CN114045167A - 一种具有光学活性的芦丁水凝胶的制备方法 - Google Patents
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Abstract
本发明公开了一种具有光学活性的芦丁水凝胶的制备方法,属于发光材料制备技术领域。本发明以过硫酸物为引发剂,引发丙烯酸和N,N'‑亚甲基双丙烯酰胺共聚得到水凝胶,干燥后,将水凝胶浸入到芦丁溶液中,充分溶胀、吸附芦丁,从而得到芦丁水凝胶。本发明的制备方法简单、快捷、成本低。使得芦丁与水凝胶之间通过氢键作用形成芦丁水凝胶,实现了芦丁与空气的隔离,解决了芦丁易被氧化的问题。且得到的芦丁水凝胶具备光学活性,可用于光学智能材料制备,具有广阔的应用前景。
Description
技术领域
本发明属于发光材料制备技术领域,具体地说,涉及一种具有光学活性的芦丁水凝胶的制备方法。
背景技术
水凝胶是近年来出现的一类新型材料,它是由亲水聚合物形成的具有三维网络结构的功能高分子材料。高度交联的聚合物网络使水凝胶具有优异的保水性能和良好的力学、化学和生物学性能。由于水凝胶具有优异的结构性能,可以加工成各种需要的形状并赋予新的功能,因此在医药、材料、化工等领域应用广泛。
芦丁是一种常见的黄酮类化合物,属于天然产物,广泛存在于植物的根、茎、叶、花、果实中,具有抗氧化、抗肿瘤、抗炎、保护心脑血管等多种生物活性,可用于食品、化妆品、医疗卫生等行业。芦丁为槲皮素的3-O-芸香糖苷,在胃肠道中容易被破坏,限制了芦丁的临床应用。为改善其在生物体内的稳定性,同时也防止芦丁暴露在空气中被氧化,,研究人员以凝胶材料为载体对芦丁进行了剂型改革。例如,魏亚超等(PLGA-PEG-PLGA温敏水凝胶的体外释药行为[J].青岛科技大学学报(自然科学版),2014,35(02):170-173.])将曲克芦丁片包裹在PLGA-PEG-PLGA水凝胶中,达到曲克芦丁片缓释的目的。蒋亚超等(芦丁水凝胶胃漂浮片制备工艺研究[J].广州化工,2021,49(15):49-51.)将芦丁用HPMC凝胶材料包裹,制备成芦丁胃漂浮片,从而达到芦丁缓释的目的。
目前,制备芦丁凝胶材料的方法主要为物理包埋法,芦丁与凝胶之间的作用力弱,在加工、运输、储存过程中有可能发生芦丁泄漏,从而使其失去作用。因此,需要开发一种新型的芦丁凝胶材料。
发明内容
针对现有技术存在的上述问题,为加强芦丁与凝胶材料之间的相互作用,本发明的目的在于提供一种芦丁水凝胶的制备方法。
为了解决上述问题,本发明所采用的技术方案如下:
一种具有光学活性的芦丁水凝胶的制备方法,将丙烯酸类水凝胶干燥后浸入到芦丁溶液中,充分溶胀、吸附芦丁,得到所述的芦丁水凝胶。
进一步地,所述的丙烯酸类水凝胶由引发剂引发丙烯酸和N,N'-亚甲基双丙烯酰胺共聚得到。
更进一步地,所述的引发剂为过硫酸类化合物。
进一步地,所述的引发剂为过硫酸铵。
更进一步地,丙烯酸与N,N'-亚甲基双丙烯酰胺的质量比为(100~600):1。
更进一步地,丙烯酸与过硫酸类化合物的质量比为(100~300):1。
更进一步地,丙烯酸和N,N'-亚甲基双丙烯酰胺均采用体积分数20%~60%的乙醇或甲醇溶液。
更进一步地,共聚反应的条件为温度控制在40~60℃,反应时间为30~60min。
进一步地,干燥方式为冷冻干燥。
进一步地,芦丁溶液为含有芦丁的醇溶液,芦丁浓度为0.5~1.5mg·mL-1。
相比于现有技术,本发明的有益效果为:
