大管电色谱技术和毛细管电色谱新型固定相研究
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摘要
毛细管电色谱(CEC)是近年来新兴的高效、快速的微分离分析技术,是色谱领域的研究热点之一。众多的科研工作者就电色谱的基本理论、柱制备技术、新型固定相合成及应用展开了大量的工作。本论文主要对大管电色谱技术和毛细管电色谱新型固定相进行了研究。
1.大管电色谱(WE)技术
CEC由于受焦耳热的限制,大多使用100μm以下的毛细管,低的载样量严重限制了其用于制备/半制备,也降低了检测的灵敏度。本论文设计并建立了一套大管电色谱系统,使用大内径石英管作为分离管道,在内部插入合适内径的毛细管作为制冷管,并通以冷却液,这样电泳过程中产生的焦耳热就可以及时地带出体系,从根本上解决了大管电色谱焦耳热的问题,使电色谱在大分离管道中进行成为可能。
利用构建的WE体系,成功地制作了丙烯酰胺整体柱。以硫脲、萘和甲苯三种中性化合物为探针化合物,在电色谱模式下对该整体柱进行了评价。实验结果表明,大管体系具有良好的散热能力,即使在625 V cm-1的高电场下也没有发现焦耳热积累的现象。对于联苯最大载样量可以达到3μg,与普通的毛细管电色谱相比,载样量提高了几百倍。此外,在该大管整体柱上还对一种食品染料进行了分离,取得了很好的分离效果。使用该整体柱还对穿心莲片中的脱水穿心莲内酯进行了测定。
在WE体系的基础上成功进行了琼脂糖凝胶电泳实验。由于引入内制冷体系,电泳过程中产生的焦耳热可以及时消除,从而实现高电场下分离,克服了常规琼脂糖凝胶电泳分离电压低、分离时间长的问题。由于使用大内径石英管进行直接紫外检测,避免了使用染色剂对人体的危害,同时灵敏度大大提高,比平板琼脂糖凝胶电泳提高1000倍。
2.磺酸化聚β-环糊精硅胶整体柱CEC
CEC具有高效性、高选择性、消耗的溶剂和手性样品少等优点,在手性化合物拆分方面也受到很多科研工作者的高度关注。本文首次制备了新型磺酸化聚β-环糊精整体柱。该环糊精整体柱通过化学键将环糊精键合到整体柱上,易于除去磺酸化过程中产生的高浓度无机盐。将其用于手性药物的拆分,得到了较好的分离效果,并且分离速度快,对测定的手性样品20 min内均能实现分离,部分样品十分钟之内即可以实现分离。
3.有机硅树状化合物填充柱CEC
本文首次将有机硅树状化合物固定相用于毛细管电色谱填充柱研究。实验结果表明,树状填料具有典型的反相色谱性质,在低的键合量情况下具有较好的疏水性能,将其用于中性化合物分离时取得了较好的效果,对于硫脲柱效将近90000 N m-1。
Capillary electrochromatography is a new micro-separation technique with high performance and fast speed. Much research is focused on its theory, column technique, new stationary phase and application. The main work of this dissertation is shown as follow:
1. Wide bore electrochromatography (WE) technique
The separation channel of CEC is restricted to capillary scale with id smaller than 100μm due to the limit of Joule heat, which results in low loadability and poor concentration detectability. In order to solve this problem, a new device was setup to perform wide bore electrochromatography. A quartz tube with millimeter id was used as the separation channel and a proper coolant was pumped through the inner cooling capillary which is coaxially inserted into the separation channel to dispel the Joule heat generated during electrophoresis. The WE system made it possible to perform electrochromatography in a wide bore tube.
Polyacrylamide monolithic column was prepared successfully on the WE system.
The column was evaluated in the electrochromatography mode using thiourea, naphthalene and biphenyl as probe compounds. Results indicated that this system can dissipate Joule heat in situ in real time, and has higher loadability compared with CEC. Agarose gel column was prepared on the WE system. Higher electric field strength could be applied across the gel column due to the inner cooling mechanism, which made the separation faster than conventional agarose gel electophoresis. At the same time, lower concentration detectablility was obtained due to direct UV detection and longer light distance.
2. Sulfated poly (β-cyclodextrin) silica-based monolithic column for CEC
A sulfated poly (β-cyclodextrin) silica-based monolithic column was prepared in capillary. Then it was evaluated in the CEC mode. Good enantiomeric separations were obtained when the column was applied in chiral separation. 3. Carbosilane dendrimer packed column for CEC
Carbosilane dendrimer modified silica was synthesized and then packed into capillary by slurry method to perform CEC. Results indicated that carbosilane dendrimer stationary phase has typical reversed phase characteristics; comparable hydrophobic selectivity was obtained even with low bonding density. Several neutral compounds were separated on the stationary phase with satisfactory efficiency. The theoretical plate number for thiourea was almost up to 90 000 N m-1.
