CN110523403B - 一种生物碱类化合物用硅胶液相色谱填料及其制备方法 - Google Patents
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Abstract
本发明涉及一种生物碱类化合物用硅胶液相色谱填料及其制备方法。包含以下步骤:将多孔硅胶微球置于强碱性水溶液中,制得活化硅胶;将水溶性钛盐及锆盐混合物溶于pH为1‑6的酸性缓冲溶液中,制得前驱体混合溶液;将活化硅胶与前驱体混合溶液按照一定比例混合搅拌反应,制得TiO2‑ZrO2/SiO2‑1;重复包覆过程,制得TiO2‑ZrO2/SiO2‑n微球;对TiO2‑ZrO2/SiO2‑n微球在300‑600℃条件下加热处理3‑12 h,得到色谱填料。本发明填料具有丰富的作用位点,较强的化学稳定性,通过控制溶液中Ti4+和Zr4+的浓度调节TiO2‑ZrO2纳米层的厚度及复合纳米层中两种金属氧化物的比例,使其具有更加丰富的作用位点,适用于更宽的pH范围。
Description
技术领域
本发明涉及液相色谱领域,具体地涉及一种生物碱类化合物用硅胶液相色谱填料及其制备方法。
背景技术
目前,生物碱类化合物种类多达12000余种,在具有重要药理活性的天然产物中占据比例超出50%,具有重要的开发潜力(梁鑫淼等,分析测试学报,2019)。该类化合物的种类繁多,结构类型多样,因此,对该类化合物分离纯化一直是亟待解决的关键科学问题。
在该类化合物的分离分析中,反相液相色谱是应用最为广泛的分离模式。碱性化合物的离子化特性使其与硅胶基质表面残余的酸性硅醇基相互作用,从而导致其色谱峰形拖尾,柱效降低。因此,发展一类化学稳定性强,色谱分离性能良好的液相色谱填料具有重要意义。
发明内容
针对上述现有技术的不足,本发明提供一种生物碱类化合物用硅胶液相色谱填料及其制备方法。该填料具有丰富的作用位点,较强的化学稳定性。
一种生物碱类化合物用硅胶液相色谱填料的制备方法,包含以下步骤:
(1)碱性溶液活化:将多孔硅胶微球置于强碱性水溶液中,在一定温度下搅拌,离心、洗涤至中性,干燥后,得活化硅胶;
(2)前驱体混合溶液制备:将水溶性钛盐及锆盐混合物溶于pH为1-6的酸性缓冲溶液中,剧烈搅拌至全部溶解,得前驱体混合溶液;
(3)单次包覆:将步骤(1)所得的活化硅胶与步骤(2)所得前驱体混合溶液按照一定比例混合搅拌反应,洗涤、干燥,制得TiO2-ZrO2/SiO2-1;
(4)重复:重复步骤(3)的包覆过程,制得TiO2-ZrO2/SiO2-n微球;其中n表示包覆次数,n为1-8之间的整数;
(5)加热固化:对步骤(4)制得的TiO2-ZrO2/SiO2-n微球在300-600℃条件下加热处理3-12 h,得到色谱填料。
优选的,所述步骤(1)中的强碱为氢氧化钠或氢氧化钾。
优选的,所述步骤(1)中的强碱性水溶液中氢氧根离子浓度为0.5-2 mol/L。
优选的,所述步骤(1)中的搅拌温度为25-45℃。
优选的,所述步骤(2)中水溶性钛盐和锆盐重量比例为1:500-500:1。
优选的,所述步骤(3)中活化硅胶与前驱体混合溶液重量比例为0.01-2 g/ml。
优选的,所述步骤(3)中混合搅拌反应时间为0.1 h-12 h。
有益效果:本发明填料可以克服目前液相色谱填料在生物碱类化合物色谱分离时峰形较差、柱效较低的弊端。使TiO2-ZrO2/SiO2复合层在多孔硅胶表面固化,得到色谱填料,具有丰富的作用位点,较强的化学稳定性,通过控制溶液中Ti4+和Zr4+的浓度调节TiO2-ZrO2纳米层的厚度及复合纳米层中两种金属氧化物的比例,使其适用于更宽的pH范围(pH=1-14)。另外,以碱性缓冲溶液为流动相时,可实现生物碱类化合物的有效分离。相比于现有的用于生物碱类化合物分离分析的填料,通过该方法所得材料具有更好的色谱分离性能。
附图说明
图1 为实施例1所得色谱填料的扫描电镜图。
图2 为实施例1所得色谱填料分离延胡索乙素、石蒜碱、吉非替尼、粉防己碱、小檗碱五种化合物的液相色谱图。
图3为实施例2所得色谱填料的扫描电镜图。
具体实施方式
实施例1
一种生物碱类化合物用硅胶液相色谱填料的制备方法,包括以下五个步骤:
碱性溶液活化:将2 g多孔硅胶微球(商品化产品,粒径5微米,孔径10 nm)置于强碱性水溶液中,在25℃条件下搅拌,离心、去离子水洗涤至中性、100℃干燥后备用;
前驱体混合溶液制备:将1g硝酸钛和1g硝酸锆混合物溶于20 mL pH=1.5的NH4AC-HCl缓冲溶液中,剧烈搅拌直至全部溶解;
单次包覆:将所得的活化硅胶加入到所得前驱体混合溶液中混合搅拌,30 min后洗涤、干燥,制得TiO2-ZrO2/SiO2-1;
重复:重复一次上述步骤的包覆反应过程,制得TiO2-ZrO2/SiO2-2微球;
