CN109134914A - 一种双敏感性纤维素基气凝胶的制备方法 - Google Patents

一种双敏感性纤维素基气凝胶的制备方法 Download PDF

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CN109134914A
CN109134914A CN201810764978.3A CN201810764978A CN109134914A CN 109134914 A CN109134914 A CN 109134914A CN 201810764978 A CN201810764978 A CN 201810764978A CN 109134914 A CN109134914 A CN 109134914A
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dac
cellulose
pdmaema
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曾宪海
闫贵花
孙勇
唐兴
林鹿
雷廷宙
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Xiamen University
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Abstract

本发明公开了一种双敏感性纤维素基气凝胶的制备方法，先后制备二醛纤维素、二醛纤维素/甲基丙烯酸二甲胺乙酯共聚物、二醛纤维素/甲基丙烯酸二甲胺乙酯/聚乙烯亚胺共聚物，然后进行冷冻干燥，即得产物；所述产物为双敏感性纤维素基气凝胶，其累积吸附量达250mg/g，其在0.2％NaCl(pH<3)，0.05mol/L NaH2PO4(pH＝3‑8)或NaOH(pH>8)的溶液中的累积释放量达63～90％，所得产物具有质量轻、生物相容性好、孔隙度高和pH/温度双敏感性等优点，可作为生物医用材料，如药物缓释、创口敷料等方面有广阔的应用前景。

Description

一种双敏感性纤维素基气凝胶的制备方法
技术领域
本发明属于天然高分子材料领域，具体涉及一种双敏感性纤维素基气凝胶的制备方法。
背景技术
传统的药物制剂通常存在很多副作用，包括胃肠道或肾脏的副作用。而且，大多数药物半衰期较短，必须每日多次剂量服用，才能维持治疗性血液水平。因此，针对药物释放、药物作用强度和药效持续时间等已成为相关学科研究的主题。
目前，已经开发了一些聚合物来实现药物缓释从而增加药效持续时间。然而，大多数药物制剂，如Pe、PP和PDMS是化学合成的且非生物降解的。目前，天然多糖或其衍生物因具有可生物降解性、可再生性和低毒性成为载药制剂研究的首选。特别是纤维素在众多天然多糖中显示出的独特性质，如较大的比表面积，高强度和刚度，易化学修饰等优势引起各研究领域的广泛关注。
常用的药物传递系统包括离子交换树脂，薄膜，微球，凝胶等。气凝胶作为一种特殊的高孔材料，引起生物医学和医药应用领域的广泛兴趣。然而，对于原始纤维素，药物负载能力很低。因此，纤维素的化学改性成为提高其实用性的重要一步。聚乙烯亚胺(PEI)含有大量的伯胺和仲胺基在分子上，表现出优异的给药性能。聚甲基丙烯酸二甲胺乙酯(PDMAEMA)含有对H+和OH-敏感的基团，对外界pH和温度的变化有较敏锐的感知。可以作为智能材料递送载体使药物靶向性直达病灶部位，进而提高药物疗效，是目前给药系统发展的一种趋势。
发明内容
本发明的目的在于克服现有技术的不足之处，提供了一种双敏感性纤维素基气凝胶的制备方法，解决了上述背景技术中的问题。
本发明解决其技术问题所采用的技术方案是：提供了一种双敏感性纤维素基气凝胶的制备方法，包括如下步骤：
