CN113372575A - 一种基于胶质多糖及纤维素衍生物温敏水凝胶及其制备方法和应用 - Google Patents
一种基于胶质多糖及纤维素衍生物温敏水凝胶及其制备方法和应用 Download PDFInfo
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Abstract
本发明公开了一种基于胶质多糖及纤维素衍生物温敏水凝胶及其制备方法和应用,利用一定配比的纤维素衍生物与胶质多糖复合形成交联的温敏水凝胶;利用大分子间范德华力、氢键等相互作用力形成了分子链间相互缠结的具有三维空间网状结构。在体温附近温度(35~37℃)能发生凝胶化转变,低于该温度为液态,而高于该温度为固态。本发明制备的胶质多糖及纤维素衍生物温敏水凝胶具有无毒无害,无刺激性,无异味,可自然降解等优点,原材料价格低廉,制备工艺简单高效,条件温和,可以在工业化生产中得到大规模的应用;可用于生物医学、化妆品等领域中,如制备医用敷料、护肤品等的载体基材。
Description
技术领域
本发明涉及生物医药材料技术领域,更具体地,涉及一种基于胶质多糖及纤维素衍生物温敏水凝胶及其制备方法和应用。
背景技术
温敏性水凝胶是一类受外部温度变化影响时,能够产生相应相态变化的智能型水凝胶。温敏水凝胶的分子中含有一定比例的亲水基团和疏水基团,温度的变化可以影响这些基团的疏水相互作用以及氢键作用,从而使凝胶的网络结构改变,导致发生体积相转变的一类凝胶,引起其相态变化的温度范围被叫做最低临界转变温度(LCST)。当外界环境低于LCST时,温敏凝胶在水溶液中溶胀,随着温度升高,达到LCST时,凝胶发生体积相变而收缩,溶胀和收缩时的体积比为溶胀比SR,所以凝胶的LCST和SR是决定其应用的关键因素,也是设计温敏凝胶的主要参数(Bokias G,et al.Polymer,2001,42:6329—6337)。
甲基纤维素是一种纤维素衍生物,其是一种非离子纤维素醚,它是通过醚化反应在纤维素中引入甲基而制成的。甲基纤维素具有独特的热胶凝性质,即在加热时形成凝胶,冷却时却又熔化,不同取代度的甲基纤维素有着不同的溶胶-凝胶转变温度,其溶胶-凝胶转变的温度范围一般为50~70℃。正因为甲基纤维素水溶液具有一定的粘稠性,和其所具有的独特的凝胶性能,它作为一种交联剂或者增稠剂被广泛应用在食品、造纸、药剂、建筑、化妆品、工业生产等行业中(Mitc hellK,etal.International Journal of Pharmaceutics,1993,100(1-3):143-154;Fu X,etal.Cement&Concrete Researc h,1996,26(4):535-538)。
甲基纤维素水溶液的凝胶转变温度会受到多方面的因素影响。一般来说,取代度越高的甲基纤维素分子水溶液凝胶转变温度就会越低;在相同浓度的情况下,分子量越小的甲基纤维素,其水溶液的凝胶转变温度越低;甲基纤维素水溶液的浓度越高,其凝胶转变温度越低,但对浓度极低(质量浓度小于等于1%)的甲基纤维素水溶液,其浓度与凝胶转变温度并没有具体的关联性(Kundu P P,et al.Polymer,2001,42(5):2015-2020)。此外,体系中所存在的无机盐离子也同样影响着其凝胶转变温度。无机离子本身多有极性,当溶液中有离子存在的时候,离子与水的吸引力会和甲基纤维素分子上羟基与水分子间的氢键竞争,导致甲基纤维素的疏水区域便更容易被暴露出来,增大了甲基纤维素的疏水性,则甲基纤维素水凝胶的溶胶-凝胶转化温度会变低(Xu,Y,etal.Langmuir.2004,20:646–652)。由于甲基纤维素水凝胶具有特殊的反向温敏性质,基于甲基纤维素温敏水凝胶体系则有着重大的研究意义。