(1)本发明制备了新型的芦丁凝胶材料,使得芦丁与水凝胶之间通过氢键作用形成芦丁水凝胶,实现了芦丁与空气的隔离,解决了芦丁易被氧化的问题。
(2)发明人意外发现,制备得到的芦丁水凝胶还具备光学活性。芦丁结构如下所示,
它具有较大的共轭体系,具有一定的聚集诱导发光效应(Aggregation-InducedEmission,AIE),但发光较弱。发明人认为,当形成芦丁水凝胶材料时,芦丁的羟基和水凝胶通过氢键相互作用,氢键的形成使得芦丁被“固定”,大大限制了芦丁分子内振动和转动,阻碍了非辐射的跃迁,体系间能量损失减小,更多的以辐射的形式释放能量,荧光发射强度显著增强。
(3)芦丁赋予水凝胶材料光学活性,水凝胶材料又易于加工,因此芦丁水凝胶材料可以用于传感器、靶向识别、光热开关等智能光学材料的制备,具有广阔的应用前景。
(4)本发明的丙烯酸类水凝胶中含有羧基,羧基可以与芦丁中的酚羟基形成氢键,作用力强,形成的芦丁水凝胶结构稳定,芦丁不易解离;丙烯酸类水凝胶的制备简单,反应条件温和,形成的水凝胶结构较强,不易破碎。
(5)本发明的制备方法简单、快捷、成本低,适于推广应用。
附图说明
图1是芦丁的红外谱图;
图2是水凝胶的红外谱图;
图3是芦丁水凝胶的红外谱图;
图4是芦丁的荧光光谱图;
图5是水凝胶的荧光光谱图;
图6是芦丁水凝胶的荧光光谱图;
图7是芦丁浓度为0.05mg·mL-1时制备的芦丁水凝胶材料的荧光光谱图;
图8是芦丁浓度为0.1mg·mL-1时制备的芦丁水凝胶材料的荧光光谱图;
图9是芦丁浓度为0.3mg·mL-1时制备的芦丁水凝胶材料的荧光光谱图。
具体实施方式
下面结合具体实施例对本发明进一步进行描述。
根据下列公式计算溶胀率:
式中:SR——水凝胶的平衡溶胀率
WS——干燥的水凝胶质量(g)
WT——溶胀平衡时水凝胶的质量(g)
实施例1
精确称取15g丙烯酸和0.075gN,N’-亚甲基双丙烯酰胺,分别溶于20mL30%乙醇溶液中,加入烧杯混合后,于60℃反应,充分搅拌,10min后,称取0.04g过硫酸铵,用5mL蒸馏水溶解,滴加至丙烯酸和N,N’-亚甲基双丙烯酰胺的混合溶液中,继续反应60min,溶液变粘稠后,停止加热,自然冷却至室温,即得清晰透明形状规则的聚丙烯酸水凝胶。
称取一定量的芦丁,将芦丁溶于50%乙醇溶液中,配制成浓度为0.5mg·mL-1溶液。将上述水凝胶切块,冷冻干燥并称重,取干燥后的水凝胶浸入到芦丁溶液中48h,充分溶胀、吸附芦丁,即得芦丁水凝胶,溶胀率为2735%。
实施例2
精确称取7.5g丙烯酸和0.03gN,N’-亚甲基双丙烯酰胺,分别溶于15mL40%乙醇溶液中,加入烧杯混合后,于50℃反应,充分搅拌,10min后,称取0.03g过硫酸铵,用5mL蒸馏水溶解,滴加至丙烯酸和N,N’-亚甲基双丙烯酰胺混合溶液中,继续反应30min,溶液变粘稠后,停止加热,自然冷却至室温,即得清晰透明形状规则的聚丙烯酸水凝胶。
称取一定量的芦丁,将芦丁溶于50%乙醇溶液中,配制成浓度为1.5mg·mL-1溶液。将上述水凝胶切块,冷冻干燥并称重,取干燥后的水凝胶浸入到芦丁溶液中48h,充分溶胀、吸附芦丁,即得芦丁水凝胶,溶胀率为2227%。
实施例3
精确称取30g丙烯酸和0.05gN,N’-亚甲基双丙烯酰胺,分别溶于25mL 50%甲醇溶液中,加入烧杯混合后,于40℃反应,充分搅拌,10min后,称取0.1g过硫酸铵,用5mL蒸馏水溶解,滴加至丙烯酸和N,N’-亚甲基双丙烯酰胺混合溶液中,继续反应40min,溶液变粘稠后,停止加热,自然冷却至室温,即得清晰透明形状规则的聚丙烯酸水凝胶。
