CN105498559A - 基于功能蛋白的复合膜 - Google Patents

基于功能蛋白的复合膜 Download PDF

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CN105498559A
CN105498559A CN201511008292.4A CN201511008292A CN105498559A CN 105498559 A CN105498559 A CN 105498559A CN 201511008292 A CN201511008292 A CN 201511008292A CN 105498559 A CN105498559 A CN 105498559A
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functional protein
aquaporin
composite membrane
active layer
solution
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CN105498559B (zh
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胡云霞
刘中云
戚龙斌
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YANTAI LVSHUIFU MEMBRANE MATERIAL Ltd.
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Yantai Institute of Coastal Zone Research of CAS
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Abstract

本发明涉及基于功能蛋白的复合膜及其制备方法，所述的复合膜由镶嵌功能蛋白的聚电解质活性层和支撑层组成，其中功能蛋白作为功能单元，在层层组装制备聚电解质活性层的过程中，直接镶嵌到形成的网络结构中，并通过交联固化提高其在活性层中的结合牢固度。所述的制备方法操作过程简单，提高了功能蛋白在复合膜中的嵌入量。所述的功能蛋白复合膜，在水处理和膜分离领域中具有广阔的应用前景。

Description

基于功能蛋白的复合膜
技术领域
本发明涉及功能蛋白复合膜技术领域，具体涉及一种由含功能蛋白的聚电解质活性层组成的复合膜及制备方法，可用于海水淡化、污水处理、染料脱除、食品加工、生物医药和疾病治疗等领域。
背景技术
淡水资源极度匮乏、能源缺口迅速扩大和环境污染日趋严重是当今制约人类文明健康及可持续发展的重要瓶颈。膜分离技术因其高效、节能、环保等优点，在污水处理、海水淡化等领域受到广泛应用。然而目前分离膜在制备及应用过程中，其通量和截留率之间存在“trade-off”效应，即提高分离膜的通量会降低膜的分离精度，而提高膜的截留率又会降低膜的通量。因此，如何打破传统分离膜存在的“trade-off”效应，同时提高膜的通量和截留率，制备高性能分离膜成为当今分离膜领域的前沿课题。
在神奇的自然界，构成生命体基本功能单元的细胞膜给获得高渗透性和高选择性的分离膜提供了有价值的启示。20世纪80年代中期，美国科学家彼得·阿格雷发现了细胞膜水通道蛋白蛋白，探明了水以高通量与高选择性方式透过细胞膜并非是简单的自由扩散过程，而是通过细胞膜上的一类功能蛋白完成的。具体来说，一个水通道蛋白AQP1分子每秒钟可以传输的水分子数量可高达30亿个（大约1014cm3/s），同时能够阻挡其它几乎所有的小分子和离子等组分（包括质子H+）。这一发现为制备高水通量分离膜提供了新思路。2007年，瑞士科学家MeierW.