CN117304515A - 一种纤维素纳米纤维增强聚离子液体水凝胶及其制备方法 - Google Patents
一种纤维素纳米纤维增强聚离子液体水凝胶及其制备方法 Download PDFInfo
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Abstract
本发明提出的是一种纤维素纳米纤维增强聚离子液体水凝胶,其结构包括聚离子液体水凝胶,纤维素纳米纤维;纤维素纳米纤维分散在聚离子液体水凝胶内;本发明的制备方法包括以下步骤:1)将纤维素纳米纤维分散于去离子水中配置成分散液;2)向分散液中加入丙烯酰胺形成均匀的混合溶液;3)向混合溶液中加入离子液体配制成凝胶预聚体;4)将N,N'‑亚甲基双丙烯酰胺水溶液加入到凝胶预聚体中形成聚合反应混合溶液;5)将热引发剂投入聚合反应混合溶液中,室温搅拌后在冰水浴下冷却,加入N,N,N',N'‑四甲基乙二胺,搅拌并脱除气泡后倒入模具中;6)将半聚合状态水凝胶进行定向冷冻处理,然后在室温下进行完全聚合。
Description
技术领域
本发明涉及一种纤维素纳米纤维增强聚离子液体水凝胶及其制备方法,属于生物医药领域。
背景技术
每年,数百万人患有由持续感染或糖尿病引起慢性不愈合伤口,这些伤口可能会给患者带来重大负担,影响他们的活动能力、生活质量和整体健康;因此,开发治疗细菌感染伤口相关并发症的有效材料已成为研究和临床实践的重要领域。
水凝胶是一种柔软、湿润且具有生物相容性的材料,由于其能够保持伤口湿润、允许小分子和亲水性生物大分子扩散并提供温和的治疗环境,水凝胶作为伤口敷料在治疗皮肤创伤方面具有广阔的应用前景。
考虑到细菌感染伤口复杂的愈合过程,皮肤组织工程的新策略集中在水凝胶敷料中添加抗菌剂,如抗生素、银纳米粒子(SNP)、多核金属配合物、阳离子抗菌聚合物等,这些药物可以提高抗菌性能并促进更有效的伤口愈合;在这些抗菌物质中,抗生素通过干扰或抑制微生物的某些代谢过程来有效抑制或杀死微生物;然而,抗生素的过度使用导致抗生素耐药细菌迅速增加,可能会让更多的人死于抗生素耐药细菌性疾病。
SNP 因其广谱抗菌活性(不会导致耐药性)及其在癌症治疗中的日益广泛使用而受到广泛关注;不幸的是,大量研究报告称,SNP 可能具有毒性,对正常神经元造成的伤害可能比对癌细胞造成的伤害更大;羧甲基壳聚糖(CMCS)是壳聚糖的衍生物,具有优异的生物相容性和生物活性,以及良好的水溶性和一定的抗菌活性;然而,CMCS的抗菌性能有限,通常需要与其他抗菌物质联合使用才能达到更强大的抗菌效果;因此,制备一种能有效对抗复杂伤口细菌感染的水凝胶伤口敷料仍然是一个重大挑战。
离子液体(ILs)是一组由有机阳离子和有机或无机阴离子组成的有机盐;由离子液体(ILs)单体形成的聚离子液体(PILs)保留了离子液体的大部分独特功能,可以集成到聚离子液体(PILs)中;在聚离子液体的抗菌作用过程中,阳离子部分首先附着在带负电荷的细菌膜表面,亲脂部分插入到磷脂双分子层中,导致膜破裂,最终导致细菌死亡;近年来,聚离子液体(PILs)因其分子可设计性、优异的抗菌性能和化学稳定性而在医用抗菌伤口敷料领域引起了广泛关注;然而,离子液体会削弱聚合物分子链之间的作用力,降低机械性能,不能满足伤口敷料所需的良好的弹性和形状恢复能力,无法应对伤口部位的各种运动,包括拉伸、压缩和扭曲。
