CN113019337A - 聚四氟乙烯硼亲和印迹膜的制备方法及其应用于选择性分离莽草酸 - Google Patents
聚四氟乙烯硼亲和印迹膜的制备方法及其应用于选择性分离莽草酸 Download PDFInfo
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Abstract
本发明属于资源利用和化工分离技术领域,涉及一种聚四氟乙烯硼亲和印迹膜的制备方法,包括:先在Tris水溶液中溶解盐酸多巴胺,充分搅拌后,调pH 8.5,浸入PVDF膜,搅拌、洗净,50℃烘干得PVDF@PDA膜;无水乙醇中溶解KH570,加入PVDF@PDA膜,加热回流、真空烘干得乙烯基改性PVDF膜;取乙烯基改性PVDF膜溶于25 mL乙腈溶液中,加入莽草酸、VPBA、EGDMA、AIBN,氮气中40℃反应2~8 h→60℃反应8~16 h→50~100℃老化2~6 h,冷却后、洗净,烘干后、洗脱,水洗至中性即得。本发明以PVDF为基底,在其表面制备分子印迹聚合物引入双重识别机制,使得具有顺式二羟基结构的莽草酸在膜表面富集,实现莽草酸的有效分离。本发明在富集分离以及纯化具有顺式二羟基结构的天然产物领域有较好的应用前景。
Description
技术领域
本发明属于资源利用和化工分离技术领域,涉及聚四氟乙烯膜基材料的制备,具体涉及一种聚四氟乙烯硼亲和印迹膜的制备方法及其应用于选择性分离莽草酸。
背景技术
莽草酸(Shikimic Acid),又名3,4,5-三羟基-1-环己烯-1-羧酸,在自然环境的植物组织中分布广泛。莽草酸的应用价值极大,具有抗肿瘤、抗血栓及脑缺血和抗炎症作用,是重要的药物合成原料,例如是合成抗禽流感病毒专利药物GS4104(达菲)的必需原料。除此以外,它还是重要的化工中间体。目前获取莽草酸的方法可以分为三大类:工业合成、微生物发酵和从植物组织中提取。其中,从植物组织中提取莽草酸资源被认为是最经济高效的方法。但是,无论利用何种手段得到的莽草酸都需经过进一步分离纯化才能应用于后续的开发环节。因此,急需选择简单高效的分离纯化方法来解决莽草酸高纯产品质量控制这一难题。
为了提高莽草酸的分离效率,科研工作者已经开展了多项研究。目前,常用的分离纯化莽草酸的方法主要有重结晶法、吸附法、柱层析法、交换树脂法。其中,吸附法因其方便快速的特点研究的最多。但目前所应用的吸附法中例如活性炭吸附、大孔树脂吸附、静电吸附都存在局限性,其中共性的缺陷是材料的非特异性吸附强、吸附容量小、方法选择性差从而导致分离效率低。因此,建立和完善新的吸附法,用于选择性识别与分离纯化莽草酸是目前急需解决的问题。
由于莽草酸分子结构中含有顺式二羟基这种能实现特异性识别的官能团,可以利用硼亲和作用实现对莽草酸的有效识别。分子印迹技术作为一种典型的可以对某一特定目标产生特异性结合的技术,在分离纯化领域有着广泛的应用。一般未经处理得到的莽草酸溶液成分复杂,仅靠单一的硼亲和识别技术很难实现高效快速的分离,因此可以引入分子印迹技术作为第二重识别机制来达到深度分离纯化的要求。再之,当前应用于分离莽草酸的材料大部分为粉体,在分离回收方面具有难度。因此,耦合膜分离技术,制备可用于选择性识别的分子印迹膜材料来满足社会对高纯莽草酸的迫切需求。
发明内容
针对上述现有技术中存在的不足,本发明的目的是公开了一种聚四氟乙烯硼亲和印迹膜的制备方法。
技术方案:
一种聚四氟乙烯硼亲和印迹膜的制备方法,包括如下步骤:
a)按照每100mL含有0.1211g Tris水溶液中溶解0.1~1.0g盐酸多巴胺,优选每100mL含有0.1211g Tris水溶液中溶解0.2g盐酸多巴胺,充分搅拌后,用盐酸调溶液pH至8.5,浸入一片聚四氟乙烯(PVDF)薄膜,搅拌3~18h后,优选12h,取出膜用蒸馏水洗净,50℃烘干得PVDF@PDA膜;
b)按照每70mL无水乙醇中溶解0.5~5mL KH570,优选每70mL无水乙醇中溶解2mLKH570,超声分散0.5h后加入一片PVDF@PDA膜,磁力搅拌下,40~100℃回流12~48h后,优选60℃回流24h,取出用蒸馏水洗净,真空30℃烘干得乙烯基改性PVDF膜;
c)取一片乙烯基改性PVDF膜溶于25mL乙腈溶液中,按照每25mL乙腈溶液加入质量比为10mg:5~50mg:50~250mg:1~10mg的莽草酸、4-乙烯基苯硼酸(VPBA)、交联剂乙二醇二甲基丙烯酸酯(EGDMA)、引发剂偶氮二异丁腈(AIBN),优选每25mL乙腈溶液加入质量比为10mg:10mg:150mg:5mg的莽草酸、VPBA、交联剂EGDMA、引发剂AIBN,在氮气保护下,40℃反应2~8h→60℃反应8~16h→50~100℃老化2~6h,优选40℃反应4h→60℃反应12h→80℃老化4h,冷却后,将膜取出洗净,烘干后置于甲醇/乙酸混合液中洗脱,水洗至中性后得到基于硼亲和作用的莽草酸分子印迹膜材料。
本发明较优公开例中,步骤a)中所述四氟乙烯(PVDF)薄膜,其直径25mm,孔径0.8μm。
本发明较优公开例中,步骤c)中所述甲醇/乙酸混合液按8:2v/v配制而成。
根据本发明所述方法制得的聚四氟乙烯硼亲和印迹膜,可应用于莽草酸的选择性吸附分离。
应用实验如下:
环境25℃,按每20mL 0.1g/L莽草酸溶液加入一片聚四氟乙烯硼亲和印迹膜计,调节溶液pH在4~10,吸附反应2~6h后,溶液中的莽草酸吸附/富集到材料表面;将反应后的材料分离出来。
按照公式(1)计算吸附量Q(mg/g),并以等量的非印迹聚合膜材料作为吸附对照。
式中:C0和C(mg/L)分别为莽草酸溶液的初始浓度和平衡浓度,V(mL)为莽草酸溶液体积,S(cm2)为吸附剂膜材料的面积。
为便于对比,非印迹聚合膜材料的制备除不加模板分子外,其余操作步骤与印迹聚合膜材料相同,并将其作为对比例。
本发明所用的PVDF膜、KH570、无水乙醇、乙腈、甲醇、乙酸、莽草酸,氢氧化钠、盐酸,国药集团化学试剂有限公司;盐酸多巴胺(DA)、三羟甲基氨基甲烷(Tris)、4-乙烯基苯硼酸(VPBA)、乙二醇二甲基丙烯酸酯(EGDMA)、偶氮二异丁腈(AIBN),上海阿拉丁生化科技股份有限公司。
本发明的特点为:
(1)所制备的莽草酸分子印迹膜材料成本低廉、制备方便;
(2)硼亲和作用与分子印迹技术相结合构筑了硼亲和与印迹孔穴二元特异性识别位点,为选择性分离纯化莽草酸提供可靠保证。
(3)相较于传统的用于莽草酸分离的粉体材料,引入膜分离技术,极大的简化了分离过程,提高了分离效率。
有益效果
本发明以一种聚四氟乙烯硼亲和印迹膜作为吸附/富集分离莽草酸的材料,提高莽草酸的吸附效率。该材料以PVDF材料为基底,通过在其表面制备分子印迹聚合物引入双重识别机制,使得具有顺式二羟基结构的莽草酸在材料表面富集,实现莽草酸的有效分离。本发明在富集分离以及纯化具有顺式二羟基结构的天然产物领域有较好的应用前景。
附图说明
图1.原始PVDF膜之SEM;
图2.PVDF@PDA膜之SEM;
图3.聚四氟乙烯硼亲和印迹膜之SEM。
具体实施方式
下面结合实施例对本发明进行详细说明,以使本领域技术人员更好地理解本发明,但本发明并不局限于以下实施例。