(1)制备DAC：将纤维素和IO4 -供体以1:0.2～2.0％的摩尔比充分混合，25～75℃避光搅拌0.5～48h，经去离子水洗涤、透析得DAC，分子量为5000-20000；
(2)制备DAC/PDMAEMA共聚物：将步骤(1)产物和PDMAEMA加入到去离子水中，N2氛围下搅拌均匀，得到混合液；调节混合液的pH≤3，并向混合液中加入CAN，在N2保护下搅拌至少5h，经透析，得到DAC/PDMAEMA共聚物，分子量为5000-20000；其中，DAC、PDMAEMA和CAN的质量比为DAC:PDMAEMA:CAN＝1.0g:5.0～50.0mg:0.5～5.0mg；
(3)制备DAC/PDMAEMA/PEI共聚物：将DAC/PDMAEMA共聚物与分子量小于10000的PEI以1:0.5～5.0的质量比充分混合，室温下搅拌进行接枝共聚，然后进行透析，即得DAC/PDMAEMA/PEI共聚物，分子量为5000-20000；
(4)制备气凝胶：取DAC/PDMAEMA/PEI共聚物的悬浮液快速冷冻，然后进行冷冻干燥，即得产物；所述产物为pH/温度双敏感性纤维素基气凝胶，其累积吸附量达250mg/g，其在0.05mol/L NaH2PO4(pH＝3-8)或0.2％NaCl(pH&lt;3)或NaOH(pH&gt;8)溶液中的累积释放量达63～90％。
在本发明一较佳实施例中，所述步骤(1)还包括制备DAC水分散体：将DAC加入去离子水中，于200～1000rpm的搅拌速度下70～150℃反应0.5h～4h，离心、浓缩后得到透明DAC水分散体。
在本发明一较佳实施例中，所述纤维素包括天然生物质纤维素和纤维素化学品，所述天然生物质纤维素包括从竹子、木材、棉花提取的纤维素；所述的纤维素化学品包括微晶纤维素、纳米纤维素。
在本发明一较佳实施例中，所述的IO4 -供体包括高碘酸、高碘酸钠、高碘酸钾。
在本发明一较佳实施例中，所述步骤(3)中加入还原剂，所述还原剂包括氢化铝锂、硼氢化钾、硼氢化钠、氰基硼氢化钠中的至少一种。
在本发明一较佳实施例中，所述步骤(4)中将产物在NaSA溶液中搅拌22～26h，测吸附量；然后在0.05mol/L、pH＝7.4的NaH2PO4溶液或质量分数为0.2％、pH＝2的NaCl溶液中测最高释放量。
本技术方案与背景技术相比，它具有如下优点：
1.本发明制备方法操作简单，原料价格低廉、来源广泛、环保，成本低，具有良好的生物相容性，符合可持续发展的要求。
2.本发明所制备的纤维素气凝胶密度小，质量轻，毒副作用小，具有较好的pH、温度敏感性，能够将药物特异性递送到胃内或肠内，从而提高药物效率和靶向性，适合用于药物缓释，医用敷料等方面，在生物医用材料方面具有广阔的应用前景。
具体实施方式
实施例1
本实施例的一种双敏感性纤维素基气凝胶的制备方法，采用生物质纤维素为原料进行制备，包括如下步骤：
(0)前处理-制备纤维素悬浮液：将200g的纸浆(竹浆)在水中浸泡1～2h，采用转速小于100rpm的机械搅拌2～5h；然后使用超微研磨机在转速1000～2000rpm，磨盘间隙从2mm逐渐降到0μm甚至更低，通过循环加料的方式对纸浆进行开纤化处理；最后采用高压均质法将分散液均质10～30次，再经一定程度的旋蒸浓缩得到稳定性良好的纤维素悬浮液(纸浆浓度为0.55wt％、竹浆浓度为0.48wt％)；
(1)制备DAC(二醛纤维素)：取100mL 0.55wt％木浆纤维素和1.5g NaIO4于250ml锥形瓶中，室温下避光搅拌6h，然后经离心、去离子水洗涤、透析得到0.42g/g的DAC水分散体；
(2)～(3)制备共聚物：取1g所得的DAC水分散体和50mg可聚合单体PDMAEMA(聚甲基丙烯酸二甲胺乙酯，分子式：C8H15NO2，分子量157.21)加入到盛有去离子水的三口烧瓶中在N2氛围下搅拌均匀，用70％的HNO3调节溶液的pH＝3，向混合液中加入5mg CAN(硝酸铈铵)继续搅拌6h，透析，即得DAC/PDMAEMA共聚物。取1g上述所得的共聚物与2.5g PEI(Mw＝600)充分混合，室温下搅拌12h，然后进行透析，并调节悬浮液浓度至约0.1％，得DAC/PDMAEMA/PEI共聚物；
