CN108610615B - 一种超分子水凝胶及其制备方法 - Google Patents
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Abstract
本发明公开了一种超分子水凝胶及其制备方法。其制备方法包括以下步骤:(1)将4‑arm‑PEG‑BPY2+和葫芦脲[8]混合,加水溶解,配制为4‑arm‑PEG‑BPY2+的浓度为1~5wt%的混合溶液;(2)配制浓度为1~5wt%的4‑arm‑PEG‑Pyr溶液,并与步骤(1)中所得混合溶液搅拌混合,得超分子水凝胶;其中,BPY2+、Pyr和葫芦脲[8]的摩尔比为0.5~1:1~2:0.3~1.5。本发明方法制备得到的超分子水凝胶,具有理想的均匀的网络结构的超分子水凝胶,机械强度高。
Description
技术领域
本发明属于生物医用材料制备技术领域,具体涉及一种超分子水凝胶及其制备方法。
背景技术
水凝胶是一类以水作为分散介质的凝胶材料,由一种或多种亲水性高分子通过共价键或非共价键的作用交联形成,具有优越的三维网络结构,稳定的空间三维结构使水凝胶保有水分而不发生结构变化,由此,水凝胶具有很好的透过性和生物相容性;但是,一般的物理交联超分子水凝胶往往具有较低的机械性能,而目前为止报道的基于主客体相互作用的超分子水凝胶的机械性能也处于较低水平,无法满足需求。
发明内容
针对现有技术中的上述不足,本发明提供一种超分子水凝胶及其制备方法,可有效解决现有超分子水凝胶机械强度不足的问题。
为实现上述目的,本发明解决其技术问题所采用的技术方案是:
一种超分子水凝胶的制备方法,包括以下步骤:
(1)将4-arm-PEG-BPY2+和葫芦脲[8]混合,加水溶解,配制为4-arm-PEG-BPY2+的浓度为1~5wt%的混合溶液;
(2)配制浓度为1~5wt%的4-arm-PEG-Pyr溶液,并与步骤(1)中所得混合溶液搅拌混合,得超分子水凝胶;其中,BPY2+、Pyr和芦脲[8]的摩尔比为0.5~1:1~2:0.3~1.5。
进一步地,步骤(1)中混合溶液中4-arm-PEG-BPY2+的浓度为2wt%。
进一步地,步骤(2)中4-arm-PEG-Pyr溶液的浓度为2wt%,BPY2+、Pyr和葫芦脲[8]的摩尔比为1:1:1。
进一步地,步骤(1)中4-arm-PEG-BPY2+的制备方法如下:
(1)将重量比为1~2:5~10的四臂PEG和无水碳酸钾置于二氯甲烷中,室温下搅拌溶解,再在冰水浴中搅拌40~50min后,加入为四臂PEG重量5%~20%的溴乙酰溴,密封,于室温中再次搅拌20~24h,离心,并用过量的无水乙醚沉析上清液,过滤,并于-90~-80℃冻干滤饼,得4-arm-PEG-Br;
(2)将4-arm-PEG-Br和4,4’-联吡啶加入无水乙腈中,于80~100℃回流20~24h,然后加入氢溴酸,浓缩冻干反应液,得4-arm-PEG-BPY2+;其中,4-arm-PEG-Br和4,4’-联吡啶的摩尔比为1~1.2:1.2~1.4。
进一步地,步骤(1)中四臂PEG和无水碳酸钾的重量比为1:5。
进一步地,步骤(2)中4-arm-PEG-Br和4,4’-联吡啶的摩尔比1:1。
进一步地,步骤(2)中4-arm-PEG-Pyr的制备方法如下:
(1)将重量比为0.3~0.36:0.38~0.46:0.23~0.28的芘丁酸、1-乙基-(3-二甲基氨基丙基)碳酰二亚胺盐酸盐和N-羟基琥珀酰亚胺加入DMF中,于室温下搅拌2~4h,得DMF混合溶液;