为了使水凝胶在长效抗菌作用的同时,还能够保持较好的能量耗散能力,在频繁的活动中保持稳定,人们提出了不同的水凝胶机械增强策略;在这些策略中,已经开发出各种类型的强韧水凝胶,包括拓扑水凝胶、滑环水凝胶、纳米复合水凝胶、微凝胶增强水凝胶,但整体的效果并不理想,比如敷料回弹性差、无法实现形状恢复、长效抗菌功能弱等问题。
发明内容
本发明提出的是一种纤维素纳米纤维增强聚离子液体水凝胶及其制备方法,其目的旨在解决现有水凝胶回弹性差、无法实现形状恢复、不具有长效抗菌功能的问题。
本发明的技术解决方案:一种纤维素纳米纤维增强聚离子液体水凝胶,其结构包括聚离子液体水凝胶,纤维素纳米纤维;纤维素纳米纤维分散在聚离子液体水凝胶内。
进一步地,所述聚离子液体水凝胶具有蜂窝状孔洞结构,蜂窝状孔洞结构的聚离子液体水凝胶中每个孔洞四周的聚离子液体水凝胶内部和表面均分布有纤维素纳米纤维。
进一步地,所述聚离子液体水凝胶为离子液体与丙烯酰胺在N, N '-亚甲基双丙烯酰胺作用下通过热引发自由基聚合反应形成;所述离子液体为乙烯基离子液体。
一种纤维素纳米纤维增强聚离子液体水凝胶的制备方法,该方法包括以下步骤:
1)将纤维素纳米纤维分散于去离子水中配置成分散液;
2)向分散液中加入丙烯酰胺形成均匀的混合溶液;
3)向混合溶液中加入离子液体并搅拌配制成凝胶预聚体;
4)将N, N '-亚甲基双丙烯酰胺水溶液加入到凝胶预聚体中搅拌形成聚合反应混合溶液;
5)将热引发剂投入聚合反应混合溶液中,室温搅拌后在冰水浴下冷却,然后加入N,N,N',N'-四甲基乙二胺,搅拌并脱除气泡后倒入模具中,放置一定时间形成半聚合状态水凝胶;
6)将模具内的半聚合状态水凝胶连同模具一起进行定向冷冻处理,然后在室温下进行完全聚合。
进一步地,所述步骤1)配置的分散液中纤维素纳米纤维与去离子水的质量比为(0.5~1.5):100;所述步骤2)制备的混合溶液中纤维素纳米纤维与丙烯酰胺的质量比为(3~5):100。
进一步地,所述离子液体在凝胶预聚体中所占的质量百分比为10 wt%~40 wt%。
进一步地,所述聚合反应混合溶液中N, N '-亚甲基双丙烯酰胺与凝胶预聚体的质量比为(1~1.5):10。
进一步地,所述热引发剂为过硫酸铵和过硫酸钾中的至少一种;所述模具的底部材料比模具四周侧壁的材料具有更好的导冷效果。
进一步地,所述热引发剂与纤维素纳米纤维的质量比为1:( 0.5~2.5);所述冰水浴的温度为0℃~4℃;所述N,N,N',N'-四甲基乙二胺与纤维素纳米纤维之间的质量比为(0.3~0.6):1;所述模具的底部材料为黄铜或紫铜,模具四周侧壁的材料为聚四氟乙烯;所述将模具内的半聚合状态水凝胶连同模具一起进行定向冷冻处理具体为将模具内的半聚合状态水凝胶连同模具一起放置于-60 ℃~-120 ℃环境中进行定向冷冻处理。
进一步地,所述纤维素纳米纤维增强聚离子液体水凝胶适用于伤口敷料。
本发明的有益效果:
1)本发明提供了一种具有超拉伸,低滞回性,且兼具长效抗菌性能的纤维素纳米纤维增强聚离子液体水凝胶;
2)本发明提供的纤维素纳米纤维增强聚离子液体水凝胶用作伤口敷料使用能具有密封伤口、预防感染、防冻、满足强附着力需要等功能;
3)本发明纤维素纳米纤维增强聚离子液体水凝胶的制备方法简单,成本低廉,便于大规模制备应用;
