CN108187644A - 乳化-光聚合制备微米级含酶凝胶微球的方法及应用 - Google Patents
乳化-光聚合制备微米级含酶凝胶微球的方法及应用 Download PDFInfo
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Abstract
本发明涉及一种乳化‑光聚合制备微米级含酶凝胶微球的方法,及其协同利用凝胶微球的吸附和催化特性去除模拟废水中的双酚A的应用。本发明采用乳化‑光聚合法,将PEG溶液和酶溶液组成的水相经过振荡,使之在矿物油中充分分散成液滴状,紫外光照射时,受到光引发剂的引发,聚合成微米级的含酶凝胶微球,再用戊二醛进行交联以提高酶的稳定性。本发明制备的微球可以自然沉淀分离,方便再次回收利用;水相可以100%转化成固体颗粒材料,且酶的包埋率可以达到100%;对双酚A具有较强的吸附能力,15min后上清液中检测不出双酚A,并且微球中包埋的酶可进一步对双酚A进行酶催化降解,提高凝胶球的重复利用次数;产物不会从凝胶球中泄露,防止二次污染。
Description
技术领域
本发明属于雌激素去除技术领域,具体涉及一种乳化-光聚合制备微米级含酶凝胶微球的方法,及其协同利用凝胶微球的吸附和催化特性去除模拟废水中的双酚A的应用。
背景技术
环境内分泌干扰物的污染问题是当前环境领域的研究热点,环境内分泌干扰物的分析检测方法、污染现状、环境化学行为、作用机制及环境毒理的研究工作也迅速开展,而环境治理方面研究的比较少,因而对水体中内分泌干扰物的去除变得日趋紧迫。近年来,国内外对于环境水中雌激素的处理方法主要有微生物降解法、吸附法、电化学法、光降解法等。这些方法在处理过程中均有显著效果,有些方法也可用于实际应用。然而,从经济性、技术性和使用性方面考虑,这些方法仍然存在一定的缺陷,如运行管理要求高、成本高、操作复杂、净化不彻底、产生有毒的副产物、以及处理范围狭窄等。因此,需研发一种更加快速、便捷、低成本且无有毒副产物产生的处理方法。
漆酶(laccase)是一种含铜的多酚氧化酶,广泛存在于真菌、植物和昆虫中。它可以在分子氧存在条件下催化氧化酚类物质,使其羟基氧化成游离自由基或醌类物质,继而通过聚合形成难溶于水的高分子化合物而沉淀。由于漆酶易于提取、来源广,因此近年来国外众多学者对于漆酶处理环境雌激素的研究特别关注。但是,液相酶去除水溶液中的污染物存在以下缺点:1、酶溶解在溶液中造成二次污染;2、酶与形成的醌反应而失活;3、无法重新利用;4、处理成本高。基于此,需要通过酶的固定化技术提高它的稳定性以及可再利用性,克服溶解酶的缺点,同时尽可能的保留酶原有的活性,这样就可以提高酶对底物的处理效率、延长酶的使用寿命和降低处理成本。综上所述,如何获得高效、稳定的固定化酶是漆酶处理雌激素研究的新方向。
发明内容
本发明的目的就在于针对上述现有技术的不足,提供一种乳化-光聚合制备微米级含酶凝胶微球的方法及应用。
本发明采用乳化-光聚合法,将PEG溶液和酶溶液组成的水相经过振荡,使之在矿物油中充分分散成液滴状,紫外光照射时,受到光引发剂的引发,聚合成微米级的含酶凝胶微球,再用戊二醛进行交联以提高酶的稳定性。
一种乳化-光聚合制备微米级含酶凝胶微球的方法,包括以下步骤:
A、油相为1mL的矿物油,内含1%的乳化剂Span 80和1%的非离子型去污剂Tween20;水相200μL,其中PEG混合液133μL(PEGDA/PEGMA=4:1),漆酶溶液67μL;
B、在水相中加入1%的光引剂HMPP,PEG、漆酶溶液和光引剂充分混匀后滴入到油相中,振荡10s后进行紫外光照3min;
C、得到的固体材料进行充分的清洗,直至油相和光引剂全部洗掉,再用0.5%的交联剂戊二醛进行交联,然后存放于4℃的冰箱进行保存。
所述漆酶溶液浓度为100mg/mL。
本发明的微米级含酶凝胶微球可应用于雌激素去除,其对双酚A具有吸附聚集的作用,能够协同利用凝胶微球的吸附和催化特性去除模拟废水中的双酚A。
与现有技术相比,本发明的有益效果在于:
1、本发明制备的微球粒径范围为几百微米,可以自然沉淀分离,方便再次回收利用;2、水相可以100%转化成固体颗粒材料,且酶的包埋率可以达到100%;3、对双酚A具有较强的吸附能力,15min后上清液中检测不出双酚A,说明双酚A全部被凝胶微球吸附,并且微球中包埋的酶可进一步对双酚A进行酶催化降解,提高凝胶球的重复利用次数;4、产物不会从凝胶球中泄露,防止二次污染。