1.大管电色谱(WE)技术
CEC由于受焦耳热的限制,大多使用100μm以下的毛细管,低的载样量严重限制了其用于制备/半制备,也降低了检测的灵敏度。本论文设计并建立了一套大管电色谱系统,使用大内径石英管作为分离管道,在内部插入合适内径的毛细管作为制冷管,并通以冷却液,这样电泳过程中产生的焦耳热就可以及时地带出体系,从根本上解决了大管电色谱焦耳热的问题,使电色谱在大分离管道中进行成为可能。
利用构建的WE体系,成功地制作了丙烯酰胺整体柱。以硫脲、萘和甲苯三种中性化合物为探针化合物,在电色谱模式下对该整体柱进行了评价。实验结果表明,大管体系具有良好的散热能力,即使在625 V cm-1的高电场下也没有发现焦耳热积累的现象。对于联苯最大载样量可以达到3μg,与普通的毛细管电色谱相比,载样量提高了几百倍。此外,在该大管整体柱上还对一种食品染料进行了分离,取得了很好的分离效果。使用该整体柱还对穿心莲片中的脱水穿心莲内酯进行了测定。
在WE体系的基础上成功进行了琼脂糖凝胶电泳实验。由于引入内制冷体系,电泳过程中产生的焦耳热可以及时消除,从而实现高电场下分离,克服了常规琼脂糖凝胶电泳分离电压低、分离时间长的问题。由于使用大内径石英管进行直接紫外检测,避免了使用染色剂对人体的危害,同时灵敏度大大提高,比平板琼脂糖凝胶电泳提高1000倍。
2.磺酸化聚β-环糊精硅胶整体柱CEC
CEC具有高效性、高选择性、消耗的溶剂和手性样品少等优点,在手性化合物拆分方面也受到很多科研工作者的高度关注。本文首次制备了新型磺酸化聚β-环糊精整体柱。该环糊精整体柱通过化学键将环糊精键合到整体柱上,易于除去磺酸化过程中产生的高浓度无机盐。将其用于手性药物的拆分,得到了较好的分离效果,并且分离速度快,对测定的手性样品20 min内均能实现分离,部分样品十分钟之内即可以实现分离。
3.有机硅树状化合物填充柱CEC
本文首次将有机硅树状化合物固定相用于毛细管电色谱填充柱研究。实验结果表明,树状填料具有典型的反相色谱性质,在低的键合量情况下具有较好的疏水性能,将其用于中性化合物分离时取得了较好的效果,对于硫脲柱效将近90000 N m-1。
Capillary electrochromatography is a new micro-separation technique with high performance and fast speed. Much research is focused on its theory, column technique, new stationary phase and application. The main work of this dissertation is shown as follow:
1. Wide bore electrochromatography (WE) technique
The separation channel of CEC is restricted to capillary scale with id smaller than 100μm due to the limit of Joule heat, which results in low loadability and poor concentration detectability. In order to solve this problem, a new device was setup to perform wide bore electrochromatography. A quartz tube with millimeter id was used as the separation channel and a proper coolant was pumped through the inner cooling capillary which is coaxially inserted into the separation channel to dispel the Joule heat generated during electrophoresis. The WE system made it possible to perform electrochromatography in a wide bore tube.
Polyacrylamide monolithic column was prepared successfully on the WE system.
The column was evaluated in the electrochromatography mode using thiourea, naphthalene and biphenyl as probe compounds. Results indicated that this system can dissipate Joule heat in situ in real time, and has higher loadability compared with CEC. Agarose gel column was prepared on the WE system. Higher electric field strength could be applied across the gel column due to the inner cooling mechanism, which made the separation faster than conventional agarose gel electophoresis. At the same time, lower concentration detectablility was obtained due to direct UV detection and longer light distance.
2. Sulfated poly (β-cyclodextrin) silica-based monolithic column for CEC
A sulfated poly (β-cyclodextrin) silica-based monolithic column was prepared in capillary. Then it was evaluated in the CEC mode. Good enantiomeric separations were obtained when the column was applied in chiral separation. 3. Carbosilane dendrimer packed column for CEC
Carbosilane dendrimer modified silica was synthesized and then packed into capillary by slurry method to perform CEC. Results indicated that carbosilane dendrimer stationary phase has typical reversed phase characteristics; comparable hydrophobic selectivity was obtained even with low bonding density. Several neutral compounds were separated on the stationary phase with satisfactory efficiency. The theoretical plate number for thiourea was almost up to 90 000 N m-1.
引文
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