关于通过共混法制备甲基纤维素温敏水凝胶的报道(Ning L et al.Journal ofMaterials Science Materials in Medicine,2012,23(8):1913-1919.),如Lin L设计了一组甲基纤维素接枝硬脂酸(MCS)共混纳米纤维素的温敏水凝胶,并加入磷酸盐调节水凝胶的凝胶行为。通过不同浓度比的实验后,制备出了体系凝胶化温度为34℃的温敏水凝胶体系。CN105288700A公开了一种医用温敏性水凝胶敷料及其制备方法,利用壳聚糖、羧丙基甲基纤维素、甘油、醋酸等制备温敏性水凝胶,在室温下的储藏形态是液态,可以通过喷涂方式覆盖整个创面并凝胶化。可见,这种在人体体温附近(35~37℃)能够发生凝胶化转变的温敏水凝胶具有广泛的应用前景。
发明内容
本发明的目的是提供一种基于胶质多糖及纤维素衍生物温敏水凝胶的制备方法,利用一定配比的纤维素衍生物和的胶质多糖,调控其反应条件制得一种交联水凝胶,在体温附近温度(35~37℃)能发生凝胶化转变,在低于该温度为液态,而高于该温度为固态。
本发明的又一目的是提供一种基于胶质多糖及纤维素衍生物温敏水凝胶。
本发明的另一目的是提供一种基于胶质多糖及纤维素衍生物温敏水凝胶的应用。
本发明上述目的通过以下技术方案实现:
一种基于胶质多糖及纤维素衍生物温敏水凝胶的制备方法,包括如下步骤:
S1.将纤维素衍生物于20~60℃溶解在水中,降温至0~35℃继续搅拌1~6小时,得到纤维素衍生物溶液;
S2.将胶质多糖于溶解于步骤S1所制备的纤维素衍生物溶液,于15~40℃混合均匀6~48小时,得到复合溶液,然后于0~10℃静置12~24小时;所述复合溶液的质量分数为2%~20%,其中,所述纤维素衍生物和胶质多糖的质量比为1:1~30;
S3.将步骤S2制备的水溶液于20~60℃水浴中静置2~20分钟后即可得到基于胶质多糖及纤维素衍生物温敏水凝胶。
胶质多糖是溶解于水中得到的水溶液有一定的黏稠性的多糖及其衍生物的总称。本发明利用一定配比的纤维素衍生物和胶质多糖,通过控制其用量以及反应条件,将其充分混合、分散,利用大分子间范德华力、氢键等相互作用力形成了分子链间相互缠结的具有三维空间网状结构的温敏性复合水凝胶,在体温附近温度(35~37℃)能发生凝胶化转变,在低于该温度为液态,而高于该温度为固态。。
优选地,步骤S1所述降温至0~30℃。见实施例2~4。
步骤S1所述纤维素衍生物溶液为无色透明的。
优选地,所述纤维素衍生物和胶质多糖的质量比为1:15~25。见实施例1~6。
优选地,所述纤维素衍生物为羟丙基纤维素、羟丙基甲基纤维素、甲基纤维素中的一种或几种。见实施例1~6。
优选地,所述胶质多糖为黄原胶、阿拉伯胶、果胶、海藻胶中的一种或几种。见实施例1~6。
更优选地,所述胶质多糖为果胶。见实施例1~2。
果胶多糖是一种胶质多糖,是普遍存在于自然界中各类植物细胞壁和细胞内层中的一种天然多糖,其是一种天然存在的无毒高分子聚合物,并且具有良好的乳化、增稠、稳定和胶凝等作用,因此被广泛应用于医学和食品等领域。
