CN113069594B - 一种超分子水凝胶及其制备方法和应用 - Google Patents
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Abstract
本申请属于高分子材料技术领域。本申请提供了一种超分子水凝胶及其制备方法和应用。超分子水凝胶制备方法包括：将明胶与吡咯混合，再加入氧化剂发生聚合，得到混合溶液；在所述混合溶液中加入单宁酸发生交联，得到所述超分子水凝胶。吡咯在氧化剂作用下发生聚合得到聚吡咯，单宁酸含有丰富的酚羟基，本申请的制备方法操作简单、成胶时间短，制得的超分子水凝胶具有良好的可塑性、电活性，可在室温下不经过外部条件刺激自愈合；具有三维多孔结构，有利于营养物质和电子的传输，具备与神经组织相匹配的力学性能，能被临床用于组织工程神经导管以及受损神经修复中，在神经损伤修复方面有很大的应用前景。
Description
技术领域
本申请属于高分子材料技术领域，尤其涉及一种超分子水凝胶及其制备方法和应用。
背景技术
周围神经是脆弱且不受保护的组织，很容易受到自然灾害、工业损伤、交通事故、战争以及系统性疾病如糖尿病和癌症等伤害。周围神经损伤已经成为困扰人类健康的一个严重问题，每年在外科创伤中大约有2.8％的病人遭受外周神经损伤。在美国，每年发生超过20万例新的周围神经损伤病例，大约花费15亿美元的医疗保健费用。欧洲每年也有30多万人遭受外周神经损伤。
水凝胶是一种高分子材料，可以通过天然和合成聚合物的化学交联或物理交联来获得，具有优良的吸水性和柔韧性，有望成为神经组织再生的候选材料。目前，由于此类材料仍存在导电性、自愈合性能和可塑形性能差的缺点，极少见应用于神经损伤修复，限制了其应用。
发明内容
有鉴于此，本申请提供了一种超分子水凝胶及其制备方法和应用，本申请的超分子水凝胶具有很好的可塑性，导电性，可在室温且无需促进愈合剂或其他外部条件变化刺激下自愈。
本申请的具体技术方案如下：
本申请提供一种超分子水凝胶的制备方法，包括如下步骤：
S1：将明胶与吡咯混合，再加入氧化剂发生聚合，得到混合溶液；
S2：在所述混合溶液中加入单宁酸发生交联，得到所述超分子水凝胶。
本申请中，吡咯先与明胶混合均匀，再在氧化剂的作用下发生聚合生成均匀分布的聚吡咯链，有效避免剧烈的聚合反应大量放热导致体系中水分蒸发形成颗粒状固体。单宁酸含有丰富的酚羟基，可分别与明胶侧链的氨基、聚吡咯的氮氢键形成氢键，加强三者的相互作用力，交联形成超分子水凝胶。本申请的制备方法操作简单、成胶时间短，制得的超分子水凝胶具有良好的可塑性、电活性，可在室温下不经过外部条件刺激自愈合；具有三维多孔结构，有利于营养物质和电子的传输，具备与神经组织相匹配的力学性能，能被临床用于组织工程神经导管以及受损神经修复中，以促进神经细胞间的交流，提供合适细胞生长的环境，以促进受损神经组织和结构的修复，在神经损伤修复方面有很大的应用前景。
优选的，所述明胶、所述吡咯和所述单宁酸的用量比为(0.4～0.6)g:(0.1～0.2)mL:(0.3～0.5)g。
优选的，所述聚合的温度为0～4℃，时间为6～12h。更优选的，所述聚合的温度为4℃，时间为12h。
优选的，所述交联的温度为25～45℃，更优选为37℃，时间为1～10s，更优选为5s。
优选的，所述混合的时间为1～10s，更优选为10s。
优选的，所述氧化剂选自过硫酸铵和/或三氯化铁；
所述氧化剂与所述吡咯的摩尔比为(0.5～1):1，更优选为1:1。
优选的，所述明胶、所述氧化剂和所述单宁酸均为水溶液。
本申请中，明胶、氧化剂和单宁酸可预先于60℃在水中溶解，震荡混合10s，得到相应的水溶液。
优选的，明胶水溶液的浓度为0.2～0.3g/mL，更优选为0.3g/mL，氧化剂水溶液的浓度为0.3-0.6g/mL，更优选为0.1mol/L，单宁酸水溶液的浓度为0.3～0.4g/mL，更优选为0.3mol/L。