和美国科学家KumarM.等人首次将水通道蛋白AqpZ嵌入嵌段共聚物微囊，研究微囊的水通透性和截盐效果，从此开启了水通道蛋白AqpZ作为功能单元构建生物功能仿生分离膜研究的序幕（ProceedingsoftheNationalAcademyofSciencesoftheUnitedStatesofAmerica,2007,104,20719-20724）。随后，丹麦水通道蛋白有限公司通过将功能蛋白首先引入到磷脂双分子层中或微囊中然后引入到基底膜上，制备含功能蛋白复合膜（CN201180060877.4，CN201110008858.9，CN200680034784.3）。专利CN201280057206.7通过将功能蛋白包裹进磷脂双分子层微囊，然后将含水通道蛋白的微囊加入间苯二胺(MPD)溶液中，以期通过和均苯三甲酰氯(TMC)单体交联植入到界面聚合制备的聚酰胺分离层来提高复合膜的分离效果。专利CN201310454532.8和专利CN201410012030.4将功能蛋白嵌入含氨基的磷脂双分子层，并将带氨基的微囊表面通过共价键或静电吸附引入到多巴胺修饰的基底或表面带负电的基底上，制备功能蛋白复合膜，提高分离膜的性能。
到目前为止，基于功能蛋白复合膜的公开专利和文献中制备功能蛋白复合膜的方法都是将功能蛋白首先引入到磷脂双分子层中或由磷脂或双亲性共聚物自组装的微囊，在通过不同的方法引入到基底层上制备复合膜。然而采用磷脂双分子层磷脂或由磷脂或双亲性共聚物自组装的微囊作为功能蛋白的支撑结构，不仅其成本高，而且过程繁琐，磷脂双分子层磷脂或由磷脂或双亲性共聚物自组装的微囊中可嵌入的功能蛋白含量较少，再引入到基底支撑层水通道蛋白含量会更少，因此在很大程度上限制了功能蛋白仿生分离膜水通量的大幅提高。
发明内容
为解决上述现有技术中存在的问题，本发明的目的在于提供一种基于功能蛋白的复合膜及其制备方法，利用层层组装技术，在组装过程中直接将功能蛋白嵌入到由聚阴阳离子电解质交替沉积形成的聚电解质活性层网络中，提高功能蛋白的嵌入量，进而提高功能蛋白复合分离膜的性能。本发明提供如下的技术方案：
一种基于功能蛋白的复合膜，其特征在于，所述的功能蛋白复合膜由含功能蛋白的聚电解质活性层和支撑层组成；
其中，所述的聚电解质活性层是通过聚阴阳离子电解质在支撑层表面层层组装得到，其中功能蛋白可分散在聚阴离子或聚阳离子电解质溶液中，在组装过程中直接嵌入到聚电解质活性层中；
其中，所述的层层组装过程为支撑层依次浸泡聚阴阳离子电解质溶液，每次取出后用去离子水清洗表面1~3次，通过聚阴阳离子电解质的自由吸附或在外加压力或电场作用下，实现其在支撑层上的交替沉积，形成聚电解质活性层，随后对聚电解质活性层进行交联固定，其中功能蛋白与聚电解质的摩尔比为0.01~100；
其中，功能蛋白选自但不仅限于水通道蛋白、离子通道蛋白和载体蛋白的一种，其中水通道蛋白包括但不仅限于水通道蛋白1、水通道蛋白2、水通道蛋白3、水通道蛋白8、水通道蛋白9、水通道蛋白z、水通道蛋白γ-TIP、水通道蛋白NIP、水通道蛋白PIP；其中离子通道蛋白包括但不仅限于钾离子通道蛋白、钠离子通道蛋白、氯离子通道蛋白；载体蛋白包括但不仅限于缬氨酶素；
其中，所述的层层组装过程中使用的聚阴离子电解质溶液包括但不仅限于聚丙烯酸(PAA)、聚苯乙烯磺酸(PSS)、海藻酸钠(SA)或聚乙烯基磺酸(PVS)溶液，溶液的浓度为0.1g/L~10g/L，溶液的pH值大于所用功能蛋白的等电点，浸泡时间为1min~60min；
其中，所述的层层组装过程中使用的聚阳离子电解质包括但不仅限于聚丙烯胺(PAH)、聚二烯丙基二甲基氯化铵(PDADMAC)、壳聚糖(CS)或聚乙烯亚胺（PEI）溶液，溶液的浓度为0.1g/L~10g/L，溶液的pH值大于所用功能蛋白的等电点，浸泡时间为1min~60min；