(2)向DMF混合溶液中加入浓度为0.8~0.15g/mL的4-arm-PEG溶液,搅拌48~50h,透析3~4天后,冻干,得4-arm-PEG-Pyr;其中,4-arm-PEG溶液和DMF混合溶液的体积比为1:1。
进一步地,步骤(1)中芘丁酸、1-乙基-(3-二甲基氨基丙基)碳酰二亚胺盐酸盐和N-羟基琥珀酰亚胺的重量比为0.3:0.38:0.23。
进一步地,步骤(2)中4-arm-PEG溶液的浓度为0.1g/mL。
采用上述方法制备得到的超分子水凝胶。
本发明的有益效果为:
1、葫芦脲[8](CB[8])由于具有特殊的疏水性笼体和亲水性端口结构使其既可与多种有机物发生疏水性的笼体作用,亦可与偶极或离子型化合物发生亲水性的端口相互作用;由此,本发明方法以贫电子的4-arm-PEG-BPY2+和富电子的4-arm-PEG-Pyr作为两种客体分子,再以葫芦脲[8]作为主体分子,在正负电荷的相互吸引,以及π-π堆积相互作用的配合下,主客体相互作用,形成具有理想的均匀的网络结构的超分子水凝胶,其机械性能较传统超分子水凝胶具有更高的机械性能,为提高主客体相互作用物理交联超分子水凝胶的机械强度的研究提供了新的思路。
2、葫芦脲[8]的刚性结构也决定了它作为主体分子时,不能通过改变形状来容纳客体分子,这就导致了与它配位络合的客体分子需要有极强的专一性和极高的络合常数,也说明了以葫芦脲[8]为主体的主客体体系具有很强的分子识别能力和很高的稳定性。
3、本发明制备超分子水凝胶的方法简单,其合成过程不需要复杂的操作以及苛刻的反应条件。
4、本发明所采用的原料均具有良好的生物相容性,毫无疑问该超分子水凝胶也具有良好的生物相容性,因此,在细胞培养,骨和软骨组织修复,药物传递及释放等相关领域的应用提供了有利条件。
附图说明
图1为本发明实施例一的超分子水凝胶制备过程。
具体实施方式
下面对本发明的具体实施方式进行描述,以便于本技术领域的技术人员理解本发明,但应该清楚,本发明不限于具体实施方式的范围,对本技术领域的普通技术人员来讲,只要各种变化在所附的权利要求限定和确定的本发明的精神和范围内,这些变化是显而易见的,一切利用本发明构思的发明创造均在保护之列。
实施例1
一种超分子水凝胶的制备方法,包括以下步骤:
(1)制备4-arm-PEG-BPY2+
a、在室温的条件下将1g的四臂PEG(4-arm-PEG,Mn=20000g/mol)和5g的无水碳酸钾溶解于30mL的二氯甲烷中,然后在冰水浴中以100~200r/min的转速磁力搅拌40min;
b、向步骤a所得产物中加入0.1g的溴乙酰溴,密封,取出冰袋,在室温的条件下,以100~200r/min的转速磁力搅拌24h;
c、于3500r/min对步骤b所得产物进行离心,离心10min后,收集上清液,并加入过量的无水乙醚沉析,然后过滤,并在-80℃的条件下冻干滤饼,得到4-arm-PEG-Br;
d、将1mol的4-arm-PEG-Br和1mol的4,4’-联吡啶同时加入至30mL的无水乙腈中,于80℃加热回流反应24h后,再加入一定量的浓度为0.1mol/L的氢溴酸,旋转蒸发浓缩反应液,冻干,得到呈淡黄色的4-arm-PEG-BPY2+;
(2)制备4-arm-PEG-Pyr
a、将0.3g的芘丁酸、0.38g的1-乙基-(3-二甲基氨基丙基)碳酰二亚胺盐酸盐和0.23g的N-羟基琥珀酰亚胺加入至50mL的N,N-二甲基甲酰胺中,在室温的条件下搅拌2h,备用;
