CN114618460A - 一种含氟色谱固定相及其制备和应用 - Google Patents
一种含氟色谱固定相及其制备和应用 Download PDFInfo
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Abstract
Description
技术领域
本发明涉及液相色谱固定相,具体地说是一种键合相中含有全氟烷基链及极性基团的含氟色谱固定相。
技术背景
反相液相色谱具有柱效高、分离能力强、保留机理清楚等优点,是液相色谱分离模式中使用最为广泛的一种,广泛应用于生物大分子、蛋白质及酶的分离分析。反相色谱是以表面非极性载体为固定相,以比固定相极性强的溶剂为流动相的一种液相色谱分离模式。反相色谱固定相大多是硅胶表面键合疏水基团,基于样品中的不同组分和疏水基团之间疏水作用的不同而分离。
含氟固定相的作为一种改性反相固定相,与常用的C8、C18固定相具有不同的分离选择性:对于普通的烃类分子,含氟固定相比C8、C18固定相表现出更弱的保留力;氟化化合物在含氟固定相上的保留力通常比在C8、C18固定相上的保留力更强,同时可以根据氟含量分离氟化化合物的混合物;当流动相中有机溶剂含量升高时,可增加许多极性和碱性化合物的保留。de Galan报道了使用含氟辛基固定相对苯及氟代苯类化合物在甲醇/水体系下进行分离分析,化合物中按照氟含量的增加顺序被洗脱出;同时在C18色谱柱上进行对比,发现无法达到这样的分辨率[de Galan,L.et al,J.Chromatogr.1981,218,443-454]。Pellati报道了使用五氟苯基固定相可以很好地对麻黄碱生物碱和辛弗林进行分离,通过对流动相的盐浓度和柱温的优化调整,可以在较短时间内达到最佳分离效果。在优化的提取条件下,成功分析了不同含麻黄基质的生物碱含量以及含麻黄的标准对照物的分析[Pellati,F.et al,J.Pharm.Biomed.Anal,2008,48,254-263]。但是当前尚未出现通过水平聚合方法制备得到含有全氟烷基链及极性基团的含氟色谱固定相的相关报道。
发明内容
本发明的目的是提供一种新型含氟色谱固定相及其制备方法。该键合相包含全氟烷基链及极性基团,其制备方法简单,适用性广泛。
本发明的技术方案是:液相色谱固定相,其特征在于结构为:
其中Silica Gel为硅胶的示意(代表硅胶),m=0-30整数,R1是C1-C10的烷基链或带有苯基的C1-C10的烷基链,R2是卤素、羧基或磺酸基中的一种或二种以上。
本发明还提供了上述固定相的制备方法,其特征在于包括如下步骤:
a.硅胶预处理:硅胶加入质量浓度为1~38wt%的强酸溶液中,加热回流搅拌1~48小时,过滤,用水洗涤至pH=6~7,所得固体于干燥箱中100~160℃条件下干燥至恒重。所得干燥硅胶置于干湿度为20%~80%的气氛中24~72小时,使硅胶吸水增重0.5%~10%;
以每克硅胶计,强酸溶液的用量5-20mL;
b.硅胶表面水平聚合:在氮气或氩气保护下,在有机溶剂中加入全氟烷基硅烷偶联剂、带卤素、羧基或磺酸基的硅烷偶联剂和步骤a所得水合硅胶,在20~130℃下反应2~48小时,过滤,依次用二氯甲烷、甲醇、体积比1:1-5的甲醇水、甲醇、四氢呋喃洗涤,所得固体于干燥箱中40~80℃条件下干燥8~24小时,得到色谱固定相;
以每克硅胶计,硅烷偶联剂的用量为0.1-2.3mmol,带卤素、羧基或磺酸基的硅烷偶联剂的用量为0.1-1.8mmol,有机溶剂的用量为6-15mL。
本发明具有如下优点:
1.结构新颖。本发明首次提出利用水平聚合方法制备得到键合相中含有全氟烷基链及极性基团的反相色谱固定相。该固定相结构中带有全氟烷基链,同时还具有卤素、羧基及磺酸基等极性基团,增加了含氟固定相的浸润性,并且具有疏水作用、静电作用、氢键作用、偶极-偶极等作用力,对绝大部分天然产物及药物具有很好的分离选择性,可广泛用于各类样品的分离分析及纯化制备。
2.本发明提供的液相色谱固定相制备过程简单可靠,有利于实现产业化。
附图说明
图1为实施例8的色谱图;
图2为实施例9的色谱图;
图3为实施例10的色谱图。
具体实施方式
下面结合实例,对本发明做进一步说明。实例仅限于说明本发明,而非对本发明的限定。
实施例1
向250mL烧瓶中加入10g硅胶,加入100mL质量浓度为38wt%的盐酸溶液中,加热回流搅拌2小时,过滤,用水洗涤至pH=6~7,所得固体于干燥箱中160℃条件下干燥至恒重。所得干燥硅胶置于干湿度为50%的气氛中24小时,使硅胶吸水增重3%;
在氮气保护下,向250mL烧瓶中加入10.3g水合硅胶,加入100mL二甲苯搅拌均匀,然后滴加5.5g 1H,1H,2H,2H-全氟辛基三氯硅烷(摩尔数为11mmol)和4.1g 2-(4-氯磺酰苯基)乙基三氯硅烷(摩尔数为12mmol)混合物,在30℃下反应3小时,过滤,依次用二氯甲烷、甲醇、体积比1:1的甲醇水、甲醇、四氢呋喃洗涤,所得固体于干燥箱中80℃条件下干燥24小时,得到色谱固定相1,结构如下:
实施例2
与实施例1不同之处在于使用三氟丙基三氯硅烷(摩尔数为23mmol)代替1H,1H,2H,2H-全氟辛基三氯硅烷(摩尔数为12mmol),得到色谱固定相2,结构如下:
实施例3
与实施例1不同之处在于使用九氟己基三氯硅烷(摩尔数为15mmol)代替1H,1H,2H,2H-全氟辛基三氯硅烷(摩尔数为12mmol),得到色谱固定相3,结构如下:
实施例4
向250mL烧瓶中加入10g硅胶,加入100mL浓度为15wt%的盐酸溶液中,加热回流搅拌2小时,过滤,用水洗涤至pH=6~7,所得固体于干燥箱中120℃条件下干燥至恒重。所得干燥硅胶置于干湿度为30%的气氛中24小时,使硅胶吸水增重4.3%;
在氮气保护下,向250mL烧瓶中加入10.43g水合硅胶,加入100mL二甲苯搅拌均匀,然后滴加10mL十七氟癸基三氯硅烷(摩尔数为17mmol)和3mL 2-(4-氯磺酰苯基)乙基三氯硅烷(摩尔数为9mmol)混合物,在80℃下反应8小时,过滤,依次用二氯甲烷、甲醇、体积比1:1的甲醇水、甲醇、四氢呋喃洗涤,所得固体于干燥箱中60℃条件下干燥24小时,得到色谱固定相4,结构如下:
实施例5
向250mL烧瓶中加入10g硅胶,加入100mL浓度为25wt%的盐酸溶液中,加热回流搅拌2小时,过滤,用水洗涤至pH=6~7,所得固体于干燥箱中160℃条件下干燥至恒重。所得干燥硅胶置于干湿度为80%的气氛中12小时,使硅胶吸水增重5.2%;
在氮气保护下,向250mL烧瓶中加入10.52g水合硅胶,加入100mL二甲苯搅拌均匀,然后滴加6mL 1H,1H,2H,2H-全氟辛基三氯硅烷(摩尔数为12mmol)和4mL氯丙基三氯硅烷(摩尔数为19mmol)混合物,在60℃下反应3小时,过滤,依次用二氯甲烷、甲醇、体积比1:1的甲醇水、甲醇、四氢呋喃洗涤,所得固体于干燥箱中80℃条件下干燥16小时,得到色谱固定相5,结构如下:
实施例6
与实施例5不同之处在于使用环戊酸三氯硅烷(摩尔数为11mmol)代替氯丙基三氯硅烷(摩尔数为19mmol),得到色谱固定相6,结构如下:
实施例7
与实施例5不同之处在于使用4-丁酸三氯硅烷(摩尔数为22mmol)代替氯丙基三氯硅烷(摩尔数为19mmol),得到色谱固定相7,结构如下:
实施例8