其中，所述的层层组装过程循环浸泡聚阴阳离子电解质溶液的次数为1~100次；
其中，所述的交联固定过程所用交联剂为含有多于一个醛基、N-羟基琥珀酰亚胺酯或环氧基，其中交联剂包括但不仅限于戊二醛、多聚甲醛、N-[α-马来酰亚胺乙酸基]琥珀酰亚胺酯、双-[2-(琥珀酰亚胺基氧羰基氧)乙基]砜、5(双-N-琥珀酰亚胺基[戊乙二醇]酯)、二琥珀酰亚胺基戊二酸、二琥珀酰亚胺基辛二酸盐、γ-缩水甘油醚氧丙基三甲氧基硅烷等；交联时间为1min~1h。
其中，所述的支撑层为多孔结构或不含孔的并且表面带电荷的或经表面修饰后带电荷的高分子或陶瓷或多孔不锈钢网的一种；
所述的功能蛋白复合膜，可用于海水淡化、污水处理、染料脱除、食品加工、生物医药和疾病治疗等领域。
本发明与现有技术相比，具有以下优点和有益效果：
1.本发明在组装过程中将功能蛋白镶嵌在聚电解质形成的网络结构中，提高了功能蛋白在膜表面的嵌入量，且通过交联提高了功能蛋白在活性层中的结合度和稳定性；
2.本发明采用层层组装方法，引入功能蛋白的方法过程简单，且不受基底材料的限制，拓展了基底膜材料的选择。
具体实施方式
下面的实施案例中将对本发明作进一步的阐述，但本发明不限于此。
实施案例1
将聚砜超滤基底膜放入浓度为2mg/mL的多巴胺Tris-HCl缓冲溶液中，置于恒温水浴振荡器上30℃下反应6h，多巴胺溶液pH值为9.0。反应结束后用乙醇和去离子水冲洗膜表面3次。然后将多巴胺修饰的膜放入pH值为9.0的PEITris-HCl缓冲溶液中反应6h，PEI浓度为1g/L，制备表面带正电荷的聚砜超滤膜基底膜。将修饰后的基底膜浸泡含水通道蛋白Z与PSS的聚阴离子电解质溶液，溶液的浓度为1g/L，水通道蛋白Z与PSS的摩尔比为0.01，浸泡时间为30min，取出后用去离子水清洗表面三次，再次浸泡浓度为1g/L的PEI聚阳离子溶液30min，取出后用去离子水清洗表面三次。依次重复上述浸泡过程15次，然后放入戊二醛溶液交联15min,制备得到功能蛋白复合分离膜。采用死端过滤装置在0.1MPa压力下测试膜的水通量大于300LMH，对亚甲基蓝染料的截留率大于95%。
实施案例2
将聚偏氟乙烯超滤基底膜放入浓度为2mg/mL的多巴胺Tris-HCl缓冲溶液中，置于恒温水浴振荡器上30℃下反应6h，多巴胺溶液pH值为9.0。反应结束后用乙醇和去离子水冲洗膜表面3次。然后将多巴胺修饰的膜放入pH值为9.0的PEITris-HCl缓冲溶液中反应6h，PEI浓度为1g/L，制备表面带正电荷的聚氟乙烯超超滤膜基底膜。将修饰后的基底膜浸泡含水通道蛋白Z与PAA的聚阴离子电解质溶液，溶液的浓度为2g/L，水通道蛋白Z与PAA的摩尔比为0.5，浸泡时间为30min，取出后用去离子水清洗表面三次，再次浸泡浓度为2g/L的PEI聚阳离子溶液30min，取出后用去离子水清洗表面三次。依次重复上述浸泡过程10次，然后放入二琥珀酰亚胺基辛二酸盐溶液交联20min,制备得到功能蛋白复合分离膜。
实施案例3
将聚碳酸酯基底膜放入浓度为2mg/mL的多巴胺Tris-HCl缓冲溶液中，置于恒温水浴振荡器上30℃下反应6h，多巴胺溶液pH值为9.0。反应结束后用乙醇和去离子水冲洗膜表面3次。然后将多巴胺修饰的膜放入pH值为9.0的PEITris-HCl缓冲溶液中反应6h，PEI浓度为1g/L，制备表面带正电荷的聚氟乙烯超超滤膜基底膜。将修饰后的基底膜浸泡含水通道蛋白Z与海藻酸钠的聚阴离子电解质溶液，溶液的浓度为1g/L，水通道蛋白Z与海藻酸钠的摩尔比为10，浸泡时间为30min，取出后用去离子水清洗表面三次，再次浸泡浓度为1g/L的PEI聚阳离子溶液30min，取出后用去离子水清洗表面三次。依次重复上述浸泡过程12次，然后放入多聚甲醛溶液交联30min,制备得到功能蛋白复合分离膜。
实施案例4