本申请还提供一种超分子水凝胶，由所述制备方法制得。
综上所述，本申请提供了一种超分子水凝胶及其制备方法和应用。超分子水凝胶制备方法包括：将明胶与吡咯混合，再加入氧化剂发生聚合，得到混合溶液；在所述混合溶液中加入单宁酸发生交联，得到所述超分子水凝胶。吡咯在氧化剂作用下发生聚合得到聚吡咯，单宁酸含有丰富的酚羟基，本申请的制备方法操作简单、成胶时间短，制得的超分子水凝胶具有良好的可塑性、电活性，可在室温下不经过外部条件刺激自愈合；具有三维多孔结构，有利于营养物质和电子的传输，具备与神经组织相匹配的力学性能，能被临床用于组织工程神经导管以及受损神经修复中，在神经损伤修复方面有很大的应用前景。
附图说明
为了更清楚地说明本申请实施例或现有技术中的技术方案，下面将对实施例或现有技术描述中所需要使用的附图作简单地介绍，显而易见地，下面描述中的附图仅仅是本申请的一些实施例，对于本领域普通技术人员来讲，在不付出创造性劳动性的前提下，还可以根据这些附图获得其它的附图。
图1为本申请实施例1产物的SEM图；
图2为本申请实施例1产物和原料的红外光谱图；
图3为本申请实施例1产物的可塑形示意图；
图4为本申请实施例1产物的自愈合能力示意图；
图5为本申请实施例1产物的自愈合及导电能力示意图；
图6为本申请实施例1产物的瞬时电流随时间变化图；
图示说明：1、聚吡咯；2、明胶；3、超分子水凝胶；4、单宁酸。
具体实施方式
为使得本申请的目的、特征、优点能够更加的明显和易懂，对本申请实施例中的技术方案进行清楚、完整地描述，显然，下面所描述的实施例仅仅是本申请一部分实施例，而非全部的实施例。基于本申请中的实施例，本领域普通技术人员在没有做出创造性劳动前提下所获得的所有其它实施例，都属于本申请保护的范围。
本申请实施例中所使用的原料和试剂为市售或自制。
本申请实施例中原料配置方法如下：
明胶溶液：将明胶(颗粒，纯度≥85％)溶于水中配成明胶浓度为0.3g/mL的溶液。
过硫酸铵溶液：将过硫酸铵(粉体，AR)溶于水中配成过硫酸铵浓度为1mol/mL的溶液。
单宁酸溶液：将单宁酸(粉体，AR)溶于水中配成单宁酸浓度为0.3g/mL的溶液。
实施例1
将2mL明胶溶液与100μL吡咯(99wt％，AR)混合，再加入过硫酸铵溶液，其中，过硫酸铵和吡咯的摩尔比为1：1，将混合溶液置于4℃环境聚合12h后加入1mL单宁酸溶液，在37℃下摇晃5s，交联，制得产物。
对制得产物进行扫描电镜(SEM)观察，结果如图1所示。图1表明，明胶、聚吡咯和单宁酸相互交联形成了孔径约为15～30μm的超分子水凝胶。
对制得的产物及原料通过傅里叶变换红外光谱进行表征，结果如图2所示。图2表明，图谱中产物的酰胺Ⅱ吸收带强度和频率没有明显变化，说明聚吡咯已成功掺入到水凝胶中，且没有新共价键的形成，主要为氢键相互作用。
将制得产物放入不同形状的模具中观察产物的形变状况，结果如图3所示。图3表明，本实施例制得产物可以被塑造成各种不同的形状，并可以在不同形状间来回变换，可塑形能强。
将制得产物制成直径为2cm的圆片，并将中心部分直径为3mm的圆形区域挖空，不施加任何刺激，观察水凝胶的自愈合能力，结果如图4所示。图4表明，在37℃下，5min后中空部分已被填充，本实施例制得产物完全愈合恢复了初始状态，具有超强自愈合能力。
将制得产物制成直径为1cm，高为2cm的圆柱体，并用导线与LED小灯泡连接，通过电化学工作站施加5V电压，并且用刀片将水凝胶切断，在不施加任何刺激的情况下观察水凝胶自愈合后的导电能力，结果如图5所示。图5表明，本实施例制得产物具有导电性，可以作为导线点亮LED小灯泡，通过自愈合恢复原始状态后导电性能也相应恢复。
