CN114904499B - 一种手性Co-L-GG掺杂的有机聚合物毛细管整体柱 - Google Patents
一种手性Co-L-GG掺杂的有机聚合物毛细管整体柱 Download PDFInfo
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Abstract
本发明公开了一种手性Co‑L‑GG掺杂的有机聚合物毛细管整体柱,其是利用四水乙酸钴和甘氨酰‑L‑谷氨酸为原料制备Co‑L‑GG,然后将其与甲基丙烯酸缩水甘油酯、乙二醇二甲基丙烯酸酯、环已醇以及偶氮二异丁腈配成聚合物混合液,填充于预处理过的毛细管中进行聚合反应,以制得所述有机聚合物毛细管整体柱。本发明制得的手性毛细管整体柱具有良好的手性选择性,可用于色氨酸、苯丙氨酸以及吡喹酮等对映体的手性分离。
Description
技术领域
本发明属于材料制备领域,具体涉及一种手性钴-(甘氨酰-L-谷氨酸)(Co-L-GG)掺杂的有机聚合物毛细管整体柱。
背景技术
市场上两千多种常用药品中,超过百分之五十的药品是手性药品。两个手性对映体在医学治疗上可能会表现出不同的治疗效果,其中一种甚至会表现出极大的毒性,因此手性分离在药物检测中显得尤为重要。色谱法作为一种强大的分离手段,在手性物质的分离分析中得到了广泛应用。色谱柱是色谱法的关键所在。毛细管色谱柱由于自身重量轻,用料省,分离速度快且效能高,自1958年被提出以来,便得到了迅速发展。
毛细管色谱柱按照固定相在管壁内部的填充方式,可大致划分为以下三种类型:毛细管开管色谱柱、毛细管填充柱、毛细管整体柱。其中,毛细管整体柱由于分离性能优异,生物相容性好,成本低,可作为固定相的材料多样,重现性好等优点,再加上其制备工艺简单,在食品、环境、医药等领域表现出较好的应用前景。
整体柱按照材料的化学性质可分为无机聚合毛细管整体柱和有机聚合物毛细管整体柱。有机聚合物整体柱是将交联剂、引发剂、单体和制孔剂混合后通入毛细管中,使这些混合物发生聚合反应,反应完全后用适合的溶剂,如甲醇,通过机械泵或手动泵冲出柱内残余的单体和制孔剂制备而成。这类整体柱的制备选材范围较广,制出的整体柱pH值适用范围宽,因而发展迅速。其中,聚丙烯酸酯整体柱因其内部含有环氧化结构,可进一步与其他官能团进行连接,使柱子的性能得以改变,因此应用较为广泛。另外,在整体柱制备过程中还可添加手性物质来进行修饰,从而提高柱子的手性选择性。
发明内容
本发明的目的在于提供一种手性钴-(甘氨酰-L-谷氨酸)(Co-L-GG)掺杂的有机聚合物毛细管整体柱,其具有手性选择性,可用于手性对映体的拆分。
为实现上述目的,本发明采用如下技术方案:
一种手性Co-L-GG掺杂的有机聚合物毛细管整体柱,其制备包括以下步骤:
(1)Co-L-GG的制备:将四水乙酸钴、甘氨酰-L-谷氨酸于聚四氟乙烯反应釜中,加入水和甲醇搅拌溶解,然后将反应釜封装好后放入烘箱中进行反应,反应结束后待其自然冷却到室温,得到浅紫红色针状晶体,用无水甲醇多次洗涤晶体后干燥,得到Co-L-GG;
(2)毛细管的预处理:将石英毛细管依次用盐酸、去离子水、氢氧化钠、去离子水、甲醇冲洗后,氮气吹干,用3-异丁烯酰氧丙基三甲基硅烷(γ-MAPS)的甲醇溶液灌注满整根毛细管,并用橡胶塞将两端堵住,于恒温水浴条件下反应过夜,取出后用甲醇冲洗掉管内多余的反应液,再次用氮气吹干;
