CN112691236A - 仿生Janus型几丁质纳米纤维膜及其制备方法 - Google Patents
仿生Janus型几丁质纳米纤维膜及其制备方法 Download PDFInfo
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Abstract
本发明属于生物高分子材料,尤其涉及仿生Janus型几丁质纳米纤维膜及其制备方法。本发明的生物聚合膜分为内外两侧,膜外侧面向软组织,由抗污染的仿细胞膜甲基丙烯酰氧乙基磷酰胆碱聚合物等组成,能抑制成纤维细胞的形成;膜内侧面向骨组织,由几丁质纳米纤维组成,能提供新的骨形成。本发明与现有的多组分生物纤维膜不同,不仅提供了所需的物理屏障,而且还提供了额外的骨再生因子,在引导骨再生等组织修复医学领域具有很高的应用潜力。
Description
技术领域
本发明属于生物高分子材料,尤其涉及仿生Janus型几丁质纳米纤维膜及其制备方法。
背景技术
目前,可吸收膜有两种类型:合成可吸收膜和天然可吸收膜。可吸收膜无需二次手术,具有成本效益高和降低患者发病率的优点。现有的用于骨植入的可吸收膜往往还存在着力学性能差、免疫反应、微生物感染、愈合不良等缺点,如可水解聚酯膜和聚乳酸膜,虽可生物降解的,但它们在使用中会产生炎症反应,阻止了植入物周围的填充;也可能会产生肉芽肿性异物反应(多核巨细胞、巨噬细胞、多形核白细胞)可以出现在嵌入膜周围。
两性离子聚合物甲基丙烯酰氧乙基磷酰胆碱(MPC)是一种含有两性离子基团的丙烯酸单体,它模拟生物膜的亲水性头基,被用于开发各种医疗应用中,已被证实能够抵抗蛋白质吸附和细胞粘附。然而直接将MPC涂覆在材料表面,难以获得较高含量的磷酰胆碱基团,影响血液相容性的进一步提高;它的亲水性较强,在材料表面容易在复杂的生理环境中发生溶解,甚至脱落,具有安全隐患,需要引入可光固化基团,来阻止其从材料表面脱落;并且其机械强度差,不适合直接作为生物医用的高分子膜材料。
发明内容
针对上述现有技术的不足,本发明提供了仿生Janus型几丁质纳米纤维膜的制备方法,目的是为了解决现有技术中用于骨植入的可吸收膜存在着力学性能差、免疫反应、微生物感染、愈合不良等缺点;以及够抵抗蛋白质吸附和细胞粘附的两性离子聚合物MPC由于机械强度差,无法直接作为生物医用的高分子膜材料的技术问题。本发明还提供了利用上述方法制备的仿生Janus型几丁质纳米纤维膜。
本发明提供的仿生Janus型几丁质纳米纤维膜的制备方法,具体技术方案如下:
仿生Janus型几丁质纳米纤维膜的制备方法,包括如下步骤:
S1,将几丁质溶于氢氧化钠中,在150℃下搅拌5-20h,冷却后,离心并用去离子水洗涤多次,获得混合物,将所述混合物用去离子水进行稀释,滴加醋酸调整pH,获得混合物溶液,选取几丁质制造纳米纤维膜,因为其具有良好的生物相容性、生物降解性和粘膜粘附性,有促进成骨细胞粘附和增殖的能力;
S2,将步骤S1中的混合物溶液进行研磨和透析,在-80℃下冷冻干燥24-72小时,获得冻干几丁质纳米纤维;
S3,将步骤S2中的冻干几丁质纳米纤维重新溶解在去离子水中,并使用超声波振荡使其均质化后,将几丁质纳米纤维悬浮液倒入平皿中,在烘箱中干燥,获得几丁质纳米纤维膜;
S4,将甲基丙烯酰氧乙基磷酰胆碱和甲基丙烯酰氧丙基三甲氧基硅溶解在异丙醇-四氢呋喃,获得单体溶液;将浓度为1%的引发剂偶氮异丁腈溶解在四氢呋喃中,获得引发剂溶液,MPC具有良好的血液相容性、组织相容性、亲水性等特殊性能,MPC可形成仿细胞膜结构,形成防污层;