通过电化学工作站的I-t测试模式，用刀片将制得产物制成直径为1cm，高为2cm的圆柱体并切断，在不施加任何刺激的情况下让水凝胶自愈合，实时测试电路中的电流大小，结果如图6所示。图6表明，本实施例制得产物在切断时电流为0，自愈合后可恢复到切断前的电流值。
以上实验结果说明，本申请实施例制得的超分子水凝胶具有三维多孔结构，具有良好的可塑性、电活性，可在室温下不经过外部条件刺激自愈合，且自愈合后可恢复到切断前的电流值，能被临床用于组织工程神经导管以及受损神经修复中，在神经损伤修复方面有很大的应用前景。
对比例1
将2mL明胶溶液与100μL吡咯(99wt％，AR)混合，再加入浓度为1mol/mL的FeCl3，其中，Fe3+和吡咯的摩尔比为1：2，将混合溶液置于4℃环境聚合12h后加入2mL单宁酸溶液，在37℃下摇晃5s，交联，制得产物。
制得产物与实施例1相比，当氧化剂和单宁酸过量时，制得产物的分散性较差，无法得到均匀产物，在不施加任何外部刺激条件下无法自愈合，导电性较弱，可塑形性相差不大。
对比例2
将2mL明胶溶液与100μL吡咯(99wt％，AR)混合，再加入过硫酸铵溶液，其中，过硫酸铵和吡咯的摩尔比为1：1，将混合溶液置于25℃环境聚合12h后加入0.5mL单宁酸溶液，在37℃下摇晃5s，交联，制得产物。
对制得产物进行导电性能测试，与实施例1相比，当单宁酸用量过少时，制得产物的导电性能较弱，电流强度低于实施例1，且自愈合性能较差，在不施加任何外部刺激条件下无法自愈合，可塑形性相差不大。
对比例3
将3mL明胶溶液与100μL吡咯(99wt％，AR)混合，再加入过硫酸铵溶液，其中，过硫酸铵和吡咯的摩尔比为1：1，将混合溶液置于4℃环境聚合12h后加入3mL单宁酸溶液，在37℃下摇晃5s，交联，制得产物。
对制得产物与实施例1相比，当吡咯用量过少时，制得产物为流动液体，无法形成水凝胶。不具备自愈合性能、可塑形性。
以上所述，以上实施例仅用以说明本申请的技术方案，而非对其限制；尽管参照前述实施例对本申请进行了详细的说明，本领域的普通技术人员应当理解：其依然可以对前述各实施例所记载的技术方案进行修改，或者对其中部分技术特征进行等同替换；而这些修改或者替换，并不使相应技术方案的本质脱离本申请各实施例技术方案的精神和范围。
Claims (9)
1.一种超分子水凝胶的制备方法，其特征在于，包括如下步骤：
S1：将明胶与吡咯混合，再加入氧化剂发生聚合，得到混合溶液；
S2：在所述混合溶液中加入单宁酸发生交联，得到所述超分子水凝胶；
所述明胶、所述吡咯和所述单宁酸的用量比为(0.4～0.6):(0.1～0.2):(0.3～0.5)；
所述氧化剂与所述吡咯的摩尔比为(0.5～1):1。
2.根据权利要求1所述的制备方法，其特征在于，所述聚合的温度为0～4℃，时间为6～12h。
3.根据权利要求1所述的制备方法，其特征在于，所述交联的温度为25～45℃，时间为1～10s。
4.根据权利要求1所述的制备方法，其特征在于，所述混合的时间为1～10s。
5.根据权利要求1所述的制备方法，其特征在于，所述氧化剂选自过硫酸铵和/或三氯化铁。
6.根据权利要求1所述的制备方法，其特征在于，所述明胶、所述氧化剂和所述单宁酸均为水溶液。
7.根据权利要求6所述的制备方法，其特征在于，明胶水溶液的浓度为0.2～0.3g/mL，氧化剂水溶液的浓度为0.3-0.6g/mL，单宁酸水溶液的浓度为0.3～0.4g/mL。
8.一种超分子水凝胶，其特征在于，由权利要求1～7任意一项所述制备方法制得。
9.权利要求1～7任意一项所述制备方法制得的超分子水凝胶或权利要求8所述超分子水凝胶在制备神经损伤修复材料中的应用。
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