优选地,所述步骤S1将纤维素衍生物先于30~50℃溶解在水中。见实施例1~6。
优选地,步骤S1所述搅拌速度为200~800转/分钟。见实施例1~6。
优选地,步骤S1所述溶剂为水。见实施例1~6。
优选地,所述水为蒸馏水、去离子水、纯水或高纯水中的一种或几种。见实施例1~6。
步骤S2胶质多糖于溶解于步骤S1所制备的纤维素衍生物溶液后得到无色透明复合溶液。
本发明保护上述制备方法制得的基于胶质多糖及纤维素衍生物温敏水凝胶。
优选地,所述温敏水凝胶的凝胶化转变温度为35~37℃。见实施例1。
本发明还保护上述基于胶质多糖及纤维素衍生物温敏水凝胶在生物医学、化妆品领域中的应用。
优选地,所述温敏水凝胶在医用敷料、护肤品的载体基材中的应用。
与现有技术相比,本发明的有益效果是:
本发明利用一定配比的纤维素衍生物与胶质多糖复合形成交联的温敏水凝胶;利用大分子间范德华力、氢键等相互作用力形成了分子链间相互缠结的具有三维空间网状结构。在体温附近温度(35~37℃)能发生凝胶化转变,低于该温度为液态,而高于该温度为固态。本发明制备的胶质多糖及纤维素衍生物温敏水凝胶相较于其他体温敏感型水凝胶而言,其原材料价格更低廉,制备工艺更简单高效,条件更温和,可以在工业化生产中得到大规模的应用;本发明制备的胶质多糖及纤维素衍生物温敏水凝胶具有无毒无害,无刺激性,无异味,可自然降解等优点,可用于生物医学、化妆品领域等中,如制备医用敷料、护肤品等的载体基材,具有广泛的应用。
附图说明
图1为本发明实施例1制备方法的工艺流程图。
图2为本发明实施例1制备的冻干样品扫描电镜图。
图3为本发明实施例1制备的水凝胶样品的流变性能表征图。
图4为本发明实施例1制备的水凝胶样品的溶胀率表征图。
图5为本发明实施例1制备的水凝胶样品的稳定性表征图。
图6为负载水杨酸的胶质多糖及纤维素衍生物温敏水凝胶在PBS缓冲液(pH=7.4)中的药物水杨酸释放曲线。
具体实施方式
下面结合具体实施方式对本发明作进一步的说明,但实施例并不对本发明做任何形式的限定。除非另有说明,本发明实施例采用的原料试剂为常规购买的原料试剂。
实施例1
一种基于胶质多糖及纤维素衍生物温敏水凝胶的制备方法,包括如下步骤:
S1.称取2.381g甲基纤维素于20mL去离子水中,升温至40℃后,搅拌20分钟,移除加热装置降温至室温继续搅拌6小时,得到无色透明溶液;
S2.在S1制备得到的甲基纤维素水溶液中加入0.119g果胶,于20℃下搅拌溶解,持续搅拌12小时,溶解完成后置于4℃下静置24小时;
S3.将S2制备得到的混合溶液至于37℃下水浴加热8分钟,即可得到基于胶质多糖及纤维素衍生物温敏水凝胶。
上述实施例1制备基于胶质多糖及纤维素衍生物温敏水凝胶的制备流程图如图1所示。
上述制备的基于胶质多糖及纤维素衍生物温敏水凝胶的冻干样品的热场扫描电镜照片如图2所示,其中基于胶质多糖及纤维素衍生物温敏水凝胶的微观形貌图中显示出了明显的三维空间网络状结构,这说明制备出的样品形成了交联的水凝胶结构。
上述制备的基于胶质多糖及纤维素衍生物温敏水凝胶在不同温度下的流变行为表征图如图3所示,通过图中储能模量(G')和损耗模量(G”)的交叉点可判断样品形成水凝胶的温度(即凝胶化转变温度)为36.5℃,接近人体体温。