4)本发明利用丙烯酰胺与离子液体的热引发自由基聚合反应构筑聚离子液体凝胶网络结构,并利用具有独特的纳米级结构和高长径比的纤维素纳米纤维(CNFs),去提高聚离子液体水凝胶的力学性能和实用性;同时利用聚离子液体水凝胶中咪唑基团与纤维素纳米纤维中的羧基基团的静电相互作用,以及聚离子液体水凝胶中氨基与纤维素纳米纤维中的羟基的氢键作用,构筑了聚离子液体-纤维素纳米纤维的动态网络结构;上述优势使得本发明纤维素纳米纤维增强聚离子液体水凝胶在2000%的拉伸状态下,也不会发生断裂;甚至在500%的循环拉伸条件下,只有较小的滞回,具有良好的回弹性和低迟滞性;
5) 本发明的纤维素纳米纤维增强聚离子液体水凝胶的抗菌特性来源于水凝胶网络结构的组分-聚离子液体凝胶网络,在体外和体内抑菌实验中表现高效抑菌功能,其对革兰氏阴性菌和革兰氏阳性菌(如实施例4中的大肠杆菌和金黄色葡萄球菌)的抑菌效率均可达100%,可有效减少患者因感染而导致伤口长期不愈合的痛苦,加速伤口愈合。
附图说明
附图1为纤维素纳米纤维增强聚离子液体水凝胶的制备示意图。
附图2为纤维素纳米纤维增强聚离子液体水凝胶用作伤口敷料的示意图。
附图3为本发明制备纤维素纳米纤维增强聚离子液体水凝胶的扫描电镜图一。
附图4为本发明制备纤维素纳米纤维增强聚离子液体水凝胶的扫描电镜图二。
附图5为L929细胞与纤维素纳米纤维增强聚离子液体水凝胶共培养24和48小时的活/死细胞染色图。
附图6为纤维素纳米纤维增强聚离子液体水凝胶超拉伸性能的照片展示图。
附图7为纤维素纳米纤维增强聚离子液体水凝胶500%拉伸循环五次后的循环曲线图。
附图8为实施例4中纤维素纳米纤维增强聚离子液体水凝胶的体外抑菌实验结果对比图。
附图9为实施例5中各组皮肤创伤处理后不同时间点的创面面积对比图。
具体实施方式
一种纤维素纳米纤维增强聚离子液体水凝胶,其结构包括聚离子液体(PILs) 水凝胶,纤维素纳米纤维;纤维素纳米纤维分散在聚离子液体(PILs) 水凝胶内。
所述聚离子液体(PILs) 水凝胶具有蜂窝状孔洞结构,蜂窝状孔洞结构的聚离子液体(PILs) 水凝胶中每个孔洞四周的聚离子液体(PILs) 水凝胶内部和表面均分布有纤维素纳米纤维。
所述聚离子液体水凝胶带有咪唑基团和氨基,所述纤维素纳米纤维带有羧基基团和羟基,聚离子液体水凝胶与纤维素纳米纤维之间通过咪唑基团和羧基基团的静电相互作用以及氨基和羟基的氢键作用交联在一起。
所述聚离子液体水凝胶为离子液体(ILs)与丙烯酰胺在N, N '-亚甲基双丙烯酰胺作用下通过热引发自由基聚合反应形成;所述离子液体(ILs)优选为乙烯基离子液体,进一步优选为1-乙烯基-3-丁基咪唑溴盐。
一种纤维素纳米纤维增强聚离子液体水凝胶的制备方法,该方法包括以下步骤:
1)将纤维素纳米纤维(CNFs)分散于去离子水中配置成分散液,通过搅拌使纤维素纳米纤维在分散液中均匀分散;
所述分散液中纤维素纳米纤维与去离子水的质量比优选为(0.5~1.5):100,分散液中纤维素纳米纤维与去离子水的质量比进一步优选为1:100;
2)向步骤1)制备的分散液中加入丙烯酰胺(AM)形成均匀的混合溶液;其中纤维素纳米纤维与丙烯酰胺的质量比优选为(3~5):100,纤维素纳米纤维与丙烯酰胺的质量比进一步优选为4:100;
3)再向步骤2)制备的均匀的混合溶液中加入离子液体(ILs)搅拌均匀配制成含有纤维素纳米纤维的丙烯酰胺-离子液体(AM-ILs)的混合溶液即凝胶预聚体,所述离子液体在凝胶预聚体中所占的质量百分比为10 wt%~40 wt%;所述离子液体(ILs)优选为乙烯基离子液体、进一步优选为1-乙烯基-3-丁基咪唑溴盐;