称取一定量的芦丁,将芦丁溶于50%乙醇溶液中,配制成浓度为1mg·mL-1溶液。将上述水凝胶切块,冷冻干燥并称重,取干燥后的水凝胶浸入到芦丁溶液中48h,充分溶胀、吸附芦丁,即得芦丁水凝胶,溶胀率为2458%。
实施例4
精确称取7.5g丙烯酸和0.03g N,N’-亚甲基双丙烯酰胺,分别溶于25mL 30%乙醇醇溶液中,加入烧杯混合后,于40℃反应,充分搅拌,10min后,称取0.03g过硫酸钾,用5mL蒸馏水溶解,滴加至丙烯酸和N,N’-亚甲基双丙烯酰胺混合溶液中,反应10min左右,溶液变粘稠,开始剧烈反应,产生大量气泡并有液体溅出,有潜在的安全问题,所得水凝胶均匀度较差并含有较多气泡,未进一步制备芦丁水凝胶。
实施例5
采用聚乙烯醇类水凝胶替代丙烯酸类水凝胶进行芦丁水凝胶的制备。具体的反应过程为:称取10g聚乙烯醇,溶于70g水中,于90℃下加热搅拌,待聚乙烯完全溶解后,将样品置于-20℃,冷冻24h。取出后于室温下放置2h,再次置于-20℃冷冻,反复冷冻3-5次,即得聚乙烯醇水凝胶,制备工艺复杂,反应条件苛刻。而且由于聚乙烯醇水凝胶通过氢键作用形成,机械强度差,在室温下易于解离,不仅影响测试,而且在制备芦丁水凝胶时发生溶解,无法得到芦丁水凝胶。
实施例6
称取一定量的芦丁,将芦丁溶于50%乙醇溶液中,配制成浓度分别为0.05、0.1和0.3mg·mL-1溶液。将实施例1所得水凝胶切块,冷冻干燥并称重,取干燥后的水凝胶浸入到芦丁溶液中48h,充分溶胀、吸附芦丁,得到芦丁水凝胶。
使用荧光光谱仪对该芦丁水凝胶的发光性能进行测试,测试条件为:激发狭缝7.5nm,发射狭缝2.5nm,激发波长380nm。结果如图7~9所示,分别显示芦丁浓度为0.05、0.1、0.3mg·mL-1时制备的芦丁水凝胶材料的发光性能。由荧光发射谱图可以看出,在400-600nm处产生一荧光发射峰,但荧光强度明显比吸附0.5mg·mL-1芦丁溶液的低。
芦丁水凝胶实现芦丁与空气的隔离的理论依据:芦丁含有酚羟基,具有较强的抗氧化活性,易被氧化成醌类化合物,消耗活性氧,从而起到抗氧化的效果。在芦丁水凝胶中,芦丁中的羟基与水凝胶中的羧基(以丙烯酸类水凝胶为例)通过氢键相互作用,酚羟基不易被氧化成醌类化合物;同时,被吸附在水凝胶内部的芦丁,与空气隔离,不易接触到活性氧,更加不易被氧化。
将水凝胶、芦丁水凝胶(实施例1)冷冻干燥,采用红外光谱仪对芦丁、水凝胶、芦丁水凝胶进行结构表征。图1为芦丁的红外谱图,3348~3423cm-1为OH的伸缩振动吸收峰,2905~2935cm-1为芦丁糖的CH2伸缩振动吸收峰,1652cm-1为C=O的伸缩振动吸收峰,1598cm-1和1504cm-1为苯环的伸缩振动吸收峰,1458cm-1为CH2的剪式振动吸收峰,1361为CH3的弯曲振动吸收峰,1012~1296为C-O的伸缩振动。图2为水凝胶的红外光谱图,2000~3600cm-1为聚丙烯酸的羧基中缔合OH的特征峰与烷基的特征峰叠加形成的山峰状吸收峰,1696cm-1处为聚丙烯酸部分羧基的C=O伸缩振动吸收峰,1446cm-1和1407cm-1为聚丙烯酸部分烷烃的弯曲振动,1232cm-1和1162cm-1为聚丙烯部分的C-O键的反对称和对称伸缩振动吸收峰。