 -或有机阴离子；
所述的表面活性剂可选自下列之一或组合：
(1)阳离子表面活性剂，选自溴化十六碳烷基三甲铵，C12-C18链长的烷基三甲基溴化铵，双十二烷基二甲基溴化铵，十六烷基氯化吡啶，十二烷基三甲基羟基铵或双十二烷基羟基铵；
(2)阴离子表面活性剂，选自十二烷基苯磺酸钠，双(2-乙基己基)琥珀酸磺酸钠，十二烷基硫酸钠或十六烷基三甲基苯磺酸钠；
(3)两性表面活性剂，选自十二烷基丙基磺基甜菜碱或十二烷基羧基甜菜碱。
2.如权利要求1所述的类水滑石-囊泡复合体，其特征在于，粒径为80～150nm。
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