4)将配好的N, N '-亚甲基双丙烯酰胺(MBA)水溶液加入到凝胶预聚体中搅拌均匀形成聚合反应混合溶液,聚合反应混合溶液中N, N '-亚甲基双丙烯酰胺(MBA)与凝胶预聚体的质量比优选为1~1.5:10,聚合反应混合溶液中N, N '-亚甲基双丙烯酰胺(MBA)与凝胶预聚体的质量比进一步优选为1.2:10;
5)将热引发剂投入聚合反应混合溶液中,室温搅拌均匀后在冰水浴下冷却完全,然后加入N,N,N',N'-四甲基乙二胺(TEMED),搅拌均匀,超声脱除气泡后,倒入底部为黄铜,四周为聚四氟乙烯的模具中,放置一定时间形成未完全聚合状态水凝胶即半聚合状态水凝胶;
所述的热引发剂为能在一定温度下引发聚合反应的化学物质;所述热引发剂优选为过硫酸铵(APS)和(过硫酸钾)KPS中的至少一种;所述热引发剂与纤维素纳米纤维的质量比优选为1: 0.5~2.5;热引发剂与纤维素纳米纤维的质量比进一步优选为1:1.5;所述冰水浴的温度优选为0℃-4℃;所述放置一定时间形成未完全聚合状态水凝胶优选放置5分钟~30分钟形成半聚合状态水凝胶;所述N,N,N',N'-四甲基乙二胺与纤维素纳米纤维之间的质量比优选为(0.3~0.6):1;N,N,N',N'-四甲基乙二胺与纤维素纳米纤维之间的质量比进一步优选为0.45:1;
6)将模具内的半聚合状态水凝胶连同模具一起放置于超低温冰箱,-60 ℃~-120℃进行超低温定向冷冻处理,优选-80 ℃进行定向冷冻处理,进而得到可定向聚合的支架,然后在室温下经过1h~3h进行完全聚合,最终形成纤维素纳米纤维增强聚离子液体水凝胶;其中,-60 ℃~-120 ℃进行超低温定向冷冻处理的时间优选为2h;室温下完全聚合的时间进一步优选为2h;底部为黄铜,四周为聚四氟乙烯的模具利用黄铜能够快速导冷的特点,对模具内的半聚合状态水凝胶实现从下往上的冷冻效果,冷冻使得水凝胶里的水从模具底部向上快速冻成冰晶,冰晶的晶核先在模具底部的黄铜处形成,然后冰晶的晶核慢慢长大形成具有蜂窝状孔洞结构的冰晶。
所述步骤1)中纤维素纳米纤维(CNFs)分散于去离子水中配置成的分散液中,大量带负电荷的羧基引起的每根CNFs之间产生了一定的静电排斥力,纤维素纳米纤维在分散液中可保持均匀分散状态,另外这些静电斥力的存在有助于分子间结构域的形成,进而为制备均匀分散的水凝胶网络提供方便;在整个制备方法中,纤维素纳米纤维(CNFs)与带有大量咪唑阳离子和氨基的聚离子液体存在静电相互作用和氢键网络,促使纤维素纳米纤维应能够均匀分散在蜂窝状微观结构的聚离子液体水凝胶内部和聚离子液体水凝胶表面以加强网络。
本发明制备的纤维素纳米纤维增强聚离子液体水凝胶适用于作为伤口敷料使用,能有效促进慢性伤口愈合,尤其对大肠杆菌和金黄色葡萄球菌具有良好的抑菌效果。
本发明制备的纤维素纳米纤维增强聚离子液体水凝胶适用于作为伤口敷料使用,在真皮修复过程中,引导成纤维细胞迁移增殖,增加新胶原沉积于血管重建,从而加速伤口愈合。