将氧化铝基底膜放入浓度为2mg/mL的多巴胺Tris-HCl缓冲溶液中，置于恒温水浴振荡器上30℃下反应6h，多巴胺溶液pH值为9.0。反应结束后用乙醇和去离子水冲洗膜表面3次。然后将多巴胺修饰的膜放入pH值为9.0的PEITris-HCl缓冲溶液中反应6h，PEI浓度为1g/L，制备表面带正电荷的氧化铝基底膜。将修饰后的基底膜浸泡含水通道蛋白Z和PAA的聚阴离子电解质溶液，溶液的浓度为0.1g/L，水通道蛋白Z与PAA的摩尔比为50，浸泡时间为30min，取出后用去离子水清洗表面三次，再次浸泡浓度为0.1g/L的PEI聚阳离子溶液30min，取出后用去离子水清洗表面三次。依次重复上述浸泡过程100次，然后放入γ-缩水甘油醚氧丙基三甲氧基硅烷溶液交联2h，制备得到功能蛋白复合分离膜。
实施案例5
将多孔不锈钢网膜放入浓度为2mg/mL的多巴胺Tris-HCl缓冲溶液中，置于恒温水浴振荡器上30℃下反应6h，多巴胺溶液pH值为9.0。反应结束后用乙醇和去离子水冲洗膜表面3次。然后将多巴胺修饰的膜放入pH值为9.0的PEITris-HCl缓冲溶液中反应6h，PEI浓度为1g/L，制备表面带正电荷的氧化铝基底膜。将修饰后的基底膜浸泡含水通道蛋白Z与PVS的聚阴离子电解质溶液，溶液的浓度为10g/L，水通道蛋白Z与PVS的摩尔比为100，浸泡时间为30min，取出后用去离子水清洗表面三次，再次浸泡浓度为10g/L的壳聚糖聚阳离子溶液30min，取出后用去离子水清洗表面三次。依次重复上述浸泡过程8次，然后放入二琥珀酰亚胺基戊二酸溶液交联10min,制备得到功能蛋白复合分离膜。
实施案例6
将聚丙烯腈静电纺丝膜经NaOH溶液处理后浸泡含水通道蛋白Z与PSS的聚阴离子电解质溶液，溶液的浓度为1g/L，水通道蛋白Z与PSS的摩尔比为0.2，浸泡时间为30min，取出后用去离子水清洗表面三次，再次浸泡浓度为1g/L的PAH聚阳离子溶液30min，取出后用去离子水清洗表面三次。依次重复上述浸泡过程20次，然后放入戊二醛溶液交联15min,制备得到功能蛋白复合分离膜。
实施案例7
将聚砜超滤基底膜放入浓度为2mg/mL的多巴胺Tris-HCl缓冲溶液中，置于恒温水浴振荡器上30℃下反应6h，多巴胺溶液pH值为9.0。反应结束后用乙醇和去离子水冲洗膜表面3次。然后将多巴胺修饰的膜放入pH值为9.0的PEITris-HCl缓冲溶液中反应6h，PEI浓度为1g/L，制备表面带正电荷的聚砜超滤膜基底膜。将修饰后的基底膜浸泡含水通道蛋白Z与PSS的聚阴离子电解质溶液，溶液的浓度为1g/L，水通道蛋白Z与PSS的摩尔比为0.5，浸泡时间为30min，取出后用去离子水清洗表面三次，再次浸泡浓度为1g/L的PDADMAC聚阳离子溶液30min，取出后用去离子水清洗表面三次。依次重复上述浸泡过程15次，然后放入戊二醛溶液交联15min,制备得到功能蛋白复合分离膜。
实施案例8-10
将聚丙烯腈静电纺丝膜经NaOH溶液处理后浸泡含功能蛋白与PSS的聚阴离子电解质溶液，溶液的浓度为1g/L，功能蛋白与PSS的摩尔比为0.2，浸泡时间为30min，取出后用去离子水清洗表面三次，再次浸泡浓度为1g/L的PAH聚阳离子溶液30min，取出后用去离子水清洗表面三次。依次重复上述浸泡过程20次，然后放入N-[α-马来酰亚胺乙酸基]琥珀酰亚胺酯或双-[2-(琥珀酰亚胺基氧羰基氧)乙基]砜或5(双-N-琥珀酰亚胺基[戊乙二醇]酯)溶液交联15min,制备得到功能蛋白复合分离膜。
实施案例11-21
将聚丙烯腈静电纺丝膜经NaOH溶液处理后浸泡含水通道蛋白1或水通道蛋白2或水通道蛋白3或水通道蛋白8或水通道蛋白9或水通道蛋白γ-TIP或水通道蛋白NIP或钾离子通道蛋白或钠离子通道蛋白或氯离子通道蛋白或缬氨酶素与PSS的聚阴离子电解质溶液，溶液的浓度为1g/L，水通道蛋白1或水通道蛋白2或水通道蛋白3或水通道蛋白8或水通道蛋白9或水通道蛋白γ-TIP或水通道蛋白NIP或钾离子通道蛋白或钠离子通道蛋白或氯离子通道蛋白或缬氨酶素与PSS的摩尔比为0.2，浸泡时间为30min，取出后用去离子水清洗表面三次，再次浸泡浓度为1g/L的PAH聚阳离子溶液30min，取出后用去离子水清洗表面三次。依次重复上述浸泡过程20次，然后放入戊二醛溶液交联15min,制备得到功能蛋白复合分离膜。