其中，PDMAEMA是一种具有温度和pH敏感性的高分子，其分子结构单元中同时存在亲水性的叔胺基、羰基和疏水性的烷基基团，两类基团在空间结构上互相匹配。
(4)制备气凝胶：取10mlDAC/PDMAEMA/PEI共聚物的均匀分散液在-196℃的液氮中快速成型，然后将其放入冷冻干燥室12h，即得产物；
称取0.1g上述产物，在0.2M NaSA溶液中搅拌24h，吸附量达到95mg/g；在0.2％NaCl(pH＝2)溶液中最高释放量达到近60％。
实施例2
实施例2与实施例1的区别在于：
(1)取2g实施例1步骤(1)的DAC水分散体于盛有100ml去离子水的圆底烧瓶中，100℃下搅拌2h，离心得浓度为3.2mg/mL的DAC水溶液。
(2)～(3)：取50ml所得的DAC水溶液和20mg可聚合单体PDMAEMA加入到盛有去离子水的三口烧瓶中在N2氛围下搅拌均匀，用70％的HNO3调节溶液的pH&lt;3，向混合液中加入5mgCAN继续搅拌6h，透析，即得DAC/PDMAEMA共聚物；取0.1g上述所得的共聚物与0.5g PEI(Mw＝600)充分混合，室温下搅拌12h，然后进行透析，并调节悬浮液浓度至约0.1％，得DAC/PDMAEMA/PEI共聚物。
(4)取10mlDAC/PDMAEMA/PEI共聚物均匀分散液在-196℃的液氮中快速成型，然后将其放入冷冻干燥室12h，即得产物。
称取0.1g产物，在0.1M NaSA溶液中搅拌24h，吸附量达到80mg/g；在0.05mol/LNaH2PO4(pH＝7.4)溶液中最高释放量达到近90％。
实施例3
(1)取100mL 0.48wt％竹浆纤维素和1.75g NaIO4于250ml锥形瓶中，室温下避光搅拌48h，然后经离心、去离子水洗涤、透析得到0.35g/g的DAC水分散体；
(2)～(3)：取1g所得的DAC水分散体和50mg可聚合单体PDMAEMA加入到盛有去离子水的三口烧瓶中在N2氛围下搅拌均匀，用70％的HNO3调节溶液的pH＝1，向混合液中加入3mgCAN继续搅拌12h，透析，即得DAC/PDMAEMA共聚物。取1g上述所得的共聚物与5.0g PEI(Mw＝1800)充分混合，室温下搅拌12h，然后进行透析，并调节悬浮液浓度至约0.1％，得DAC/PDMAEMA/PEI共聚物。
(4)取10ml DAC/PDMAEMA/PEI共聚物均匀分散液在-196℃的液氮中快速成型，然后将其放入冷冻干燥室12h，即得产物。
(3)称取0.1g产物，在0.5M NaSA溶液中搅拌24h，吸附量达到90mg/g；在0.2％NaCl(pH＝2)溶液中最高释放量达到近63％。
实施例4
(1)取2g实施例3中得到的DAC水分散体于盛有100ml去离子水的圆底烧瓶中，100℃下搅拌2h，离心得浓度为2.1mg/mL的DAC水溶液。
(2)～(3)取50ml所得的DAC水溶液和20mg可聚合单体PDMAEMA加入到盛有去离子水的三口烧瓶中在N2氛围下搅拌均匀，用70％的HNO3调节溶液的pH＝2，向混合液中加入2mgCAN继续搅拌24h，透析，即得DAC/PDMAEMA共聚物。取0.1g上述所得的共聚物与0.5g PEI(Mw＝1800)充分混合，室温下搅拌12h，然后进行透析，并调节悬浮液浓度至约0.1％，得DAC/PDMAEMA/PEI共聚物。
(4)取10ml步骤(1)所得的共聚物均匀分散液在-196℃的液氮中快速成型，然后将其放入冷冻干燥室12h，即得产物。