加热固化:对制得的TiO2-ZrO2/SiO2-2微球在500℃条件下加热处理8 h,使TiO2-ZrO2复合层在多孔硅胶表面固化,得到TiO2-ZrO2/SiO2-2色谱填料。
将所得TiO2-ZrO2/SiO2-2色谱填料采用干法填充30 cm× 0.53mm i.d.弹性石英毛细管柱,分离延胡索乙素、石蒜碱、吉非替尼、粉防己碱、小檗碱五种化合物,色谱条件:流动相:乙腈/pH=10的20mM醋酸铵水溶液=89/11;流速:10.0μL/min;柱温:25 oC;紫外检测波长:280nm。色谱图对应本发明图2,从图2中可看出,碱性药类化合物得到较好的色谱分离。
本发明首先采用强碱处理硅胶,使其表面容易吸附Ti4+和Zr4+。利用静电作用,在Ti4+和Zr4+的酸性缓冲溶液条件下使氧化钛-锆纳米层均匀沉积于多孔硅胶内、外表面。然后进行焙烧处理,使硅胶表面的硅羟基与TiO2-ZrO2纳米层表面的铝Ti-OH和Zr-OH之间发生脱水反应形成Si-O-Ti/Zr键,使TiO2-ZrO2复合纳米层在硅胶内、外表面固化。通过调节沉积次数,可以控制TiO2-ZrO2纳米层厚度,获得不同性能的TiO2-ZrO2/SiO2-n液相色谱填料。
本申请有效简化了实验步骤。本申请所得分离结果好,将TiO2-ZrO2/SiO2-2材料填充30cm× 0.53mm i.d弹性石英毛细管柱,在亲水作用模式下分离延胡索乙素、吉非替尼、粉防己碱、盐酸石蒜碱、小檗碱,色谱条件:流动相:乙腈/pH=9.0的20mM醋酸铵水溶液=80/20;流速:12 .0μL/min;柱温:25℃;紫外检测波长:280nm。色谱图如图2所示,延胡索乙素、吉非替尼、粉防己碱、盐酸石蒜碱、小檗碱的色谱分离柱效分别为32,000塔板数/米,34,000塔板数/米,42,000塔板数/米,40,000塔板数/米,48,000塔板数/米。
实施例2:
一种生物碱类化合物用硅胶液相色谱填料的制备方法,包括以下五个步骤:
碱性溶液活化:将3 g多孔硅胶微球(粒径5微米,孔径20 nm)置于强碱性水溶液中,在45℃条件下搅拌,离心、去离子水洗涤至中性、80℃干燥后备用;
前驱体混合溶液制备:将2g硝酸钛和1g硝酸锆混合物溶于30 mL pH=3的NH4AC-HCl缓冲溶液中,剧烈搅拌直至全部溶解;
单次包覆:将所得的活化硅胶加入到所得前驱体混合溶液中混合搅拌,2h后洗涤、干燥,制得TiO2-ZrO2/SiO2-1;
重复:重复上述步骤的包覆反应过程多次,制得TiO2-ZrO2/SiO2-5微球;
加热固化:对制得的TiO2-ZrO2/SiO2-5微球在600℃条件下加热处理12h,使TiO2-ZrO2复合层在多孔硅胶表面固化,得到TiO2-ZrO2/SiO2-5色谱填料。
本发明可用其他的不违背本发明的精神或主要特征的具体形式来概述。因此,无论从哪一点来看,本发明的上述实施方案都只能认为是对本发明的说明而不能限制本发明,权利要求书指出了本发明的范围,而上述的说明并未指出本发明的范围,因此,在与本发明的权利要求书相当的含义和范围内的任何改变,都应认为是包括在本发明的权利要求书的范围内。
Claims (7)
1.一种生物碱类化合物用硅胶液相色谱填料的制备方法,其特征在于, 包含以下步骤:
(1)碱性溶液活化:将多孔硅胶微球置于强碱性水溶液中,在一定温度下搅拌,离心、洗涤至中性,干燥后,得活化硅胶;其中,强碱性水溶液中氢氧根离子浓度为0.5-2 mol/L;
(2)前驱体混合溶液制备:将水溶性钛盐及锆盐混合物溶于pH为1-6的酸性缓冲溶液中,剧烈搅拌至全部溶解,得前驱体混合溶液;
(3)单次包覆:将步骤(1)所得的活化硅胶与步骤(2)所得前驱体混合溶液按照一定比例混合搅拌反应,洗涤、干燥,制得TiO2-ZrO2/SiO2-1;
(4)重复:重复步骤(3)的包覆过程,制得TiO2-ZrO2/SiO2-n微球;其中n表示包覆次数,n为1-8之间的整数;
(5)加热固化:对步骤(4)制得的TiO2-ZrO2/SiO2-n微球在300-600℃条件下加热处理3-12 h,得到色谱填料。
2.如权利要求1所述的制备方法,其特征在于,所述步骤(1)中的强碱为氢氧化钠或氢氧化钾。
3.如权利要求1所述的制备方法,其特征在于,所述步骤(1)中的反应溶液温度为25-45℃。
4.如权利要求1所述的制备方法,其特征在于,所述步骤(2)中水溶性钛盐和锆盐重量比例为1:500-500:1。
5.如权利要求1所述的制备方法,其特征在于,所述步骤(3)中活化硅胶与前驱体混合溶液重量比例为0.01-2 g/ml。
6.如权利要求1所述的制备方法,其特征在于,所述步骤(3)中混合搅拌反应时间为0.1h-12 h。
7.一种如权利要求1-6任一项所述生物碱类化合物用硅胶液相色谱填料的制备方法制备得到的色谱填料。
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