b、将5g的4-arm-PEG加入到50mL的水中,搅拌溶解,然后在60℃的条件下,将配置得到的4-arm-PEG溶液加入至步骤a所得产物中,继续搅拌48h,然后置于透析袋中透析3天,并且,透析期间需进行多次换水,以保证透析充分;
c、冻干步骤b所得的透析液,得到目标产物4-arm-PEG-Pyr;
(3)将0.1mol的4-arm-PEG-BPY2+和0.4mol的葫芦脲[8]混合,加入适量的蒸馏水溶解,在室温下磁力搅拌4h,配制得到4-arm-PEG-BPY2+的浓度为2wt%的溶液;
(4)取0.1mol的4-arm-PEG-Pyr,加入适量蒸馏水溶解,并在室温下磁力搅拌数分钟,配制成4-arm-PEG-Pyr浓度为2wt%的溶液,然后加入步骤(3)制备得到的溶液,搅拌混合,即制备得到具有理想的均匀的网络结构的超分子水凝胶。
实施例2
一种超分子水凝胶的制备方法,包括以下步骤:
(1)制备4-arm-PEG-BPY2+
a、在室温的条件下将1g的四臂PEG(4-arm-PEG,Mn=20000g/mol)和7g的无水碳酸钾溶解于30mL的二氯甲烷中,然后在冰水浴中以100~200r/min的转速磁力搅拌40min;
b、向步骤a所得产物中加入0.1g的溴乙酰溴,密封,取出冰袋,在室温的条件下,以100~200r/min的转速磁力搅拌24h;
c、于3500r/min对步骤b所得产物进行离心,离心10min后,收集上清液,并加入过量的无水乙醚沉析,然后过滤,并在-80℃的条件下冻干滤饼,得到4-arm-PEG-Br;
d、将1mol的4-arm-PEG-Br和1.1mol的4,4’-联吡啶同时加入至30mL的无水乙腈中,于80℃加热回流反应24h后,再加入一定量的浓度为0.1mol/L的氢溴酸,旋转蒸发浓缩反应液,冻干,得到呈淡黄色的4-arm-PEG-BPY2+;
(2)制备4-arm-PEG-Pyr
a、将0.3g的芘丁酸、0.38g的1-乙基-(3-二甲基氨基丙基)碳酰二亚胺盐酸盐和0.23g的N-羟基琥珀酰亚胺加入至50mL的N,N-二甲基甲酰胺中,在室温的条件下搅拌2h,备用;
b、将5g的4-arm-PEG加入到50mL的水中,搅拌溶解,然后在60℃的条件下,将配置得到的4-arm-PEG溶液加入至步骤a所得产物中,继续搅拌48h,然后置于透析袋中透析3天,并且,透析期间需进行多次换水,以保证透析充分;
c、冻干步骤b所得的透析液,得到目标产物4-arm-PEG-Pyr;
(3)将0.1mol的4-arm-PEG-BPY2+和0.4mol的葫芦脲[8]混合,加入适量的蒸馏水溶解,在室温下磁力搅拌4h,配制得到4-arm-PEG-BPY2+的浓度为1.5wt%的溶液;
(4)取0.1mol的4-arm-PEG-Pyr,加入适量蒸馏水溶解,并在室温下磁力搅拌数分钟,配制成4-arm-PEG-Pyr浓度为1.5wt%的溶液,然后加入步骤(3)制备得到的溶液,搅拌混合,即制备得到具有理想的均匀的网络结构的超分子水凝胶。
实施例3
一种超分子水凝胶的制备方法,包括以下步骤:
(1)制备4-arm-PEG-BPY2+
a、在室温的条件下将1g的四臂PEG(4-arm-PEG,Mn=20000g/mol)和10g的无水碳酸钾溶解于30mL的二氯甲烷中,然后在冰水浴中以100~200r/min的转速磁力搅拌40min;
b、向步骤a所得产物中加入0.1g的溴乙酰溴,密封,取出冰袋,在室温的条件下,以100~200r/min的转速磁力搅拌24h;
c、于3500r/min对步骤b所得产物进行离心,离心10min后,收集上清液,并加入过量的无水乙醚沉析,然后过滤,并在-80℃的条件下冻干滤饼,得到4-arm-PEG-Br;