(3)毛细管整体柱的制备:将步骤(1)制得的Co-L-GG分散于十二烷醇中,超声处理使其分散均匀,然后加入甲基丙烯酸缩水甘油酯、乙二醇二甲基丙烯酸酯、环已醇以及偶氮二异丁腈,涡旋混合均匀,得到聚合物混合液;将所得聚合物混合液填充于预处理过的毛细管中,于恒温水浴条件下进行聚合反应,最后用无水甲醇进行清洗,即得所述手性Co-L-GG掺杂的有机聚合物毛细管整体柱。
进一步地,步骤(1)中所用四水乙酸钴与甘氨酰-L-谷氨酸的质量比为5:4;所述反应的温度为80℃,时间为2h;所述干燥的温度为110℃。
进一步地,步骤(2)中所述3-异丁烯酰氧丙基三甲基硅烷的甲醇溶液中3-异丁烯酰氧丙基三甲基硅烷的体积含量为50%;所述反应的温度为60℃。
进一步地,步骤(3)中所用Co-L-GG与十二烷醇的质量体积比为0.05-0.1g/3mL;所用十二烷醇与甲基丙烯酸缩水甘油酯、乙二醇二甲基丙烯酸酯、环已醇的体积比为3:3:1:3;所用偶氮二异丁腈与Co-L-GG的质量比为4:(5-10),所述聚合反应的温度为60℃,时间为12h。
上述手性Co-L-GG掺杂的有机聚合物毛细管整体柱可用于色氨酸、苯丙氨酸或吡喹酮等对映体的分离。
本发明的显著优点在于:
本发明利用甘氨酰-L-谷氨酸和四水乙酸钴反应合成了手性金属有机骨架材料Co-L-GG,然后将Co-L-GG与交联剂(乙二醇二甲基丙烯酸酯)、聚合单体(甲基丙烯酸缩水甘油酯)、引发剂(偶氮二异丁腈)和制孔剂(十二烷醇和环己醇)通过热引发自由基聚合法制备手性Co-L-GG掺杂的有机聚合物毛细管整体柱。由于Co-L-GG具有手性且含有多个活性官能团(如氨基、亚胺基、羰基等),因而能够与带有羧基、羰基等官能团的手性化合物发生相互作用,从而使所得手性Co-L-GG掺杂的有机聚合物毛细管整体柱对色氨酸、苯丙氨酸以及吡喹酮等多种手性化合物具有拆分能力。
附图说明
图1为合成Co-L-GG的反应示意图。
图2为实施例1所得Co-L-GG晶体的粉末X射线衍射图。
图3为实施例1所得Co-L-GG晶体的红外光谱图。
图4为实施例2所制备的手性Co-L-GG掺杂的有机聚合物毛细管整体柱的横截面扫描电镜图。
图5为实施例2制备的手性Co-L-GG掺杂的有机聚合物毛细管整体柱与对比例制备的未掺杂的有机聚合物毛细管整体柱的红外光谱图对比图。
图6为实施例3中D-色氨酸和L-色氨酸的分离色谱图。
图7为实施例3中D-吡喹酮和L-吡喹酮的分离色谱图。
图8为实施例3中D-苯丙氨酸和L-苯丙氨酸的分离色谱图。
具体实施方式
为了使本发明所述的内容更加便于理解,下面结合具体实施方式对本发明所述的技术方案做进一步的说明,但是本发明不仅限于此。
实施例1
提前设定烘箱温度至80℃,用分析天平称取150 mg四水乙酸钴、120mg甘氨酰-L-谷氨酸于50 mL聚四氟乙烯反应釜中,先后加入12 mL水和12 mL甲醇,用玻璃棒搅拌20 min使原料溶解,然后将反应釜封装好后放入烘箱中,按设定好的温度反应2 h;反应结束后待其自然冷却至室温,得到Co-L-GG的浅紫红色针状晶体,用无水甲醇多次洗涤晶体后,将晶体放入110℃真空干燥箱中烘干,备用。
将合成的Co-L-GG晶体进行粉末X射线衍射表征,结果如图1所示。由图可知,所得Co-L-GG粉末的X射线衍射图与其晶体数据模拟图基本一致,这证明了Co-L-GG晶体的成功制备。
将合成的Co-L-GG晶体进行红外光谱表征,结果如图2所示。由图可知,制备出的Co-L-GG晶体在1654cm-1与1577cm-1处有两个特征吸收峰,这是Co-L-GG特有的仲酰胺官能团的吸收峰,进一步证明了Co-L-GG的成功制备。