Claims (10)

1.一种基于功能蛋白的复合膜，其特征在于，所述的功能蛋白复合膜由含功能蛋白的聚电解质活性层和支撑层组成。
2.根据权利要求1所述的基于功能蛋白的复合膜，其特征在于，所述的聚电解质活性层是通过聚阴阳离子电解质在支撑层表面层层组装得到，其中功能蛋白可分散在聚阴离子或聚阳离子电解质溶液中，在组装过程中直接嵌入到聚电解质活性层中。
3.根据权利要求1或2所述的基于功能蛋白的复合膜，其特征在于，所述聚电解质活性层的层层组装过程为支撑层依次浸泡聚阴阳离子电解质溶液，每次取出后用去离子水清洗表面1~3次，通过聚阴阳离子电解质的自由吸附或在外加压力或电场作用下，实现其在支撑层上的交替沉积，形成聚电解质活性层，随后对聚电解质活性层进行交联固定，其中功能蛋白与聚电解质的摩尔比为0.01~100。
4.根据权利要求1、2或3所述的基于功能蛋白的复合膜，其特征在于，聚电解质活性层中含有功能蛋白，功能蛋白选自但不仅限于水通道蛋白、离子通道蛋白和载体蛋白的一种，其中水通道蛋白包括但不仅限于水通道蛋白1、水通道蛋白2、水通道蛋白3、水通道蛋白8、水通道蛋白9、水通道蛋白z、水通道蛋白γ-TIP、水通道蛋白NIP、水通道蛋白PIP；其中离子通道蛋白包括但不仅限于钾离子通道蛋白、钠离子通道蛋白、氯离子通道蛋白；载体蛋白包括但不仅限于缬氨酶素。
5.根据权利要求2或3所述的基于功能蛋白的复合膜，其特征在于，所述聚电解质活性层的层层组装过程中使用的聚阴离子电解质溶液包括但不仅限于聚丙烯酸(PAA)、聚苯乙烯磺酸(PSS)、海藻酸钠(SA)或聚乙烯基磺酸(PVS)溶液，溶液的浓度为0.1g/L~10g/L，溶液的pH值大于所用功能蛋白的等电点，浸泡时间为1min~60min。
6.根据权利要求2或3所述的基于功能蛋白的复合膜，其特征在于，所述的聚电解质活性层的层层组装过程中使用的聚阳离子电解质包括但不仅限于聚丙烯胺(PAH)、聚二烯丙基二甲基氯化铵(PDADMAC)、壳聚糖(CS)或聚乙烯亚胺（PEI）溶液，溶液的浓度为0.1g/L~10g/L，溶液的pH值大于所用功能蛋白的等电点，浸泡时间为1min~60min。
7.根据权利要求2或3所述的基于功能蛋白的复合膜，其特征在于，所述聚电解质活性层的层层组装过程循环浸泡聚阴阳离子电解质溶液的次数为1~100次。
8.根据权利要求2或3所述的基于功能蛋白的复合膜，其特征在于，所述的聚电解质活性层的交联固定过程所用交联剂为含有不少于两个官能团的分子，所述的两个及两个以上的官能团可为同一种，也可为不同种官能团，其官能团可为但不限于氨基、羧基、羟基、酰氯、醛基、N-羟基琥珀酰亚胺酯、马来酸酐、环氧基、硅氧烷等，常用的交联剂包括但不仅限于戊二醛、多聚甲醛、N-[α-马来酰亚胺乙酸基]琥珀酰亚胺酯、双-[2-(琥珀酰亚胺基氧羰基氧)乙基]砜、5(双-N-琥珀酰亚胺基[戊乙二醇]酯)、二琥珀酰亚胺基戊二酸、二琥珀酰亚胺基辛二酸盐、γ-缩水甘油醚氧丙基三甲氧基硅烷等；交联时间为1min~1h。
9.根据权利要求2或3所述的基于功能蛋白复合膜，其特征在于，所述的支撑层为多孔结构或不含孔的并且表面带电荷的或经表面修饰后带电荷的高分子膜或陶瓷膜或多孔不锈钢网的一种。
10.根据权利要求1所述的基于功能蛋白复合膜，其特征在于，可用于海水淡化、污水处理、染料脱除、食品加工、生物医药和疾病治疗等领域。
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