本发明以纤维素纳米纤维(CNFs),离子液体(ILs)、丙烯酰胺(AM)为原料制备纤维素纳米纤维增强聚离子液体水凝胶;如图1所示,离子液体(ILs)与丙烯酰胺(AM)在N, N '-亚甲基双丙烯酰胺(MBA)作用下通过热引发自由基聚合反应形成聚丙烯酰胺--离子液体(PAM-ILs)水凝胶即聚离子液体(PILs)水凝胶;同时,本发明将具有独特纳米级结构、大比表面积、高拉伸强度、可调节表面电荷的纤维素纳米纤维(CNFs)引入,与聚离子液体水凝胶网络存在大量的静电相互作用和氢键作用(附图1),这会使得聚离子液体水凝胶网络的机械性能得到大幅提升;同时,对未聚合完全的凝胶网络,-60 ℃~-120 ℃进行的超低温定向冷冻处理,使得水凝胶里的水被快速冻成冰晶,冰晶形成蜂窝状的孔洞结构,蜂窝状孔洞结构的冰晶作为可定向聚合的支架,即蜂窝状的孔洞结构支架;再在室温下完全聚合,便可获得具有连通细胞结构的纤维素纳米纤维增强聚离子液体水凝胶,该纤维素纳米纤维增强聚离子液体水凝胶具有优异的弹性、机械拉伸性能和良好的压缩性能以及低滞回的性能。
本发明纤维素纳米纤维增强聚离子液体水凝胶的制备过程中聚离子液体水凝胶中咪唑基团与纤维素纳米纤维中的羧基基团的静电相互作用,有利于构筑聚离子液体-纤维素阴阳离子网络结构,使得聚离子液体(PILs)水凝胶能够浇注在纤维素纳米纤维(CNFs)上,聚离子液体(PILs)水凝胶作为“混凝土相”, 纤维素纳米纤维作为“增强相”,聚离子液体水凝胶紧密包裹纤维素纳米纤维,纤维素纳米纤维起到了增强聚离子液体水凝胶的机械性能和桥接聚离子液体(PILs)水凝胶的作用;离子液体在纤维素纳米纤维增强聚离子液体水凝胶中起到抗菌剂和电解质的双重作用;纤维素纳米纤维增强聚离子液体水凝胶中同时存在化学交联和物理交联;物理交联包括聚离子液体与纤维素纳米纤维之间的氢键作用,以及纤维素纳米纤维表面的羧基与聚离子液体的咪唑阳离子之间的静电相互作用,使得该纤维素纳米纤维增强聚离子液体水凝胶具有较好的机械性能。
如附图4所示,白色箭头指向处明显可见大量纤维束;纤维素纳米纤维在聚离子液体(PILs)水凝胶蜂窝状孔洞的光滑表面上呈现分散排列,聚离子液体(PILs)水凝胶作为聚离子共聚物基质,这表明纤维素纳米纤维与聚离子共聚物基质表面具有很强的附着力,从而有助于增强聚离子液体水凝胶的桥接网络;同时,对最终制备的纤维素纳米纤维增强聚离子液体水凝胶进行SEM表征,如附图4,在横截面处观察到大量纤维素纳米纤维均匀分散,在这种形态中,聚离子液体基质充当“混凝土相”,纤维素纳米纤维(CNFs)充当“增强相”,这提高了水凝胶的力学性能,增强了对裂纹扩展的抵抗力,从而增强了复合水凝胶的机械性能,提高了聚离子液体水凝胶的力学性能和实用性。
本发明制备方法所使用原料中的离子液体本身具有抗菌功能,因此最终制备的纤维素纳米纤维增强聚离子液体水凝胶中无需额外负载抗菌药物或抗菌性功能纳米粒子就能具有良好的长效杀菌功能,本发明整个纤维素纳米纤维增强聚离子液体水凝胶的制备过程工艺简单。
本发明经过全面的体外和体内实验系统地验证了离子液体(ILs)的引入赋予纤维素纳米纤维增强聚离子液体水凝胶抑制细菌生长和加速感染伤口愈合过程的能力,本发明所制备的纤维素纳米纤维增强聚离子液体水凝胶作为伤口敷料使用时是一种能够用于促进慢性伤口愈合的伤口敷料。