图3为芦丁水凝胶的红外谱图,2000~3600cm-1为OH的伸缩振动吸收峰,其中3347cm-1和3422cm-1处的吸收峰与芦丁的羟基伸缩振动吸收峰相符,2858cm-1和2935cm-1处CH2的伸缩振动与芦丁糖的CH2伸缩振动吸收峰相近。1700cm-1处为聚丙烯酸部分羧基的C=O伸缩振动吸收峰,1650cm-1为芦丁部分C=O伸缩振动峰相符,1596cm-1和1500cm-1为芦丁部分苯环的伸缩振动吸收峰,1449cm-1和1404cm-1为聚丙烯酸部分烷烃的弯曲振动,1358cm-1为甲基的弯曲振动吸收峰,1010~1290cm-1为C-O的伸缩振动,其中,1232cm-1和1161cm-1为聚丙烯部分的C-O键的反对称和对称伸缩振动吸收峰。红外数据显示,芦丁水凝胶同时拥有芦丁和聚丙烯酸水凝胶的特征吸收峰,且部分吸收峰位移发生变化,特别是芦丁水凝胶中OH吸收峰的形状也发生变化,表明芦丁与水凝胶通过氢键作用形成芦丁水凝胶。
使用荧光光谱仪对芦丁、水凝胶和芦丁水凝胶(实施例1)的发光性能进行测试,测试条件为:激发狭缝7.5nm,发射狭缝2.5nm,激发波长380nm。结果如图4~6所示。图4为芦丁的荧光发射谱图,芦丁在380nm激发下,在400nm-600nm处产生一荧光发射峰,最大发射峰分别在465nm、486nm和530nm处。图5为水凝胶的荧光发射谱图,在400nm-600nm范围内荧光发射峰较弱,在401nm、422nm和484nm处有若干小鼓包。图6为芦丁水凝胶的荧光发射谱图,在400nm-600nm处产生一较强的荧光发射峰,最大发射峰分别在427nm、443nm、486nm和530nm处,与芦丁和水凝胶的荧光发射峰相符,且荧光强度明显增强,峰型亦发生变化,进一步表明,芦丁水凝胶中芦丁与水凝胶通过氢键相互作用,协同作用使得芦丁水凝胶具有优良的光学性能。
Claims (10)
1.一种具有光学活性的芦丁水凝胶的制备方法,其特征在于,将丙烯酸类水凝胶干燥后浸入到芦丁溶液中,充分溶胀、吸附芦丁,得到所述的芦丁水凝胶。
2.根据权利要求1所述的制备方法,其特征在于,所述的丙烯酸类水凝胶由引发剂引发丙烯酸和N,N'-亚甲基双丙烯酰胺共聚得到。
3.根据权利要求2所述的制备方法,其特征在于,所述的引发剂为过硫酸类化合物,优选为过硫酸铵。
4.根据权利要求2所述的制备方法,其特征在于,丙烯酸与N,N'-亚甲基双丙烯酰胺的质量比为(100~600):1。
5.根据权利要求2或4所述的制备方法,其特征在于,丙烯酸与引发剂的质量比为(100~300):1。
6.根据权利要求2所述的制备方法,其特征在于,共聚反应的条件为温度控制在40~60℃,反应时间为30~60min。
7.根据权利要求2所述的制备方法,其特征在于,丙烯酸和N,N'-亚甲基双丙烯酰胺均采用体积分数为20%~60%的乙醇或甲醇溶液。
8.根据权利要求7所述的制备方法,其特征在于,具体的共聚方法为:将丙烯酸溶液和N,N'-亚甲基双丙烯酰胺溶液混合,在40~60℃下反应,5~15min后加入过硫酸铵,继续反应30~60min,溶液变粘稠后,停止加热,自然冷却至室温,即得所述的芦丁水凝胶。
9.根据权利要求1所述的具有光学活性的芦丁水凝胶的制备方法,其特征在于,干燥方式为冷冻干燥。
10.根据权利要求1所述的具有光学活性的芦丁水凝胶的制备方法,其特征在于,芦丁溶液为含有芦丁的醇溶液,芦丁浓度为0.5~1.5mg·mL-1。
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