称取0.1g产物，在2.0M NaSA溶液中搅拌24h，吸附量达到64mg/g；在0.2％NaCl(pH＝2)溶液中最高释放量达到近50％。
实施例5
本实施例采用的是微晶纤维素，为购置于市面的纤维素化学品，无需经步骤(0)的生物质纤维素为原料制备纤维素悬浮液，具体步骤如下：
(1)取1g微晶纤维素和0.5g NaIO4于250ml锥形瓶中，室温下避光搅拌6h，然后经离心、去离子水洗涤、透析得到0.51g/g的DAC水分散体；
(2)取1g所得的DAC水分散体和30mg可聚合单体PDMAEMA加入到盛有去离子水的三口烧瓶中在N2氛围下搅拌均匀，用70％的HNO3调节溶液的pH＝2，向混合液中加入5mg CAN继续搅拌12h，透析，即得DAC/PDMAEMA共聚物。
(3)取1g上述所得的共聚物与0.5g PEI(Mw＝600)充分混合，室温下搅拌12h，然后进行透析，并调节悬浮液浓度至约0.1％，得DAC/PDMAEMA/PEI共聚物。
(4)取10ml DAC/PDMAEMA/PEI共聚物均匀分散液在-196℃的液氮中快速成型，然后将其放入冷冻干燥室12h，即得产物。
称取0.1g产物，在1.0M NaSA溶液中搅拌24h，吸附量达到82mg/g；在NaOH(pH＝10.0)溶液中最高释放量达到近87％。
实施例6
实施例6同样采用购置于市面的纤维素化学品，无需经步骤(0)的生物质纤维素为原料制备纤维素悬浮液：
(1)取1g纳米纤维素和2.0g NaIO4于250ml锥形瓶中，室温下避光搅拌6h，然后经离心、去离子水洗涤、透析得到0.44g/g的DAC水分散体；
(2)取1g所得的DAC水分散体和5mg可聚合单体PDMAEMA加入到盛有去离子水的三口烧瓶中在N2氛围下搅拌均匀，用HNO3调节溶液的pH＝2，向混合液中加入5mg CAN继续搅拌6h，透析，即得DAC/PDMAEMA共聚物。
(3)取1g上述所得的共聚物与5.0g PEI(Mw＝10000)充分混合，室温下搅拌12h，然后进行透析，并调节悬浮液浓度至约0.1％，得DAC/PDMAEMA/PEI共聚物。
(4)取10ml DAC/PDMAEMA/PEI共聚物均匀分散液在-196℃的液氮中快速成型，然后将其放入冷冻干燥室12h，即得产物。
称取0.1g产物，在0.01M NaSA溶液中搅拌24h，吸附比例为56％；在0.05mol/LNaH2PO4(pH＝5.7)溶液中最高释放量达到近60％。
实施例7
(1)取1g纳米纤维素和1.0g NaIO4于250ml锥形瓶中，室温下避光搅拌60h，然后经离心、去离子水洗涤、透析得到0.37g/g的DAC水分散体；
(2)取1g所得的DAC水分散体和50mg可聚合单体PDMAEMA加入到盛有去离子水的三口烧瓶中在N2氛围下搅拌均匀，用HNO3调节溶液的pH＝2，向混合液中加入5mg CAN继续搅拌12h，透析，即得DAC/PDMAEMA共聚物。
(3)取1g上述所得的共聚物与2.5g PEI(Mw＝1800)充分混合，添加室温下搅拌12h，然后进行透析，并调节悬浮液浓度至约0.1％，得DAC/PDMAEMA/PEI共聚物。
(4)取10ml DAC/PDMAEMA/PEI共聚物均匀分散液在-196℃的液氮中快速成型，然后将其放入冷冻干燥室12h，即得产物。
称取0.1g产物，在0.02M NaSA溶液中搅拌24h，吸附比例为70％；在0.2％NaCl(pH＝2)溶液中最高释放量达到近55％。
实施例8
(1)取1g纳米纤维素和1.0g NaIO4于250ml锥形瓶中，室温下避光搅拌60h，然后经离心、去离子水洗涤、透析得到0.37g/g的DAC水分散体；
(2)取1g所得的DAC水分散体和50mg可聚合单体PDMAEMA加入到盛有去离子水的三口烧瓶中在N2氛围下搅拌均匀，用HNO3调节溶液的pH＝2，向混合液中加入5mg CAN继续搅拌12h，透析，即得DAC/PDMAEMA共聚物。