除非另外限定,这里所使用的术语(包含科技术语)应当解释为具有如本发明所属技术领域的技术人员所共同理解到的相同意义。还将理解到,这里所使用的术语应当解释为具有与它们在本说明书和相关技术的内容中的意义相一致的意义,并且不应当以理想化或过度的形式解释,除非这里特意地如此限定。
实施例1
一种聚四氟乙烯硼亲和印迹膜的制备方法,包括如下步骤:
a)按照每100mL含有0.1211g Tris水溶液中溶解0.1g盐酸多巴胺,充分搅拌后,用盐酸调溶液pH至8.5,将一片市售聚四氟乙烯(PVDF)薄膜(直径25mm,孔径0.8μm)浸入上述溶液中,搅拌3h后,取出,膜材料用蒸馏水洗涤五次,50℃烘干得PVDF@PDA膜材料;
b)按照每70mL无水乙醇中溶解0.5mL KH570,超声分散0.5h后加入一片PVDF@PDA膜,磁力搅拌下,40℃回流12h后,取出用蒸馏水洗净,真空30℃烘干得乙烯基改性PVDF膜材料;
c)取一片乙烯基改性PVDF膜材料溶于25mL乙腈溶液中,按照每25mL乙腈溶液加入质量比为10mg:5mg:50mg:1mg的莽草酸、4-乙烯基苯硼酸(VPBA)、交联剂乙二醇二甲基丙烯酸酯(EGDMA)、引发剂偶氮二异丁腈(AIBN),在氮气保护下,40℃反应2h后60℃反应8h→50℃老化2h,冷却后,将膜取出洗净,烘干后置于甲醇/乙酸混合液(8:2v/v)中洗脱,水洗至中性后即得。
应用实验如下:
环境25℃,按每20mL 0.1g/L莽草酸溶液加入一片聚四氟乙烯硼亲和印迹膜计,调节溶液pH在4,吸附反应2h后,溶液中的莽草酸吸附/富集到材料表面;将反应后的材料分离出来。所制备的吸附剂对莽草酸的吸附量达到0.4039mg/cm2。作为对比,等量的非印迹膜材料在同样的条件下对莽草酸的吸附量有0.3352mg/cm2。
实施例2
一种聚四氟乙烯硼亲和印迹膜的制备方法,包括如下步骤:
a)按照每100mL含有0.1211g Tris水溶液中溶解0.5g盐酸多巴胺,充分搅拌后,用盐酸调溶液pH至8.5,将一片市售聚四氟乙烯(PVDF)薄膜(直径25mm,孔径0.8μm)浸入上述溶液中,搅拌9h后,取出,膜材料用蒸馏水洗涤五次,50℃烘干得PVDF@PDA膜材料;
b)按照每70mL无水乙醇中溶解1mL KH570,超声分散0.5h后加入一片PVDF@PDA膜,磁力搅拌下,80℃回流24h后,取出用蒸馏水洗净,真空30℃烘干得乙烯基改性PVDF膜材料;
c)取一片乙烯基改性PVDF膜材料溶于25mL乙腈溶液中,按照每25mL乙腈溶液加入质量比为10mg:25mg:100mg:3mg的莽草酸、4-乙烯基苯硼酸(VPBA)、交联剂乙二醇二甲基丙烯酸酯(EGDMA)、引发剂偶氮二异丁腈(AIBN),在氮气保护下,40℃反应2h后60℃反应12h→60℃老化3h,冷却后,将膜取出洗净,烘干后置于甲醇/乙酸混合液(8:2v/v)中洗脱,水洗至中性后即得。
应用实验如下:
环境25℃,按每20mL 0.1g/L莽草酸溶液加入一片聚四氟乙烯硼亲和印迹膜计,调节溶液pH在6,吸附反应4h后,溶液中的莽草酸吸附/富集到材料表面;将反应后的材料分离出来。所制备的吸附剂对莽草酸的吸附量达到5.673mg/cm2;作为对比,等量的非印迹膜材料在同样的条件下对莽草酸的吸附量有1.0379mg/cm2。
实施例3
一种聚四氟乙烯硼亲和印迹膜的制备方法,包括如下步骤:
a)按照每100mL含有0.1211g Tris水溶液中溶解0.2g盐酸多巴胺,充分搅拌后,用盐酸调溶液pH至8.5,将一片市售聚四氟乙烯(PVDF)薄膜(直径25mm,孔径0.8μm)浸入上述溶液中,搅拌12h后,取出,膜材料用蒸馏水洗涤五次,50℃烘干得PVDF@PDA膜材料;