本发明通过引入纤维素纳米纤维使聚离子液体水凝胶呈现出有序互连的细胞结构,具有优异的拉伸性、出色的弹性和低滞后性;在聚离子液体水凝胶的抗菌作用过程中,首先阳离子部分附着在带负电荷的细菌膜表面,亲脂部分插入到磷脂双分子层中,导致膜破裂,最终导致细菌死亡,阳离子为聚离子液体中乙烯基离子液体上的咪唑阳离子,纤维素纳米纤维增强聚离子液体水凝胶是由丙烯酰胺与乙烯基离子液体自由基共聚(形成聚离子液体),再通过纤维素纳米纤维增强合成;本发明制备的纤维素纳米纤维增强聚离子液体水凝胶作为伤口敷料除抗菌外还能够提供密封伤口的粘附性,具有良好的生物相容性,并在创面周围保持湿润环境,能持续高效的抑制细菌的增值;在真皮修复过程中,引导成纤维细胞迁移增殖,增加新胶原沉积于血管重建,从而加速伤口愈合,提高伤口愈合质量。
以下结合实施例对本发明进行详细阐述,但这些实施例仅为例示说明之用,而不应被解释为对本发明实施的限制。
实施例1
一种纤维素纳米纤维增强聚离子液体水凝胶的制备方法,该方法包括:
将纤维素纳米纤维(CNFs)分散于去离子水中配置成分散液,通过搅拌使纤维素纳米纤维在分散液中均匀分散;分散液中纤维素纳米纤维与去离子水的质量比为1:100;向上述制备的分散液中加入丙烯酰胺(AM)形成均匀的混合溶液,其中纤维素纳米纤维与丙烯酰胺的质量比为4:100;再向上述制备的均匀的混合溶液中加入离子液体(ILs)搅拌均匀配制成含有纤维素纳米纤维的丙烯酰胺-离子液体(AM-ILs)的混合溶液即凝胶预聚体,所述离子液体(ILs)为1-乙烯基-3-丁基咪唑溴盐,所述离子液体在凝胶预聚体中所占的质量百分比为30 wt%;再将配好的N, N '-亚甲基双丙烯酰胺(MBA)水溶液加入到凝胶预聚体中搅拌均匀形成聚合反应混合溶液,聚合反应混合溶液中N, N '-亚甲基双丙烯酰胺(MBA)与凝胶预聚体的质量比为1.2:10;再将过硫酸铵(APS)投入聚合反应混合溶液中,过硫酸铵(APS)与纤维素纳米纤维的质量比为1:1.5,室温搅拌均匀后在冰水浴下冷却完全,然后加入N,N,N',N'-四甲基乙二胺(TEMED),搅拌均匀,超声脱除气泡后,倒入底部为黄铜、四周为聚四氟乙烯的模具中,放置20分钟形成未完全聚合状态的水凝胶即半聚合状态水凝胶;所述N,N,N',N'-四甲基乙二胺与纤维素纳米纤维之间的质量比为0.45:1;最后,将模具内的半聚合状态水凝胶连同模具一起放置于超低温冰箱,进行-80 ℃的超低温定向冷冻处理2h,然后在室温下经过2h进行完全聚合,最终形成纤维素纳米纤维增强聚离子液体水凝胶。
所制备的纤维素纳米纤维增强聚离子液体水凝胶形貌结构采用扫描电子显微镜进行观察,如附图3、附图4所示;如附图3中A图所示,加入纤维素纳米纤维后,从纵剖面上观察到均匀的片层结构,间距为15 μm,相邻层相互连接并形成网络,纤维素纳米纤维增强聚离子液体水凝胶的横截面呈现有序且相互连接的细胞网络结构(附图3中B图);为了更清楚地解释纤维素纳米纤维的增强原因,对纤维素纳米纤维增强聚离子液体水凝胶的截面进行了SEM表征;在附图4中,观察到丰富的纤维素纳米纤维,纤维素纳米纤维几乎均匀分布,在这种形态下,聚离子液体基质作为“混凝土相”,纤维素纳米纤维作为“增强相”,提高了聚离子液体水凝胶的力学性能。
实施例2