d、将1mol的4-arm-PEG-Br和1.1mol的4,4’-联吡啶同时加入至30mL的无水乙腈中,于80℃加热回流反应24h后,再加入一定量的浓度为0.1mol/L的氢溴酸,旋转蒸发浓缩反应液,冻干,得到呈淡黄色的4-arm-PEG-BPY2+;
(2)制备4-arm-PEG-Pyr
a、将0.3g的芘丁酸、0.38g的1-乙基-(3-二甲基氨基丙基)碳酰二亚胺盐酸盐和0.23g的N-羟基琥珀酰亚胺加入至50mL的N,N-二甲基甲酰胺中,在室温的条件下搅拌2h,备用;
b、将5g的4-arm-PEG加入到50mL的水中,搅拌溶解,然后在60℃的条件下,将配置得到的4-arm-PEG溶液加入至步骤a所得产物中,继续搅拌48h,然后置于透析袋中透析3天,并且,透析期间需进行多次换水,以保证透析充分;
c、冻干步骤b所得的透析液,得到目标产物4-arm-PEG-Pyr;
(3)将0.1mol的4-arm-PEG-BPY2+和0.4mol的葫芦脲[8]混合,加入适量的蒸馏水溶解,在室温下磁力搅拌4h,配制得到4-arm-PEG-BPY2+的浓度为3wt%的溶液;
(4)取0.1mol的4-arm-PEG-Pyr,加入适量蒸馏水溶解,并在室温下磁力搅拌数分钟,配制成4-arm-PEG-Pyr浓度为3wt%的溶液,然后加入步骤(3)制备得到的溶液,搅拌混合,即制备得到具有理想的均匀的网络结构的超分子水凝胶。
实施例4
一种超分子水凝胶的制备方法,包括以下步骤:
(1)制备4-arm-PEG-BPY2+
a、在室温的条件下将1g的四臂PEG(4-arm-PEG,Mn=20000g/mol)和10g的无水碳酸钾溶解于30mL的二氯甲烷中,然后在冰水浴中以100~200r/min的转速磁力搅拌40min;
b、向步骤a所得产物中加入0.1g的溴乙酰溴,密封,取出冰袋,在室温的条件下,以100~200r/min的转速磁力搅拌24h;
c、于3500r/min对步骤b所得产物进行离心,离心10min后,收集上清液,并加入过量的无水乙醚沉析,然后过滤,并在-80℃的条件下冻干滤饼,得到4-arm-PEG-Br;
d、将1mol的4-arm-PEG-Br和1.2mol的4,4’-联吡啶同时加入至30mL的无水乙腈中,于80℃加热回流反应24h后,再加入一定量的浓度为0.1mol/L的氢溴酸,旋转蒸发浓缩反应液,冻干,得到呈淡黄色的4-arm-PEG-BPY2+;
(2)制备4-arm-PEG-Pyr
a、将0.3g的芘丁酸、0.38g的1-乙基-(3-二甲基氨基丙基)碳酰二亚胺盐酸盐和0.23g的N-羟基琥珀酰亚胺加入至50mL的N,N-二甲基甲酰胺中,在室温的条件下搅拌2h,备用;
b、将5g的4-arm-PEG加入到50mL的水中,搅拌溶解,然后在60℃的条件下,将配置得到的4-arm-PEG溶液加入至步骤a所得产物中,继续搅拌48h,然后置于透析袋中透析3天,并且,透析期间需进行多次换水,以保证透析充分;
c、冻干步骤b所得的透析液,得到目标产物4-arm-PEG-Pyr;
(3)将0.1mol的4-arm-PEG-BPY2+和0.4mol的葫芦脲[8]混合,加入适量的蒸馏水溶解,在室温下磁力搅拌4h,配制得到4-arm-PEG-BPY2+的浓度为5wt%的溶液;
(4)取0.1mol的4-arm-PEG-Pyr,加入适量蒸馏水溶解,并在室温下磁力搅拌数分钟,配制成4-arm-PEG-Pyr浓度为5wt%的溶液,然后加入步骤(3)制备得到的溶液,搅拌混合,即制备得到具有理想的均匀的网络结构的超分子水凝胶。