使用实施例1所得色谱固定相1装填4.6×50mm色谱柱,用于中性和碱性化合物的分离分析,该固定相对碱性化合物具有强保留的特性。如图1所示,色谱条件为:
色谱柱:4.6×50mm;
样品:中性和碱性化合物混标(尿嘧啶1mg/mL,对羟基苯甲酸丁酯1.2mg/mL,地昔帕明2mg/mL,阿米替林2.5mg/mL);
溶剂:A:乙腈,B:水,C:100mM甲酸铵(pH=3.2);
洗脱:A:B:C=70:20:10(V/V/V);
流速:1.5mL/min;
柱温:30℃;
检测:DAD(190nm-400nm)&UV(254nm);
实施例9
使用实施例5所得色谱固定相5装填4.6×50mm色谱柱,用于浸润性测试样品的分离分析。如图2所示,填料在纯水浸润后,胸腺嘧啶的保留未发生变化,说明填料具有耐纯水的特性。色谱条件为:
色谱柱:4.6×50mm;
样品:浸润性测试混标(尿嘧啶1mg/mL,胞嘧啶1.2mg/mL,胸腺嘧啶2mg/mL);
溶剂:A:水,B:100mM甲酸铵(pH=3.2);
洗脱:A:B=90:10(V/V);
流速:1.0mL/min;
柱温:30℃;
检测:DAD(190nm-400nm)&UV(254nm);
实施例10
使用实施例5所得色谱固定相5装填4.6×50mm色谱柱,用于碱性化合物的分离分析,对碱性药物化合物具有良好的分离选择性。如图3所示,色谱条件为:
色谱柱:4.6×50mm;
样品:碱性混标(普萘洛尔3mg/mL,阿米替林3.2mg/mL,地昔帕明3mg/mL,小檗碱2mg/mL);
溶剂:A:乙腈,B:100mM甲酸铵(pH=3.2);
洗脱:A:B=90:10(V/V);
流速:1.5mL/min;
柱温:30℃;
检测:DAD(190nm-400nm)&UV(254nm)。
Claims (10)
2.按照权利要求1所述的色谱固定相,其特征在于:每克硅胶上含有0.5-2.3mmol全氟烷基链;每克硅胶上含有0.1-1.8mmol极性基团。
3.一种权利要求1或2所述的固定相的制备方法,其特征在于,包括如下步骤:
a.硅胶预处理:硅胶加入质量浓度为1~38wt%的强酸溶液中,加热回流搅拌1~48小时,过滤,固体用水洗涤至pH=6~7,所得固体于干燥箱中100~160℃条件下干燥至恒重;所得干燥硅胶置于干湿度为20%~80%的气氛中24~72小时,使硅胶吸水增重干燥硅胶质量的0.5%~10%,得水合硅胶;
b.硅胶表面水平聚合:在氮气和/或氩气保护下,在有机溶剂中加入全氟烷基硅烷偶联剂,以及带卤素、羧基或磺酸基的硅烷偶联剂中的一种或二种以上,和步骤a所得水合硅胶;在25~100℃下反应3~48小时,过滤,依次用二氯甲烷、甲醇、体积比1:1-5的甲醇水、甲醇、四氢呋喃洗涤,所得固体于干燥箱中40~80℃条件下干燥8~24小时,得到色谱固定相。
4.按照权利要求3所述的制备方法,其特征在于:步骤a所用的强酸为盐酸、硝酸、硫酸中的一种。
7.按照权利要求3所述的制备方法,其特征在于:步骤b所用的有机溶剂为二氯甲烷、甲苯、二甲苯、正庚烷、异辛烷中的一种。
8.按照权利要求3所述的制备方法,其特征在于:
步骤a所用的强酸溶液的用量为每克硅胶5-20mL;
步骤b所用的有机溶剂的用量为每克硅胶6-15mL;
步骤b所用的全氟烷基硅烷偶联剂的用量为每克硅胶0.5-2.3mmol;
步骤b所用的带卤素、羧基或磺酸基的硅烷偶联剂的用量为每克硅胶0.1-1.8mmol。
9.一种权利要求1或2所述的固定相在色谱分离过程中的应用。
10.按照权利要求9所述的应用,其特征在于:色谱分离模式为反相色谱分离和阳离子交换分离。
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