S5,将步骤S4中的部分引发剂溶液和异丙醇加入三颈烧瓶中,在80℃下进行油浴,将剩余部分的引发剂溶液与步骤S4中的单体溶液混合控制速度在3-4h滴加到反应瓶中,反应结束后,用乙醚反复沉淀多次,除去上清液,过滤分离聚合物,再真空干燥处理,获得二元共聚物;
S6,将步骤S5中的二元共聚物溶解在乙醇中制备共聚物溶液,将共聚物溶液少量多次缓慢涂抹在步骤S3中的几丁质纳米纤维膜上,溶剂蒸发后,获得复合膜;
S7,将步骤S6中的复合膜在真空室温条件下保持10-20小时,再在100-200℃稳定1-3小时,获得仿生Janus型几丁质纳米纤维膜。再在100-200℃高温下稳定1-3小时,其目的为促进TSMA部分的-Si-(OCH3)3基团与几丁质的羟基(-OH)和胺(-NH2)基团之间形成硅烷键(-Si-O-)。
在某些实施方式中,在步骤S1中,所述几丁质中乙酰基的含量为90-100%,从实验效果和经济层面上考虑,优选98%;所述混合物用去离子水稀释至1-2%;所述醋酸的质量浓度为35%-40%,所述pH调整为3.5-4.5。
在某些实施方式中,在步骤S2中,所述研磨为采用磨床以1000-3000rpm的转速研磨;所述透析为用透析膜在4℃的去离子水中透析。
在某些实施方式中,在步骤S3中,所述几丁质纳米纤维悬浮液倒入直径60mm的平皿中,所述每个平皿的倾倒量为10-30mL;所述烘箱温度为30℃,所述干燥的时间为8-36小时。
在某些实施方式中,在步骤S4中,所述甲基丙烯酰氧乙基磷酰胆碱(MPC)的分子量为5-50万;所述甲基丙烯酰氧丙基三甲氧基硅(TSMA)的摩尔浓度为10-50%;所述异丙醇-四氢呋喃中,异丙醇与四氢呋喃的体积比为5-10:1;所述单体溶液的浓度为10-30mg/mL。TSMA易水解,与MPC形成聚合物可以增强其对物质的粘结力,提高复合材料机械性能。TSMA的摩尔浓度优化比例为20moL%的TSMA,因为聚合中较高的TSMA摩尔含量(>20%)易产生不溶性共聚物。
在某些实施方式中,在步骤S5中,所述上清液采用真空探针去除;所述真空干燥处理的温度为30℃,时间为18-36小时。
在某些实施方式中,在步骤S6中,所述乙醇的浓度为8-15mg/ml;所述共聚物溶液以50-200μL/min的速度缓慢涂抹在几丁质纳米纤维膜上。
在某些实施方式中,所述去离子水级别高于等于EW-Ⅲ,细菌含量低于等于100cfu/mL。
本发明还提供了根据上述方法制备的仿生Janus型几丁质纳米纤维膜。
本发明具有以下有益效果:本发明的制备方法以几丁质为原料,采用部分脱乙酰和湿法研磨的方法制备出几丁质纳米纤维材料。以甲基丙烯酸甲酯(MPC)和甲基丙烯酰氧丙基三甲氧基硅(TSMA)为原料,采用无规共聚的方法合成了仿细胞膜防污层-PMT共聚物(MPC-co-TSMA)。本发明制备的仿生Janus型几丁质纳米纤维膜将几丁质纳米纤维和含磷酰胆碱的二元共聚物(PMT共聚物)结合引导骨再生,综合了两者材料的优点,具有双面使用性。膜外侧面向软组织,由PMT共聚物层组成,起到屏障作用,能抑制成纤维细胞的形成,以及抑制成纤维细胞或上皮细胞的迁移,从而加速创伤的愈合;膜内侧面向骨组织,由几丁质纳米纤维组成,成骨细胞增殖和分化,能提供新的骨形成。从而与现有的多组分辅助剂不同,这不仅提供了所需的物理屏障,而且还提供了额外的再生因子。