用实施例1制备的纤维素纳米纤维增强聚离子液体水凝胶进行活/死细胞染色实验:使用小鼠成纤维细胞(L929)通过活/死细胞双染色试剂盒测试纤维素纳米纤维增强聚离子液体水凝胶的细胞毒性;将L929细胞接种于装有DMEM培养基的24孔板中,在5% CO2培养箱中37℃培养12小时;将纤维素纳米纤维增强聚离子液体水凝胶置于细胞小室(Transwell)插入物中;纤维素纳米纤维增强聚离子液体水凝胶与细胞共培养24小时和48小时后,使用活/死细胞双染色试剂盒评估样品的细胞毒性;随后,在显微镜(DMI8,Leica)下观察细胞的生长状况;钙黄绿素(Calcine-AM)用于标记活细胞,而碘化丙啶(PI)用于对死细胞进行染色;具体细胞活死染的情况可见附图5;箭头处所指为死细胞,大片亮点所指为活细胞,可见死细胞的数量非常少;证明制备的纤维素纳米纤维增强聚离子液体水凝胶具有良好的生物相容性。
实施例3
用实施例1制备的纤维素纳米纤维增强聚离子液体水凝胶进行拉伸性能测试:为了直观说明纤维素纳米纤维增强聚离子液体水凝胶良好的超拉伸性能和低滞回的力学稳定性,通过万能试验机(Instron 5934,美国)对纤维素纳米纤维增强聚离子液体水凝胶循环拉伸的性能进行力学测试;制备直径为4 mm、长度为10 cm的圆柱形纤维素纳米纤维增强聚离子液体水凝胶,样品并以50 mm/min进行拉伸测试;如附图7所示,对其进行500%的应变,循环五次拉伸实验时,其滞回应变很小;当其拉伸长度达到自身2000%的时候依然保持完好,无断裂迹象,如附图6所示。
实施例4
对纤维素纳米纤维增强聚离子液体水凝胶进行抑菌性能测试:
准备浓度为1×106CFU/mL大肠杆菌(E. coli)和金黄葡萄球菌(S. aureus.)的菌液, 然后,将大肠杆菌和金黄色葡萄球菌(500 μL)转移到含有5 g 纤维素纳米纤维增强聚丙烯酰胺水凝胶(制备过程没有加入离子液体ILs)或者含有5 g 纤维素纳米纤维增强聚离子液体水凝胶的灭菌 Luria-Bertani 肉汤(LB)培养基(30 mL)中,在摇床上以 120 rpm、37oC 培养 24 h; 随后,各组取出菌液500 μL,稀释;然后,将20 μL稀释的细菌悬浮液均匀地铺在新鲜的Luria Bertani肉汤琼脂平板上;最后,37 ℃培养12h后计数菌落数,每组至少检测两次;显然,如附图8所示,与空白对照组相比,纤维素纳米纤维增强聚丙烯酰胺水凝胶组(无ILs)的细菌数量更高,说明缺少离子液体的纤维素纳米纤维增强聚丙烯酰胺水凝胶缺乏抗菌活性;相反,纤维素纳米纤维增强聚离子液体水凝胶随着离子液体添加量的增高,其对大肠杆菌和金黄色葡萄球菌上的细菌抑制率越来越高。
实施例5
对纤维素纳米纤维增强聚离子液体水凝胶进行细菌感染创面修复实验:
(1) 小鼠背部创伤模型
共12只小鼠,其种类、年龄、体格等各方面均相似, 每个鼠一个创口;首先使用外科手术的方法在雄性斯泼累格·多雷(SD)大鼠背部创建一个直径约10 mm的全层伤口, 然后在伤口上接种细菌(106 CFU/mL的大肠杆菌)2天,生产细菌感染模型;造模期间小鼠单笼饲养,放置玩具陪伴,自由饮水、进食;造模型结束后,每个小鼠创口无明显区别,细菌感染部位发白,外周发红,周围组织水肿明显。
(2) 动物分组
将12只鼠随机分为4组:
A组为对照组,给药剂量为200 μL(磷酸缓冲盐溶液)PBS/伤口,外敷; B组为商用3M抗菌凝胶( Tegaderm TM CHG 1658R,USA),外敷; C组为无离子液体(ILs)水凝胶,外敷;D组为(有ILs水凝胶)纤维素纳米纤维增强离子液体水凝胶,外敷。
