CN114618457A - 一种双硝基取代的苯基色谱固定相及其制备和应用 - Google Patents
一种双硝基取代的苯基色谱固定相及其制备和应用 Download PDFInfo
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- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/281—Sorbents specially adapted for preparative, analytical or investigative chromatography
- B01J20/286—Phases chemically bonded to a substrate, e.g. to silica or to polymers
- B01J20/287—Non-polar phases; Reversed phases
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D15/00—Separating processes involving the treatment of liquids with solid sorbents; Apparatus therefor
- B01D15/08—Selective adsorption, e.g. chromatography
- B01D15/26—Selective adsorption, e.g. chromatography characterised by the separation mechanism
- B01D15/32—Bonded phase chromatography
- B01D15/325—Reversed phase
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D15/00—Separating processes involving the treatment of liquids with solid sorbents; Apparatus therefor
- B01D15/08—Selective adsorption, e.g. chromatography
- B01D15/26—Selective adsorption, e.g. chromatography characterised by the separation mechanism
- B01D15/32—Bonded phase chromatography
- B01D15/325—Reversed phase
- B01D15/327—Reversed phase with hydrophobic interaction
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- B—PERFORMING OPERATIONS; TRANSPORTING
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Abstract
Description
技术领域
本发明涉及液相色谱固定相,具体地说是一种双硝基取代的苯基色谱固定相。
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。
苯基固定相作为反相固定相中使用较多的一种固定相,对中性化合物具有良好的分离选择性。Matysova等报道了利用苯己基固定相对驱虫剂中双羟萘酸噻嘧啶、奥芬达唑、芬苯达唑、丁基羟基茴香醚具有良好的分离效果[Matysova.L.et al,Anal.Methods,2012,4,1592-1597]。Powell报道了根据不同苯基固定相对结构相似的类固醇进行选择性分析,结果证明含有联苯配体的固定相在分离不饱和程度不同的类固醇样品时效果最好,二苯基固定相对类固醇差向异构体的分离效果优于联苯基固定相[Powell.M.et al,Anal.Methods,2013,5,5014–5018]。但是单一的苯基结构固定相在对分析样品的选择上具有一定的限制性。
发明内容
本发明的目的是提供一种新型含双硝基的苯基色谱固定相及其制备方法。该键合相上的苯基被双硝基取代,并通过极性基团连接到硅胶表面,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),R是带有氨基、酰胺基、酯基、苯基、偶氮基、醚键、脲基中的一种或二种以上官能团的C1-C10的烷基链。
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8~24小时,得酸化后硅胶;
以每克硅胶计,强酸溶液的用量6-20mL;
b.硅烷化反应引入苯环及多功能基团:在氮气或氩气保护下,在有机溶剂中加入硅烷偶联剂、碱性催化剂和经80-200℃干燥8~18小时的硅胶,在40~130℃下反应8~24小时,过滤,依次用甲醇、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,得到硝基键合相;