附图说明
图1是本发明提供的仿生Janus型几丁质纳米纤维膜的制备方法的流程图;
图2是本发明实施例1提供的仿生Janus型几丁质纳米纤维膜的断层扫描电镜图;
图3是本发明实施例1提供的仿生Janus型几丁质纳米纤维膜的断层扫描电镜图。
具体实施方式
为使本发明的目的、技术方案和优点更加清楚明白,以下结合具体实施例,并参照附图1-3,对本发明进一步详细说明。
实施例1
本实施例提供的仿生Janus型几丁质纳米纤维膜的制备方法,具体技术方案如下:
仿生Janus型几丁质纳米纤维膜的制备方法,包括如下步骤:
S1,将几丁质(本实施例的几丁质中乙酰基含量为98%)溶于浓度为20%的NaOH中,在150℃下搅拌5h,冷却后,离心并用去离子水洗涤多次,获得混合物,将所述混合物用去离子水(级别不低于EW-Ⅲ,细菌含量不高于100cfu/mL)稀释成浓度为1.5%的混合物溶液,接着滴加质量浓度为35%的醋酸使该混合物溶液pH值维持在4。
S2,采用高性能磨床以1500rpm的转速研磨步骤S1中的混合物溶液进行研磨,然后用透析膜在4℃的去离子水中透析,并将透析后的溶液在-80℃下冷冻干燥24小时,获得冻干几丁质纳米纤维。
S3,将步骤S2中的冻干几丁质纳米纤维重新溶解在去离子水中,并使用超声波振荡使其均质化后,将几丁质纳米纤维悬浮液倒入直径60mm的平皿中,每个平皿的倾倒量为20mL,在30℃烘箱中干燥24小时,获得几丁质纳米纤维膜,即ChN膜。
S4,MPC和20%TSMA溶解在异丙醇-四氢呋喃(iPA-THF,异丙醇与四氢呋喃的体积比为5:1)中制备20mg/mL的单体溶液。将浓度为1%的引发剂偶氮异丁腈(AIBN)溶解在THF中,获得引发剂溶液。
S5,将步骤S4中的1/3的引发剂溶液和异丙醇加入三颈烧瓶中,在80℃下进行油浴,将剩余的2/3部分的引发剂溶液与步骤S4中的单体溶液混合控制速度在3-4h滴加到反应瓶中,反应结束后,用乙醚反复沉淀3次,用真空探针除去上清液,过滤分离聚合物,再在30℃下真空干燥24小时,获得二元共聚物(PMT共聚物)。
S6,将步骤S5中的PMT共聚物溶解在浓度为10mg/ml的乙醇中制备PMT溶液,将PMT溶液以100μL/min的速度缓慢涂抹在步骤S3中的几丁质纳米纤维膜上,溶剂蒸发后,从而在几丁质层上形成均匀的PMT层,获得复合膜。
S7,将步骤S6中的复合膜在真空室温条件下保持12小时,再在200℃稳定1小时,获得仿生Janus型几丁质纳米纤维膜。
本实施例中使用的乙醇、乙醚为药用乙醇、药用乙醚,能与多数有机溶剂混溶,先使用乙醇溶解再使用乙醚洗涤沉淀是为了带走更多的水分,除去未反应的单体和残留的引发剂,使其能快速干燥。
本实施例还提供了利用上述方法制备的仿生Janus型几丁质纳米纤维膜,结构如图2-3所示。
实施例2
本实施例提供的仿生Janus型几丁质纳米纤维膜的制备方法,具体技术方案如下:
仿生Janus型几丁质纳米纤维膜的制备方法,包括如下步骤:
S1,将40g的几丁质(本实施例的几丁质中乙酰基含量为90%)溶于浓度为20%的800mL NaOH中,在150℃下搅拌10h,冷却后,离心并用去离子水洗涤多次,获得混合物,将所述混合物用去离子水(级别不低于EW-Ⅲ,细菌含量不高于100cfu/mL)稀释成浓度为1.5%的混合物溶液,接着滴加质量浓度为40%的醋酸使该混合物溶液pH值维持在4。