对比例
与实施例1相比,采用聚乙烯醇枝BPY2+(PVA-BPY2+)代替4-arm-PEG-BPY2+,再用海藻酸钠接枝Pyr(SA-BPY2+)代替4-arm-PEG-Pyr,其余步骤均与实施例1相同。
于相同条件下检测对比例和实施例1~4制备得到的超分子水凝胶的压缩模量,其结果显示,对比例制备得到的超分子水凝胶的压缩模量仅为0.04MPa,而实施例1~4制备得到的超分子水凝胶的压缩模量均能达到1MPa以上,其中,尤以实施例1为最佳,其压缩模量达到了2.16MPa。
由此说明,只有在本发明方法的试剂和步骤的配合下,才能制备得到网络结构均匀,机械强度更高的超分子水凝胶。
Claims (7)
1.一种超分子水凝胶的制备方法,其特征在于,包括以下步骤:
(1)将4-arm-PEG-BPY2+和葫芦脲[8]混合,加水溶解,配制为4-arm-PEG-BPY2+的浓度为1~5wt%的混合溶液;所述4-arm-PEG-BPY2+的制备方法如下:
a、将重量比为1~2:5~10的四臂PEG和无水碳酸钾置于二氯甲烷中,室温下搅拌溶解,再在冰水浴中搅拌40~50min后,加入为四臂PEG重量5%~20%的溴乙酰溴,密封,于室温中再次搅拌20~24h,离心,并用过量的无水乙醚沉析上清液,过滤,并于-90~-80℃冻干滤饼,得4-arm-PEG-Br;
b、将4-arm-PEG-Br和4,4’-联吡啶加入无水乙腈中,于80~100℃回流20~24h,然后加入氢溴酸,浓缩冻干反应液,得4-arm-PEG-BPY2+;其中,4-arm-PEG-Br和4,4’-联吡啶的摩尔比为1~1.2:1.2~1.4;
(2)配制浓度为1~5wt%的4-arm-PEG-Pyr溶液,并与步骤(1)中所得混合溶液搅拌混合,得超分子水凝胶;其中,BPY2+、Pyr和葫芦脲[8]的摩尔比为0.5~1:1~2:0.3~1.5;
所述4-arm-PEG-Pyr的制备方法如下:
1)将重量比为0.3~0.36:0.38~0.46:0.23~0.28的芘丁酸、1-乙基-(3-二甲基氨基丙基)碳酰二亚胺盐酸盐和N-羟基琥珀酰亚胺加入DMF中,于室温下搅拌2~4h,得DMF混合溶液;
2)向DMF混合溶液中加入浓度为0.15~0.8g/mL的4-arm-PEG溶液,搅拌48~50h,透析3~4天后,冻干,得4-arm-PEG-Pyr;其中,4-arm-PEG溶液和DMF混合溶液的体积比为1:1。
2.根据权利要求1所述的超分子水凝胶的制备方法,其特征在于,步骤(1)中所述混合溶液中4-arm-PEG-BPY2+的浓度为2wt%。
3.根据权利要求1所述的超分子水凝胶的制备方法,其特征在于,步骤(2)中所述4-arm-PEG-Pyr溶液的浓度为2wt%,BPY2+、Pyr和葫芦脲[8]的摩尔比为1:1:1。
4.根据权利要求1所述的超分子水凝胶的制备方法,其特征在于,所述四臂PEG和无水碳酸钾的重量比为1:5。
5.根据权利要求1所述的超分子水凝胶的制备方法,其特征在于,所述4-arm-PEG-Br和4,4’-联吡啶的摩尔比1:1。
6.根据权利要求1所述的超分子水凝胶的制备方法,其特征在于,所述芘丁酸、1-乙基-(3-二甲基氨基丙基)碳酰二亚胺盐酸盐和N-羟基琥珀酰亚胺的重量比为0.3:0.38:0.23。
7.采用权利要求1~6任一项所述方法制备得到的超分子水凝胶。
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