附图说明
图1为乳化—光聚合制备微米级含酶凝胶微球的方法的示意图;
图2为含酶凝胶微球的外观;
图3为含酶凝胶微球的粒径分布图;
图4为含酶凝胶微球对模拟BPA废水的酶降解过程图;
图5为含酶凝胶微球对不同浓度的BPA废水的酶降解效率图。
具体实施方式
下面结合实施例对本发明作进一步说明,但本发明不仅限于此。
实施例1
A、油相为1mL的矿物油,内含1%的乳化剂Span 80和1%的非离子型去污剂Tween20;水相200μL,其中PEG混合液占133μL(PEGDA/PEGMA=4:1),漆酶溶液浓度100mg/mL,共67μL;
B、在水相中加入1%的光引剂HMPP,PEG、漆酶溶液和光引剂充分混匀后滴入到油相中,振荡10s后进行紫外光照3min;
C、得到的固体材料进行充分的清洗,直至油相和光引剂全部洗掉。
称取制备的材料30mg,加入25mg/L的双酚A溶液,于室温下进行反应,10h后BPA的酶降解能力在pH3、pH5和pH7条件下分别达到56%、66%和60%。
实施例2
A、油相为1mL的矿物油,内含1%的Span 80和1%的非离子型去污剂Tween 20;水相200μL,其中PEG混合液占133μL(PEGDA/PEGMA=4:1),Tris-HCl 67μL;
B、在PEG混合溶液中加入1%的光引剂HMPP,充分混匀后滴入到油相中,振荡10s后进行紫外光照3min;
C、得到的固体材料进行充分的清洗,直至油相和光引剂全部洗掉。
称取制备的材料30mg,加入pH 5的25~200mg/L的双酚A溶液0.5mL,于室温下进行反应,15min后上清液中检测不到双酚A,即双酚A被全部吸附到了凝胶微球上,说明材料对双酚A这种污染物具有较好的富集作用。
实施例3
A、油相为1mL的矿物油,内含1%的Span 80和1%的非离子型去污剂Tween 20;水相200μL,其中PEG混合液占133μL(PEGDA/PEGMA=4:1),含酶溶液(失活的酶对于对照试验)67μL;
B、在水相中加入1%的光引剂HMPP,PEG、酶溶液和光引剂充分混匀后滴入到油相中,振荡10s后进行紫外光照3min;
C、得到的固体材料进行充分的清洗,直至油相和光引剂全部洗掉。
称取制备的材料30mg,加入pH 5的25mg/L的双酚A溶液0.5mL,于室温下进行反应,每1h后移除上清液,加入新鲜的双酚A溶液,循环14次后,含酶微球的重复利用性较好,且产生的酶降解产物“困”在微球中,不会造成二次污染。
如图2-图5所示,本发明所制备的含酶凝胶微球为圆形,微米级,表面粗糙,其粒径主要集中在250μm左右,酶的包埋率可以达到100%,光聚合转化率达到100%;其对双酚A具有吸附聚集的作用,且吸附作用和酶的催化特性对协同去除双酚A具有较好的效果。协同利用凝胶微球对双酚A的吸附和酶催化特性,不仅可以快速的富集污染物,而且微球中酶的作用使得双酚A发生降解,释放了吸附位点,方便了重复利用,并且产生的聚合沉淀“困”在凝胶微球中,不会发生二次污染。
Claims (3)
1.一种乳化-光聚合制备微米级含酶凝胶微球的方法,其特征在于,包括以下步骤:
A、油相为1mL的矿物油,内含1%的乳化剂Span 80和1%的非离子型去污剂Tween 20;水相200μL,其中PEG混合液133μL(PEGDA/PEGMA=4:1),漆酶溶液67μL;
B、在水相中加入1%的光引剂HMPP,PEG、漆酶溶液和光引剂充分混匀后滴入到油相中,振荡10s后进行紫外光照3min;
C、得到的固体材料进行充分的清洗,直至油相和光引剂全部洗掉,再用0.5%的交联剂戊二醛进行交联,然后存放于4℃的冰箱进行保存。
2.根据权利要求1所述的一种乳化-光聚合制备微米级含酶凝胶微球的方法,其特征在于:所述漆酶溶液浓度为100mg/mL。
3.根据权利要求1所述的一种乳化-光聚合制备微米级含酶凝胶微球的应用,其特征在于:用于雌激素去除,其对双酚A具有吸附聚集的作用,能够协同利用凝胶微球的吸附和催化特性去除模拟废水中的双酚A。
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