S2,采用高性能磨床以2000rpm的转速研磨步骤S1中的混合物溶液进行研磨,然后用透析膜在4℃的去离子水中透析,并将透析后的溶液在-80℃下冷冻干燥36小时,获得冻干几丁质纳米纤维。
S3,将步骤S2中的冻干几丁质纳米纤维重新溶解在去离子水中,并使用超声波振荡使其均质化后,将几丁质纳米纤维悬浮液倒入直径60mm的平皿中,每个平皿的倾倒量为10mL,在30℃烘箱中干燥12小时,获得几丁质纳米纤维膜,即ChN膜。
S4,MPC和20%TSMA溶解在异丙醇-四氢呋喃(iPA-THF,异丙醇与四氢呋喃的体积比为8:1)中制备28mg/mL的单体溶液。将浓度为1%的引发剂偶氮异丁腈(AIBN)溶解在THF中,获得引发剂溶液。
S5,将步骤S4中的1/3的引发剂溶液和异丙醇加入三颈烧瓶中,在80℃下进行油浴,将剩余的2/3部分的引发剂溶液与步骤S4中的单体溶液混合控制速度在3-4h滴加到反应瓶中,反应结束后,用乙醚反复沉淀3次,用真空探针除去上清液,过滤分离聚合物,再在30℃下真空干燥24小时,获得二元共聚物(PMT共聚物)。
S6,将步骤S5中的PMT共聚物溶解在浓度为10mg/ml的乙醇中制备PMT溶液,将PMT溶液以100μL/min的速度缓慢涂抹在步骤S3中的几丁质纳米纤维膜上,溶剂蒸发后,从而在几丁质层上形成均匀的PMT层,获得复合膜。
S7,将步骤S6中的复合膜在真空室温条件下保持12小时,再在150℃稳定1小时,获得仿生Janus型几丁质纳米纤维膜。
本实施例中使用的乙醇、乙醚为药用乙醇、药用乙醚,能与多数有机溶剂混溶,先使用乙醇溶解再使用乙醚洗涤沉淀是为了带走更多的水分,除去未反应的单体和残留的引发剂,使其能快速干燥。
本实施例还提供了利用上述方法制备的仿生Janus型几丁质纳米纤维膜。
实施例3
本实施例提供的仿生Janus型几丁质纳米纤维膜的制备方法,具体技术方案如下:
仿生Janus型几丁质纳米纤维膜的制备方法,包括如下步骤:
S1,将几丁质(本实施例的几丁质中乙酰基含量为100%)溶于浓度为20%的NaOH中,在150℃下搅拌20h,冷却后,离心并用去离子水洗涤多次,获得混合物,将所述混合物用去离子水(级别不低于EW-Ⅲ,细菌含量不高于100cfu/mL)稀释成浓度为1%的混合物溶液,接着滴加质量浓度为38%的醋酸使该混合物溶液pH值维持在4.5。
S2,采用高性能磨床以1000rpm的转速研磨步骤S1中的混合物溶液进行研磨,然后用透析膜在4℃的去离子水中透析,并将透析后的溶液在-80℃下冷冻干燥72小时,获得冻干几丁质纳米纤维。
S3,将步骤S2中的冻干几丁质纳米纤维重新溶解在去离子水中,并使用超声波振荡使其均质化后,将几丁质纳米纤维悬浮液倒入直径60mm的平皿中,每个平皿的倾倒量为30mL,在30℃烘箱中干燥36小时,获得几丁质纳米纤维膜,即ChN膜。
S4,MPC和10%TSMA溶解在异丙醇-四氢呋喃(iPA-THF,异丙醇与四氢呋喃的体积比为10:1)中制备10mg/mL的单体溶液。将浓度为1%的引发剂偶氮异丁腈(AIBN)溶解在THF中,获得引发剂溶液。
S5,将步骤S4中的1/3的引发剂溶液和异丙醇加入三颈烧瓶中,在80℃下进行油浴,将剩余的2/3部分的引发剂溶液与步骤S4中的单体溶液混合控制速度在3-4h滴加到反应瓶中,反应结束后,用乙醚反复沉淀3次,用真空探针除去上清液,过滤分离聚合物,再在30℃下真空干燥18小时,获得二元共聚物(PMT共聚物)。