上述制备基于胶质多糖及纤维素衍生物温敏水凝胶的溶胀率表征图如图4所示,将制备得到的基于胶质多糖及纤维素衍生物温敏水凝胶冻干后,再置于37℃下的去离子水中吸水溶胀,每间隔一段时间取出凝胶擦干表面水分后称重计算,可以得到制备样品的溶胀率随时间的变化曲线图,由图可知,上述制备得到的复合水凝胶在约70分钟后达到了吸水溶胀平衡,其最大平衡溶胀比约为23。
上述制备得到的基于胶质多糖及纤维素衍生物温敏水凝胶在37℃条件下在水中的稳定性能测试:取1mL上述复合水凝胶溶液置于10mL离心管下端,待其在37℃下完全凝胶化后,加入9mL去离子水。将其放入37℃恒温箱中震荡,每隔一段时间,去除上方多余的去离子水,冻干剩下的凝胶并称重计算,上述制备得到的复合水凝胶的稳定性如图5所示,从图中可以看出该复合凝胶在3天左右降解了一半,在8天后降解了大部分,因此该复合凝胶可用于较短时间内有效的医疗、化妆品领域。
实施例2
一种基于胶质多糖及纤维素衍生物温敏水凝胶的制备方法,包括如下步骤:
S1.取0.500g羟丙基甲基纤维素于20mL去离子水中,升温至20℃后,搅拌10分钟,移除加热装置至于0℃冰水中降温继续搅拌2小时,得到无色透明溶液;
S2.在S1制备得到的甲基纤维素水溶液中加入0.100g果胶,于25℃下搅拌溶解,整个搅拌溶解过程持续24小时,随后降温至8℃下静置12小时;
S3.将S2制备得到的混合溶液至于40℃下水浴加热15分钟,即可得到果胶/羟丙基甲基纤维素温敏水凝胶。
实施例3
一种基于胶质多糖及纤维素衍生物温敏水凝胶的制备方法,包括如下步骤:
S1.取2.500g羟丙基纤维素于20mL去离子水中,升温至60℃后,搅拌溶解30分钟,移除加热装置降温至4℃继续搅拌5小时,得到无色透明溶液;
S2.在S1制备得到的羟丙基纤维素水溶液中加入0.500g黄原胶,30℃下搅拌溶解,持续搅拌24小时,溶解完成后置于4℃下静置24小时;
S3.将S2制备得到的混合溶液至于25℃下水浴加热5分钟,即可得到黄原胶/羟丙基纤维素温敏水凝胶。
实施例4
一种基于胶质多糖及纤维素衍生物温敏水凝胶的制备方法,包括如下步骤:
S1.取1.875g甲基纤维素于20mL去离子水中,升温至50℃后,搅拌分散,待其分散完全后,移除加热装置降温至8℃继续搅拌6小时,得到无色透明溶液;
S2.在S1制备得到的甲基纤维素水溶液中加入0.125g卡拉胶,于25℃下搅拌溶解,整个搅拌溶解过程持续24小时,溶解完成后置于4℃下静置24小时;
S3.将S2制备得到的混合溶液至于37℃下水浴加热10分钟,即可得到卡拉胶/甲基纤维素温敏水凝胶。
实施例5
一种基于胶质多糖及纤维素衍生物温敏水凝胶的制备方法,包括如下步骤:
S1.取1.500g羟丙基甲基纤维素于20mL超纯水中,升温至40℃后,搅拌溶解60分钟,移除加热装置降温至室温下继续搅拌2小时,得到无色透明溶液;
S2.在S1制备得到的羟丙基甲基纤维素水溶液中加入0.150g阿拉伯胶,于40℃下搅拌溶解,整个搅拌溶解过程持续12小时,溶解完成后置于8℃下静置12小时;
S3.将S2制备得到的混合溶液至于40℃下水浴加热7分钟,即可得到阿拉伯胶/羟丙基甲基纤维素温敏水凝胶。
实施例6
一种基于胶质多糖及纤维素衍生物温敏水凝胶的制备方法,包括如下步骤:
S1.取2.500g羟丙基甲基纤维素于20mL去离子水中,升温至40℃后,搅拌溶解30分钟,移除加热装置降温至室温下继续搅拌6小时,得到无色透明溶液;