以每克硅胶计,硅烷偶联剂的用量为0.1-2.4mmol,有机溶剂的用量为6-15mL,碱性催化剂的用量为2-20mmol。
本发明具有如下优点:
1.结构新颖。本发明首次提出双硝基取代的苯基色谱固定相。该固定相结构中由于苯环邻对位存在双硝基,固定相的电负性较强,同时带有氨基、酯基等极性基团及疏水性的苯环,具有疏水作用、π-π作用力、氢键作用力、静电作用、偶极-偶极等作用力,该固定相具有良好的分离选择性,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5的色谱图;
图2为实施例6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24小时,得酸化后硅胶;
在氮气保护下,向100mL烧瓶中加入10g经160℃干燥16小时的硅胶(粒径为5μm,孔径为10nm)、10mL 3-(2,4-二硝基苯基氨基)丙基三乙氧基硅烷(摩尔数为24mmol)、6g N,N-二甲基吡啶和60mL二甲苯,在110℃下反应6小时,过滤,依次用甲醇、甲醇水、甲醇、四氢呋喃洗涤,所得固体在干燥箱中80℃条件下干燥16个小时,得到色谱固定相1,结构如下:
实施例2
操作过程和条件同实施例1,与实施例1不同之处在于,使用3-(2,4-二硝基苯基脲基)丙基三乙氧基硅烷(摩尔数为22mmol)代替3-(2,4-二硝基苯基氨基)丙基三乙氧基硅烷(摩尔数为24mmol),得到色谱固定相2,结构如下:
实施例3
向250mL烧瓶中加入10g硅胶,加入80mL浓度为10wt%的盐酸溶液中,加热回流搅拌48小时,过滤,用水洗涤至pH=6~7,所得固体于干燥箱中200℃条件下干燥12小时,得酸化后硅胶;
在氩气保护下,向100mL烧瓶中加入10g经200℃干燥6小时的硅胶(粒径为3.5μm,孔径为30nm)、10mL 2,4-硝基苄基(3-三乙氧基硅基丙基氨基)甲酸酯(摩尔数为22mmol)、3mL吡啶和100mL二氯甲烷,在40℃下反应48小时,过滤,依次用甲醇、甲醇水、甲醇、四氢呋喃洗涤,所得固体在干燥箱中100℃条件下干燥12个小时,得到色谱固定相3,结构如下:
实施例4
操作过程和条件同实施例3,与实施例3不同之处在于,使用2,4-硝基-4'(N-乙基-N-三甲氧基硅基氨基甲酸酯)氨基偶氮苯(摩尔数为14mmol)代替4,5-二甲氧基-2-硝基苄基(3-三乙氧基硅基丙基氨基)甲酸酯(摩尔数为22mmol),得到色谱固定相4,结构如下:
实施例5
使用实施例1所得色谱固定相1装填4.6×50mm色谱柱,用于非极性化合物的分离分析。如图1所示,色谱条件为:
色谱柱:4.6×50mm;
样品:非极性化合物混标(尿嘧啶1mg/mL,硝基苯1mg/mL,萘2mg/mL,芴2.2mg/mL);
溶剂:A:乙腈,B:水;
洗脱:A:B=60:40(V/V);
流速:1.5mL/min;
柱温:30℃;
检测波长:PDA(190nm-400nm)&UV(254nm);
实施例6
使用实施例1所得色谱固定相1装填4.6×50mm色谱柱,用于中性化合物与碱性化合物的分离分析。如图2所示,填料对中性化合物尿嘧啶及对羟基苯甲酸丁酯保留较弱,对碱性化合物阿米替林的保留较强,具有良好的分离选择性,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,阿米替林2.5mg/mL);
溶剂:A:乙腈,B:200mM甲酸铵(pH=3.2);
洗脱:A:B=70:30(V/V);
流速:1.5mL/min;
柱温:30℃;
检测波长:PDA(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0.2-4.8mmol硝基基团。
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8~24小时,得酸化后硅胶;
b.硅烷化反应引入苯环及多功能基团:在氮气或氩气保护下,在有机溶剂中加入硅烷偶联剂、碱性催化剂和经80-200℃干燥8~18小时的硅胶,在40~130℃下反应8~24小时,过滤,依次用甲醇、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,得到双硝基键合相。
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。
6.按照权利要求3所述的制备方法,其特征在于:步骤b所用的有机溶剂为非极性的二氯甲烷、甲苯、二甲苯、正庚烷、异辛烷中的一种。
7.按照权利要求3所述的制备方法,其特征在于:步骤b所用的碱性催化剂为二异丙基乙胺、三乙胺、N,N-二甲基吡啶、吡啶、咪唑中的一种。
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6-20mL;
步骤b所用的有机溶剂的用量为每克硅胶6-15mL;
步骤b所用的硅烷偶联剂的用量为每克硅胶0.1-2.4mmol;
步骤b所用的碱性催化剂的用量为每克硅胶2-20mmol。
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。
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