S6,将步骤S5中的PMT共聚物溶解在浓度为8mg/ml的乙醇中制备PMT溶液,将PMT溶液以50μL/min的速度缓慢涂抹在步骤S3中的几丁质纳米纤维膜上,溶剂蒸发后,从而在几丁质层上形成均匀的PMT层,获得复合膜。
S7,将步骤S6中的复合膜在真空室温条件下保持10小时,再在100℃稳定3小时,获得仿生Janus型几丁质纳米纤维膜。
本实施例中使用的乙醇、乙醚为药用乙醇、药用乙醚,能与多数有机溶剂混溶,先使用乙醇溶解再使用乙醚洗涤沉淀是为了带走更多的水分,除去未反应的单体和残留的引发剂,使其能快速干燥。
本实施例还提供了利用上述方法制备的仿生Janus型几丁质纳米纤维膜。
实施例4
本实施例提供的仿生Janus型几丁质纳米纤维膜的制备方法,具体技术方案如下:
仿生Janus型几丁质纳米纤维膜的制备方法,包括如下步骤:
S1,将几丁质(本实施例的几丁质中乙酰基含量为90%)溶于浓度为20%的NaOH中,在150℃下搅拌20h,冷却后,离心并用去离子水洗涤多次,获得混合物,将所述混合物用去离子水(级别不低于EW-Ⅲ,细菌含量不高于100cfu/mL)稀释成浓度为2%的混合物溶液,接着滴加质量浓度为38%的醋酸使该混合物溶液pH值维持在3.5。
S2,采用高性能磨床以3000rpm的转速研磨步骤S1中的混合物溶液进行研磨,然后用透析膜在4℃的去离子水中透析,并将透析后的溶液在-80℃下冷冻干燥72小时,获得冻干几丁质纳米纤维。
S3,将步骤S2中的冻干几丁质纳米纤维重新溶解在去离子水中,并使用超声波振荡使其均质化后,将几丁质纳米纤维悬浮液倒入直径60mm的平皿中,每个平皿的倾倒量为10mL,在30℃烘箱中干燥8小时,获得几丁质纳米纤维膜,即ChN膜。
S4,MPC和50%TSMA溶解在异丙醇-四氢呋喃(iPA-THF,异丙醇与四氢呋喃的体积比为10:1)中制备30mg/mL的单体溶液。将浓度为1%的引发剂偶氮异丁腈(AIBN)溶解在THF中,获得引发剂溶液。
S5,将步骤S4中的1/3的引发剂溶液和异丙醇加入三颈烧瓶中,在80℃下进行油浴,将剩余的2/3部分的引发剂溶液与步骤S4中的单体溶液混合控制速度在3-4h滴加到反应瓶中,反应结束后,用乙醚反复沉淀3次,用真空探针除去上清液,过滤分离聚合物,再在30℃下真空干燥18小时,获得二元共聚物(PMT共聚物)。
S6,将步骤S5中的PMT共聚物溶解在浓度为15mg/ml的乙醇中制备PMT溶液,将PMT溶液以200μL/min的速度缓慢涂抹在步骤S3中的几丁质纳米纤维膜上,溶剂蒸发后,从而在几丁质层上形成均匀的PMT层,获得复合膜。
S7,将步骤S6中的复合膜在真空室温条件下保持20小时,再在100℃稳定3小时,获得仿生Janus型几丁质纳米纤维膜。
本实施例中使用的乙醇、乙醚为药用乙醇、药用乙醚,能与多数有机溶剂混溶,先使用乙醇溶解再使用乙醚洗涤沉淀是为了带走更多的水分,除去未反应的单体和残留的引发剂,使其能快速干燥。
本实施例还提供了利用上述方法制备的仿生Janus型几丁质纳米纤维膜。
上述仅本发明较佳可行实施例,并非是对本发明的限制,本发明也并不限于上述举例,本技术领域的技术人员,在本发明的实质范围内,所作出的变化、改型、添加或替换,也应属于本发明的保护范围。
Claims (9)
1.仿生Janus型几丁质纳米纤维膜的制备方法,其特征在于,包括如下步骤:
S1,将几丁质溶于氢氧化钠中,在150℃下搅拌5-20h,冷却后,离心并用去离子水洗涤多次,获得混合物,将所述混合物用去离子水进行稀释,滴加醋酸调整pH,获得混合物溶液;
S2,将步骤S1中的混合物溶液进行研磨和透析,在-80℃下冷冻干燥24-72小时,获得冻干几丁质纳米纤维;
S3,将步骤S2中的冻干几丁质纳米纤维重新溶解在去离子水中,并使用超声波振荡使其均质化后,将几丁质纳米纤维悬浮液倒入平皿中,在烘箱中干燥,获得几丁质纳米纤维膜;
S4,将甲基丙烯酰氧乙基磷酰胆碱和甲基丙烯酰氧丙基三甲氧基硅溶解在异丙醇-四氢呋喃,获得单体溶液;将浓度为1%的引发剂偶氮异丁腈溶解在四氢呋喃中,获得引发剂溶液;
S5,将步骤S4中的部分引发剂溶液和异丙醇加入三颈烧瓶中,在80℃下进行油浴,将剩余部分的引发剂溶液与步骤S4中的单体溶液混合控制速度在3-4h滴加到反应瓶中,反应结束后,用乙醚反复沉淀多次,除去上清液,过滤分离聚合物,再真空干燥处理,获得二元共聚物;
S6,将步骤S5中的二元共聚物溶解在乙醇中制备共聚物溶液,将共聚物溶液少量多次缓慢涂抹在步骤S3中的几丁质纳米纤维膜上,溶剂蒸发后,获得复合膜;
S7,将步骤S6中的复合膜在真空室温条件下保持10-20小时,再在100-200℃稳定1-3小时,获得仿生Janus型几丁质纳米纤维膜。
2.根据权利要求1所述的仿生Janus型几丁质纳米纤维膜的制备方法,其特征在于,在步骤S1中,所述几丁质中乙酰基的含量为90-100%;所述混合物用去离子水稀释至1-2%;所述醋酸的质量浓度为35%-40%,所述pH调整为3.5-4.5。
3.根据权利要求1所述的仿生Janus型几丁质纳米纤维膜的制备方法,其特征在于,在步骤S2中,所述研磨为采用磨床以1000-3000rpm的转速研磨;所述透析为用透析膜在4℃的去离子水中透析。
4.根据权利要求1所述的仿生Janus型几丁质纳米纤维膜的制备方法,其特征在于,在步骤S3中,所述几丁质纳米纤维悬浮液倒入直径60mm的平皿中,所述每个平皿的倾倒量为10-30mL;所述烘箱温度为30℃,所述干燥的时间为8-36小时。
5.根据权利要求1所述的仿生Janus型几丁质纳米纤维膜的制备方法,其特征在于,在步骤S4中,所述甲基丙烯酰氧乙基磷酰胆碱的分子量为5-50万;所述甲基丙烯酰氧丙基三甲氧基硅的摩尔浓度为10-50%;所述异丙醇-四氢呋喃中,异丙醇与四氢呋喃的体积比为5-10:1;所述单体溶液的浓度为10-30mg/mL。
6.根据权利要求1所述的仿生Janus型几丁质纳米纤维膜的制备方法,其特征在于,在步骤S5中,所述上清液采用真空探针去除;所述真空干燥处理的温度为30℃,时间为18-36小时。
7.根据权利要求1所述的仿生Janus型几丁质纳米纤维膜的制备方法,其特征在于,在步骤S6中,所述乙醇的浓度为8-15mg/ml;所述共聚物溶液以50-200μL/min的速度缓慢涂抹在几丁质纳米纤维膜上。
8.根据权利要求1所述的仿生Janus型几丁质纳米纤维膜的制备方法,其特征在于,所述去离子水级别高于等于EW-Ⅲ,细菌含量低于等于100cfu/mL。
9.仿生Janus型几丁质纳米纤维膜,其特征在于,根据权利要求1-8任一项所述的方法制备的仿生Janus型几丁质纳米纤维膜。
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