(3)取1g上述所得的共聚物与2.5g PEI(Mw＝600)充分混合，添加0.1g的硼氢化钠室温下搅拌2h，然后进行透析，并调节悬浮液浓度至约0.1％，得DAC/PDMAEMA/PEI共聚物。
(2)取10ml DAC/PDMAEMA/PEI共聚物均匀分散液在-196℃的液氮中快速成型，然后将其放入冷冻干燥室12h，即得产物。
称取0.1g产物，在0.05M NaSA溶液中搅拌24h，吸附量达到91mg/g；在0.05mol/LNaH2PO4(pH＝7.4)溶液中最高释放量达到近70％。
本领域技术人员可知，当本发明的技术参数在如下范围内变化时，可以预期得到与上述实施例相同或相近的技术效果：所述步骤(3)中加入还原剂，所述还原剂包括氢化铝锂、硼氢化钾、硼氢化钠、氰基硼氢化钠中的至少一种。
以上所述，仅为本发明较佳实施例而已，故不能依此限定本发明实施的范围，即依本发明专利范围及说明书内容所作的等效变化与修饰，皆应仍属本发明涵盖的范围内。

Claims (6)

1.一种双敏感性纤维素基气凝胶的制备方法，其特征在于，包括如下步骤：
(1)制备DAC：将纤维素和IO4 -供体以1:0.2～2.0％的摩尔比充分混合，25～75℃避光搅拌0.5～48h，经去离子水洗涤、透析得DAC，分子量为5000-20000；
(2)制备DAC/PDMAEMA共聚物：将步骤(1)产物和PDMAEMA加入到去离子水中，N2氛围下搅拌均匀，得到混合液；调节混合液的pH≤3，并向混合液中加入CAN，在N2保护下搅拌至少5h，经透析，得到DAC/PDMAEMA共聚物，分子量为5000-20000；其中，DAC、PDMAEMA和CAN的质量比为DAC:PDMAEMA:CAN＝1.0g:5.0～50.0mg:0.5～5.0mg；
(3)制备DAC/PDMAEMA/PEI共聚物：将DAC/PDMAEMA共聚物与分子量小于10000的PEI以1:0.5～5.0的质量比充分混合，室温下搅拌进行接枝共聚，然后进行透析，即得DAC/PDMAEMA/PEI共聚物，分子量为5000-20000；
(4)制备气凝胶：取DAC/PDMAEMA/PEI共聚物的悬浮液快速冷冻，然后进行冷冻干燥，即得产物；所述产物为pH/温度双敏感性纤维素基气凝胶，其累积吸附量达250mg/g，其在0.05mol/L NaH2PO4(pH＝3-8)或0.2％NaCl(pH&lt;3)或NaOH(pH&gt;8)的累积释放量达63～90％。
2.根据权利要求1所述的一种双敏感性纤维素基气凝胶的制备方法，其特征在于，所述步骤(1)还包括制备DAC水分散体：将DAC加入去离子水中，于200～1000rpm的搅拌速度下70～150℃反应0.5h～4h，离心、浓缩后得到透明DAC水分散体。
3.根据权利要求1所述的一种双敏感性纤维素基气凝胶的制备方法，其特征在于：所述纤维素包括天然生物质纤维素和纤维素化学品，所述天然生物质纤维素包括从竹子、木材、棉花提取的纤维素；所述的纤维素化学品包括微晶纤维素、纳米纤维素。
4.根据权利要求1所述的一种双敏感性纤维素基气凝胶的制备方法，其特征在于：所述的IO4 -供体包括高碘酸、高碘酸钠、高碘酸钾。
5.根据权利要求1所述的一种双敏感性纤维素基气凝胶的制备方法，其特征在于：所述步骤(3)中加入还原剂，所述还原剂包括氢化铝锂、硼氢化钾、硼氢化钠、氰基硼氢化钠中的至少一种。
6.根据权利要求1所述的一种双敏感性纤维素基气凝胶的制备方法，其特征在于：所述步骤(4)中将产物在NaSA溶液中搅拌22～26h，测吸附量；然后在0.05mol/L、pH＝7.4的NaH2PO4溶液或质量分数为0.2％、pH＝2的NaCl溶液中测最高释放量。
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