S2.在S1制备得到的羟丙基甲基纤维素水溶液中加入0.100g海藻胶,于常温下搅拌溶解,整个搅拌溶解过程持续24小时,溶解完成后置于0℃下静置12小时;
S3.将S2制备得到的混合溶液至于30℃下水浴加热20分钟,即可得到海藻胶/羟丙基甲基纤维素温敏水凝胶。
应用
一种负载水杨酸药物的胶质多糖及纤维素衍生物温敏水凝胶的制备方法,包括如下步骤:
S1.称取2.381g甲基纤维素于20mL去离子水中,升温至40℃后,搅拌20分钟,移除加热装置降温至室温继续搅拌6小时,得到无色透明溶液;
S2.在S1制备得到的甲基纤维素水溶液中加入0.119g果胶,于20℃下搅拌溶解,持续搅拌12小时,溶解完成后置于4℃下静置24小时;
S3.在S2制备得到的混合溶液中加入0.045g水杨酸,制备出含有水杨酸质量分数为0.2%的混合溶液,至于37℃下水浴加热8分钟,即可得到负载水杨酸的胶质多糖及纤维素衍生物温敏水凝胶。
图6为上述制备的负载胶质多糖及纤维素衍生物温敏水凝胶在PBS缓冲液(pH=7.4)中的药物水杨酸释放曲线。可看到大约在释放时间为5h时达到释放平衡,水杨酸释放率为89%,表明水杨酸/果胶/MC水凝胶具有较好的缓释水杨酸的性能。
显然,本发明的上述实施例仅仅是为清楚地说明本发明所作的举例,而并非是对本发明的实施方式的限定。对于所属领域的普通技术人员来说,在上述说明的基础上还可以做出其它不同形式的变化或变动。这里无需也无法对所有的实施方式予以穷举。凡在本发明的精神和原则之内所作的任何修改、等同替换和改进等,均应包含在本发明权利要求的保护范围之内。
Claims (10)
1.一种基于胶质多糖及纤维素衍生物温敏水凝胶的制备方法,其特征在于,包括如下步骤:
S1.将纤维素衍生物于20~60℃溶解在水中,降温至0~35℃继续搅拌1~6小时,得到纤维素衍生物溶液;
S2.将胶质多糖于溶解于步骤S1所制备的纤维素衍生物溶液,于15~40℃混合均匀6~48小时,得到复合溶液,然后于0~10℃静置12~24小时;所述复合溶液的质量分数为2%~20%,其中,所述纤维素衍生物和胶质多糖的质量比为1:1~30;
S3.将步骤S2制备的水溶液于20~60℃水浴中静置2~20分钟后即可得到基于胶质多糖及纤维素衍生物温敏水凝胶。
2.根据权利要求1所述制备方法,其特征在于,所述纤维素衍生物和胶质多糖的质量比为1:15~25。
3.根据权利要求1或2所述制备方法,其特征在于,所述纤维素衍生物为羟丙基纤维素、羟丙基甲基纤维素、甲基纤维素中的一种或几种。
4.根据权利要求1所述制备方法,其特征在于,所述胶质多糖为黄原胶、阿拉伯胶、果胶、海藻胶中的一种或几种。
5.根据权利要求1所述制备方法,其特征在于,所述步骤S1将纤维素衍生物先于30~50℃溶解在水中。
6.根据权利要求1所述制备方法,其特征在于,步骤S1所述搅拌速度为200~800转/分钟。
7.根据权利要求1所述制备方法,其特征在于,步骤S1所述溶剂为水。
8.权利要求1~7任一项所述制备方法制得的基于胶质多糖及纤维素衍生物温敏水凝胶。
9.根据权利要求8所述基于胶质多糖及纤维素衍生物温敏水凝胶,其特征在于,所述温敏水凝胶的凝胶化转变温度为35~37℃。
10.权利要求8或9所述基于胶质多糖及纤维素衍生物温敏水凝胶在生物医学、化妆品领域中的应用。
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