b)按照每70mL无水乙醇中溶解2mL KH570,超声分散0.5h后加入一片PVDF@PDA膜,磁力搅拌下,60℃回流24h后,取出用蒸馏水洗净,真空30℃烘干得乙烯基改性PVDF膜材料;
c)取一片乙烯基改性PVDF膜材料溶于25mL乙腈溶液中,按照每25mL乙腈溶液加入质量比为10mg:10mg:150mg:5mg的莽草酸、4-乙烯基苯硼酸(VPBA)、交联剂乙二醇二甲基丙烯酸酯(EGDMA)、引发剂偶氮二异丁腈(AIBN),在氮气保护下,40℃反应4h,60℃反应12h,80℃老化4h,冷却后,将膜取出洗净,烘干后置于甲醇/乙酸混合液(8:2v/v)中洗脱,水洗至中性后即得。
应用实验如下:
环境25℃,按每20mL 0.1g/L莽草酸溶液加入一片聚四氟乙烯硼亲和印迹膜计,调节溶液pH在8,吸附反应4h后,溶液中的莽草酸吸附/富集到材料表面;将反应后的材料分离出来。所制备的吸附剂对莽草酸的吸附量达到19.7035mg/cm2;作为对比,等量的非印迹聚合物在同样的条件下对莽草酸的吸附量有6.9073mg/cm2。
在此比例的基础上,对所制备的印迹材料进行了形貌表征,附图1和附图2是原始PVDF膜材料和PVDF@PDA膜材料的SEM图,可以看出材料具有良好的孔结构,经多巴胺改性后材料粗糙度明显增加。印迹之后,材料表面附着一层由球形印迹聚合物形成的印迹层(图3莽草酸分子印迹膜材料SEM)。
实施例4
一种聚四氟乙烯硼亲和印迹膜的制备方法,包括如下步骤:
a)按照每100mL含有0.1211g Tris水溶液中溶解0.8g盐酸多巴胺,充分搅拌后,用盐酸调溶液pH至8.5,将一片市售聚四氟乙烯(PVDF)薄膜(直径25mm,孔径0.8μm)浸入上述溶液中,搅拌6h后,取出,膜材料用蒸馏水洗涤五次,50℃烘干得PVDF@PDA膜材料;
b)按照每70mL无水乙醇中溶解3.5mL KH570,超声分散0.5h后加入一片PVDF@PDA膜,磁力搅拌下,40℃回流48h后,取出用蒸馏水洗净,真空30℃烘干得乙烯基改性PVDF膜材料;
c)取一片乙烯基改性PVDF膜材料溶于25mL乙腈溶液中,按照每25mL乙腈溶液加入质量比为10mg:35mg:200mg:6mg的莽草酸、4-乙烯基苯硼酸(VPBA)、交联剂乙二醇二甲基丙烯酸酯(EGDMA)、引发剂偶氮二异丁腈(AIBN),在氮气保护下,40℃反应6h,60℃反应16h,75℃老化2h,冷却后,将膜取出洗净,烘干后置于甲醇/乙酸混合液(8:2v/v)中洗脱,水洗至中性后即得。
应用实验如下:
环境25℃,按每20mL 0.1g/L莽草酸溶液加入一片聚四氟乙烯硼亲和印迹膜计,调节溶液pH在7,吸附反应2h后,溶液中的莽草酸吸附/富集到材料表面;将反应后的材料分离出来。所制备的吸附剂对莽草酸的吸附量达到11.3039mg/cm2;作为对比,等量的非印迹聚合物在同样的条件下对莽草酸的吸附量有5.4137mg/cm2。
实施例5
一种聚四氟乙烯硼亲和印迹膜的制备方法,包括如下步骤:
a)按照每100mL含有0.1211g Tris水溶液中溶解1.0g盐酸多巴胺,充分搅拌后,用盐酸调溶液pH至8.5,将一片市售聚四氟乙烯(PVDF)薄膜(直径25mm,孔径0.8μm)浸入上述溶液中,搅拌18h后,取出,膜材料用蒸馏水洗涤五次,50℃烘干得PVDF@PDA膜材料;
b)按照每70mL无水乙醇中溶解5mL KH570,超声分散0.5h后加入一片PVDF@PDA膜,磁力搅拌下,100℃回流48h后,取出用蒸馏水洗净,真空30℃烘干得乙烯基改性PVDF膜材料;