(3)在伤口造模后,分别将A组、B组、C组、D组敷料涂抹或者覆盖到小鼠伤口上,并于造模后第0、3、7、14日观察每组创面情况(见图9);在第14天,加ILs的纤维素纳米纤维增强离子液体水凝胶治疗组感染创面几乎完全愈合,4个治疗组创面开放面积分别为20.3%、15.1%、9.2%、1.5%,加ILs的纤维素纳米纤维增强离子液体水凝胶组创面愈合率显著高于其他三组,表明加ILs的纤维素纳米纤维增强离子液体水凝胶组创面愈合率最高。
Claims (10)
1.一种纤维素纳米纤维增强聚离子液体水凝胶,其特征是包括聚离子液体水凝胶,纤维素纳米纤维;纤维素纳米纤维分散在聚离子液体水凝胶内。
2.根据权利要求1所述的一种纤维素纳米纤维增强聚离子液体水凝胶,其特征是所述聚离子液体水凝胶具有蜂窝状孔洞结构,蜂窝状孔洞结构的聚离子液体水凝胶中每个孔洞四周的聚离子液体水凝胶内部和表面均分布有纤维素纳米纤维。
3. 根据权利要求1所述的一种纤维素纳米纤维增强聚离子液体水凝胶,其特征是所述聚离子液体水凝胶为离子液体与丙烯酰胺在N, N '-亚甲基双丙烯酰胺作用下通过热引发自由基聚合反应形成;所述离子液体为乙烯基离子液体。
4.一种纤维素纳米纤维增强聚离子液体水凝胶的制备方法,其特征是包括以下步骤:
1)将纤维素纳米纤维分散于去离子水中配置成分散液;
2)向分散液中加入丙烯酰胺形成均匀的混合溶液;
3)向混合溶液中加入离子液体并搅拌配制成凝胶预聚体;
4)将N, N '-亚甲基双丙烯酰胺水溶液加入到凝胶预聚体中搅拌形成聚合反应混合溶液;
5)将热引发剂投入聚合反应混合溶液中,室温搅拌后在冰水浴下冷却,然后加入N,N,N',N'-四甲基乙二胺,搅拌并脱除气泡后倒入模具中,放置一定时间形成半聚合状态水凝胶;
6)将模具内的半聚合状态水凝胶连同模具一起进行定向冷冻处理,然后在室温下进行完全聚合。
5.根据权利要求4所述的一种纤维素纳米纤维增强聚离子液体水凝胶的制备方法,其特征是所述步骤1)配置的分散液中纤维素纳米纤维与去离子水的质量比为(0.5~1.5):100;所述步骤2)制备的混合溶液中纤维素纳米纤维与丙烯酰胺的质量比为(3~5):100。
6. 根据权利要求4所述的一种纤维素纳米纤维增强聚离子液体水凝胶的制备方法,其特征是所述离子液体在凝胶预聚体中所占的质量百分比为10 wt%~40 wt%。
7. 根据权利要求4所述的一种纤维素纳米纤维增强聚离子液体水凝胶的制备方法,其特征是所述聚合反应混合溶液中N, N '-亚甲基双丙烯酰胺与凝胶预聚体的质量比为(1~1.5):10。
8.根据权利要求4所述的一种纤维素纳米纤维增强聚离子液体水凝胶的制备方法,其特征是所述热引发剂为过硫酸铵和过硫酸钾中的至少一种;所述模具的底部材料比模具四周侧壁的材料具有更好的导冷效果。
9. 根据权利要求4所述的一种纤维素纳米纤维增强聚离子液体水凝胶的制备方法,其特征是所述热引发剂与纤维素纳米纤维的质量比为1: (0.5~2.5);所述冰水浴的温度为0℃~4℃;所述N,N,N',N'-四甲基乙二胺与纤维素纳米纤维之间的质量比为(0.3~0.6):1;所述模具的底部材料为黄铜或紫铜,模具四周侧壁的材料为聚四氟乙烯;所述将模具内的半聚合状态水凝胶连同模具一起进行定向冷冻处理具体为将模具内的半聚合状态水凝胶连同模具一起放置于-60 ℃~-120 ℃环境中进行定向冷冻处理。
10.根据权利要求1所述的一种纤维素纳米纤维增强聚离子液体水凝胶,其特征是适用于伤口敷料。
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