实施例2
将裸石英毛细管用1M盐酸冲洗30min,去离子水冲洗20min,1M氢氧化钠溶液冲洗1h,去离子水冲洗30min,甲醇冲洗20min,之后用氮气吹干待用。用体积含量为50%的3-异丁烯酰氧丙基三甲基硅烷(γ-MAPS)甲醇溶液灌注满整个毛细管空柱,并用橡胶塞将两端堵住,放入60℃超级恒温水浴锅中反应过夜。取出后用甲醇冲洗掉管内多余的γ-MAPS甲醇溶液,再次用氮气吹干。
分别称取实施例1制备的Co-L-GG晶体5mg和10mg,将其各自分散在300µL十二烷醇中,超声处理1h使其分散均匀,然后加入300µL甲基丙烯酸缩水甘油酯、100µL乙二醇二甲基丙烯酸酯、300µL环已醇以及4mg偶氮二异丁腈,放入1.5 mL离心管内涡旋混合均匀,得到聚合物混合液。将所得聚合物混合液填充于预处理过的毛细管中,在超级恒温水浴锅中60℃下进行12h的聚合反应,最后用无水甲醇对所制备的毛细管整体柱进行清洗。
为了观察聚合物整体柱材料在毛细管内的情况,截取5mm长的毛细管整体柱进行扫描电镜分析,结果如图4所示(其中a和b分别为5mg Co-L-GG制备的有机聚合物毛细管整体柱在10µm和50µm尺度下的扫描电镜图,c和d分别为10mg Co-L-GG制备的有机聚合物毛细管整体柱在10µm和50µm尺度下的扫描电镜图)。由图片对比可知,聚合物整体柱孔道分布较均匀,且聚合物整体柱材料与毛细管内壁结合得很好,不同Co-L-GG添加量制备的有机聚合物毛细管整体柱的扫描电镜图差异不大。
对比例
将300µL甲基丙烯酸缩水甘油酯、100µL乙二醇二甲基丙烯酸酯、300µL环已醇、300µL十二烷醇以及4mg偶氮二异丁腈超声混合均匀,放入1.5 mL离心管内涡旋混合均匀,得到聚合物混合液。将其填充于预处理过的毛细管中,在超级恒温水浴锅中60℃下进行12h的聚合反应,最后用无水甲醇对所制备的毛细管整体柱进行清洗,得到未掺杂的有机聚合物毛细管整体柱。
将实施例2得到的手性Co-L-GG掺杂的有机聚合物毛细管整体柱(Co-L-GG添加量10mg)材料和对比例得到的未掺杂的有机聚合物毛细管整体柱材料分别用红外光谱图进行表征,结果见图5。由图可知,手性Co-L-GG掺杂的整体柱材料的红外光谱图比未掺杂的整体柱材料在1500~1700cm-1波数范围内多了两个特征吸收峰,分别为1659cm-1和1576cm-1处,正是Co-L-GG晶体的特征吸收峰所在位置,这说明手性Co-L-GG已成功掺杂到有机聚合物毛细管整体柱中。
实施例3
手性对映体拆分实验在TriSep-3000高效微流电动液相色谱仪上完成。用去离子水配制0.1mg/mL的样品溶液(一些难溶或不溶于水的手性对映体则用体积比为1:1的乙醇与去离子水溶解),将配制好的所有样品溶液用0.22µm尼龙薄膜过滤器过滤,置于冰箱冷藏,使用时再取出。用20mM的磷酸二氢钠溶液(pH 3.5-5.5)与乙腈按一定比例混合,配制成高效微流电动液相色谱的流动相。所用流动相需放在超声波清洗器内超声10min去除气泡。进样前需让流动相在毛细管整体柱内平衡15min,待基线平稳,管内压强基本保持不变,即可开始注射样品进行手性拆分,每次注射样品量为10微升。
采用分离度(Rs)作为有机聚合物毛细管整体柱的性能评价参数,其计算公式为:
,