c)取一片乙烯基改性PVDF膜材料溶于25mL乙腈溶液中,按照每25mL乙腈溶液加入质量比为10mg:50mg:250mg:10mg的莽草酸、4-乙烯基苯硼酸(VPBA)、交联剂乙二醇二甲基丙烯酸酯(EGDMA)、引发剂偶氮二异丁腈(AIBN),在氮气保护下,40℃反应8h后60℃反应16h→100℃老化6h,冷却后,将膜取出洗净,烘干后置于甲醇/乙酸混合液(8:2v/v)中洗脱,水洗至中性后即得。
应用实验如下:
环境25℃,按每20mL 0.1g/L莽草酸溶液加入一片聚四氟乙烯硼亲和印迹膜计,调节溶液pH在10,吸附反应6h后,溶液中的莽草酸吸附/富集到材料表面;将反应后的材料分离出来。所制备的吸附剂对莽草酸的吸附量达到14.5011mg/cm2;作为对比,等量的非印迹聚合物在同样的条件下对莽草酸的吸附量有5.0735mg/cm2。
以上所述仅为本发明的实施例,并非因此限制本发明的专利范围,凡是利用本发明说明书所作的等效结构或等效流程变换,或直接或间接运用在其他相关的技术领域,均同理包括在本发明的专利保护范围内。
Claims (10)
1.一种聚四氟乙烯硼亲和印迹膜的制备方法,其特征在于,包括如下步骤:
a)按照每100 mL含有0.1211 g Tris水溶液中溶解0.1~1.0 g盐酸多巴胺,充分搅拌后,用盐酸调溶液pH至8.5,浸入一片聚四氟乙烯PVDF薄膜,搅拌3~18 h后,取出膜用蒸馏水洗净,50℃烘干得PVDF@PDA膜;
b)按照每70 mL无水乙醇中溶解0.5~5 mL KH570,超声分散0.5 h后加入一片PVDF@PDA膜,磁力搅拌下,40~100℃回流12~48 h后,取出用蒸馏水洗净,真空30℃烘干得乙烯基改性PVDF膜;
c)取一片乙烯基改性PVDF膜溶于25 mL乙腈溶液中,按照每25 mL乙腈溶液加入质量比为10 mg:5~50mg:50~250 mg:1~10 mg的莽草酸、4-乙烯基苯硼酸VPBA、交联剂乙二醇二甲基丙烯酸酯EGDMA、引发剂偶氮二异丁腈AIBN,在氮气保护下,40℃反应2~8 h→60℃反应8~16 h→50~100℃老化2~6 h,冷却后,将膜取出洗净,烘干后置于甲醇/乙酸(8:2 v/v)混合液中洗脱,水洗至中性后即得。
2.根据权利要求1所述聚四氟乙烯硼亲和印迹膜的制备方法,其特征在于:步骤a)中所述按照每100 mL含有0.1211 g Tris水溶液中溶解0.2g盐酸多巴胺。
3.根据权利要求1所述聚四氟乙烯硼亲和印迹膜的制备方法,其特征在于:步骤a)中所述浸入一片聚四氟乙烯PVDF薄膜,搅拌12 h。
4.根据权利要求1所述聚四氟乙烯硼亲和印迹膜的制备方法,其特征在于:步骤a)中所述四氟乙烯PVDF薄膜,其直径25 mm,孔径0.8μm。
5.根据权利要求1所述聚四氟乙烯硼亲和印迹膜的制备方法,其特征在于:步骤b)中所述按照每70 mL无水乙醇中溶解2mL KH570。
6.根据权利要求1所述聚四氟乙烯硼亲和印迹膜的制备方法,其特征在于:步骤b)中所述磁力搅拌下,60℃回流24 h。
7.根据权利要求1所述聚四氟乙烯硼亲和印迹膜的制备方法,其特征在于:步骤c)中所述按照每25 mL乙腈溶液加入质量比为10 mg:10 mg:150 mg:5 mg的莽草酸、VPBA、交联剂EGDMA、引发剂AIBN。
8.根据权利要求1所述聚四氟乙烯硼亲和印迹膜的制备方法,其特征在于:步骤c)中所述40℃反应4 h→60℃反应12 h→80℃老化4 h。
9.根据权利要求1-8任一所述方法制得的聚四氟乙烯硼亲和印迹膜。
10.一种如权利要求9所述聚四氟乙烯硼亲和印迹膜的应用,其特征在于:将其应用于莽草酸的选择性吸附分离。
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