其中,t 1 为第一个对映体峰出现的保留时间,t 2 为第二个对映体峰出现的保留时间;W 1/2(1) 为第一个对映体峰的半峰宽,W 1/2(2) 为第二个对映体峰的半峰宽。
一、手性拆分色氨酸对映体
对色氨酸及其对映体进行手性拆分,其实验条件如下:流动相为乙腈和20 mM pH4.0的磷酸二氢钠溶液(50:50,v/v),反压阀750 PSI,流速0.05 mL/min,检测波长214 nm,-15 kV电压。其色谱图如图6所示,计算得到色氨酸对映体的分离度为1.972。
二、手性拆分吡喹酮对映体
对吡喹酮及其对映体进行手性拆分,其实验条件如下:流动相为乙腈和20 mM pH4.0的磷酸二氢钠溶液(70:30,v/v),反压阀750 PSI,流速0.05 mL/min,检测波长214 nm,-15 kV电压。其色谱图如图7所示,计算得到吡喹酮对映体的分离度为1.460。
三、手性拆分苯丙氨酸对映体
对苯丙氨酸及其对映体进行手性拆分,其实验条件如下:流动相为乙腈和20 mMpH 4.0的磷酸二氢钠溶液(70:30,v/v),反压阀750 PSI,检测波长214 nm,-15 kV电压。其色谱图如图8所示,计算得到苯丙氨酸对映体的分离度为1.229。
以上所述仅为本发明的较佳实施例,凡依本发明申请专利范围所做的均等变化与修饰,皆应属本发明的涵盖范围。
Claims (3)
1.一种手性Co-L-GG掺杂的有机聚合物毛细管整体柱在液相分离手性对映体中的应用,其特征在于,所述手性对映体为色氨酸、苯丙氨酸或吡喹酮及其对映体;
所述整体柱的制备包括以下步骤:
(1)Co-L-GG的制备:将四水乙酸钴、甘氨酰-L-谷氨酸于聚四氟乙烯反应釜中,加入水和甲醇搅拌溶解,然后将反应釜封装好后放入烘箱中进行反应,反应结束后待其自然冷却到室温,得到浅紫红色针状晶体,用无水甲醇多次洗涤晶体后干燥,得到Co-L-GG;
(2)毛细管的预处理:将石英毛细管依次用盐酸、去离子水、氢氧化钠、去离子水、甲醇冲洗后,氮气吹干,用3-异丁烯酰氧丙基三甲基硅烷的甲醇溶液灌注满整根毛细管,并用橡胶塞将两端堵住,于恒温水浴条件下反应过夜,取出后用甲醇冲洗掉管内多余的反应液,再次用氮气吹干;
(3)毛细管整体柱的制备:将步骤(1)制得的Co-L-GG分散于十二烷醇中,超声处理使其分散均匀,然后加入甲基丙烯酸缩水甘油酯、乙二醇二甲基丙烯酸酯、环已醇以及偶氮二异丁腈,涡旋混合均匀,得到聚合物混合液;将所得聚合物混合液填充于预处理过的毛细管中,于恒温水浴条件下进行聚合反应,最后用无水甲醇进行清洗,即得所述手性Co-L-GG掺杂的有机聚合物毛细管整体柱;
步骤(3)中所用Co-L-GG与十二烷醇的质量体积比为0.05-0.1g/3mL;所用十二烷醇与甲基丙烯酸缩水甘油酯、乙二醇二甲基丙烯酸酯、环已醇的体积比为3:3:1:3;所用偶氮二异丁腈与Co-L-GG的质量比为4:(5-10),所述聚合反应的温度为60℃,时间为12h。
2.根据权利要求1所述的应用,其特征在于,步骤(1)中所用四水乙酸钴与甘氨酰-L-谷氨酸的质量比为5:4;所述反应的温度为80℃,时间为2h;所述干燥的温度为110℃。
3.根据权利要求1所述的应用,其特征在于,步骤(2)中所述3-异丁烯酰氧丙基三甲基硅烷的甲醇溶液中3-异丁烯酰氧丙基三甲基硅烷的体积含量为50%;所述反应的温度为60℃。
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