摘要
利用分步键合法制备了酰胺和咪唑基离子液体双极性基团共嵌入的十八烷基修饰硅胶色谱固定相,并通过离子交换制备了2种具有不同阴离子配位的固定相(Sil-IL-AMC18-Cl和Sil-IL-AMC18-Tf2N).采用红外光谱和元素分析对2种固定相进行了表征,发现红外光谱中均在1460和661 cm^(-1)处出现了咪唑环上C=C的伸缩振动峰和C=N的弯曲振动峰,在2927和2856 cm^(-1)处出现了─CH的不对称和对称伸缩振动峰,证明氨基咪唑离子液体键合成功;而原有919 cm^(-1)处的伯胺N─H面外变形振动峰消失,说明十八烷基酰氯与氨基已键合.元素分析结果表明,Sil-IL-AMC18-Cl的氮元素含量为3.07%,碳元素含量为16.73%,氢元素含量为3.07%,Sil-IL-AMC18-Tf2N的氮元素含量为2.88%,碳元素含量为15.98%,氢元素含量为2.95%,说明确已制得Sil-ILAMC18-Cl和Sil-IL-AMC18-Tf2N色谱固定相.考察了2种固定相的色谱分离模式与分离性能,结果表明:(1)在反相色谱模式(RPLC)下,相较于商品化C18色谱柱,两种固定相均具有更高的柱效;(2)由于具有双极性基团,相较于传统亲水改性C18硅胶固定相具有更强的亲水能力,因此可以实现亲水色谱模式(HILIC);(3)在反相/亲水(RPLC/HILIC)混合色谱模式下,可同时分离亲水性和疏水性物质.通过考察发现,Sil-IL-AMC18-Cl固定相比Sil-IL-AMC18-Tf2N固定相有更强的亲水性能,因此在HILIC色谱模式下将Sil-IL-AMC18-Cl固定相应用于8种碱基核苷类物质的分离,可实现该类强亲水性物质的基线分离,进样重复性RSD=0.03%~0.25%(n=9);在RPLC色谱模式下将Sil-IL-AMC18-Tf2N固定相应用于6种苯胺类物质的分离,不仅可以实现基线分离,而且可明显改善苯胺类物质的峰拖尾现象,进样重复性RSD=0.05%~0.10%(n=9).
In this work,octadecyl-modified silica chromatographic stationary phases with amide and imidazolebased ionic liquid bipolar groups co-embedded were prepared by stepwise bonding and two stationary phases with different anionic coordinations(Sil-IL-AMC18-Cl and Sil-IL-AMC18-Tf2N)were prepared by ion-exchange,which were characterized by means of infrared spectroscopy and elemental analysis.Both stationary phases showed C=C stretching vibration peaks and C=N bending vibration peaks on the imidazole ring at 1460 and 661 cm^(-1),and asym⁃metric and symmetric stretching vibration peaks of─CH at 2927 and 2856 cm^(-1),which proved the bonding of amino-imidazole ionic liquid.And the original 919 cm^(-1) of primary amine N─H out-of-plane deformation vibration peak dis⁃appeared,indicating that octadecanoyl chloride is bonded with amino.The results of elemental analysis showed that Sil-IL-AMC18-Cl contained 3.07%of nitrogen,16.73%of carbon and 3.07%of hydrogen,and Sil-IL-AMC18-Tf2N contained 2.88%of nitrogen,15.98%of carbon and 2.95%of hydrogen,which indicated that Sil-IL-AMC18-Cl and Sil-IL-AMC18-Tf2N chromatographic stationary phases were prepared.The chromatographic separation modes and performance of Sil-IL-AMC18-Cl and Sil-IL-AMC18-Tf2N stationary phases were investigated,and the results showed that:(1)the two stationary phases had higher column efficiency than commercial C18 columns in the reversed-phase chromatographic mode(RPLC);(2)since the stationary phase has a bipolar group,it has a stronger hydrophilic ability compared to the traditional hydrophilic modified C18 silica stationary phase,and thus hydrophilic chromato⁃graphic mode(HILIC)can be realized;(3)simultaneous separation of hydrophilic and hydrophobic substances in mixed reversed-phase/hydrophilic(RPLC/HILIC)chromatographic mode.It was found that Sil-IL-AMC18-Cl stationary phase had stronger hydrophilic properties compared to Sil-IL-AMC18-Tf2N stationary phase,so in the HILIC chromatographic mode Sil-IL-AMC18-Cl stationary phase was used for the separation of 8 base nucleosides,which could realize the baseline separation of this kind of strong hydrophilic substances,and the RSD of the injection repeatability was 0.03%-0.25%(n=9);in the RPLC chromatographic mode,Sil-IL-AMC18-Tf2N stationary phase was used for the separation of 6 anilines,which not only could realize the baseline separation,but also improved the peak trailing problem of anilines,and the RSD of the injection repeatability was 0.05%-0.10%(n=9).
作者
陈贝怡
观文娜
靳钊
刘婷婷
周睿
CHEN Beiyi;GUAN Wenna;JIN Zhao;LIU Tingting;ZHOU Rui(School of Polymer Science and Engineering,Qingdao University of Science and Technology,Qingdao 266045,China;Qingdao Institute of Bioenergy and Bioprocess Technology,Chinese Academy of Sciences,Qingdao 266101,China)
出处
《高等学校化学学报》
SCIE
EI
CAS
CSCD
北大核心
2024年第4期19-28,共10页
Chemical Journal of Chinese Universities
基金
中国科学院仪器设备功能开发技术创新项目资助。
关键词
亲水改性C18硅胶填料
混合模式液相色谱固定相
碱基核苷
苯胺
Hydrophilic modified C18 silica gel filler
Mixed-mode liquid chromatography stationary phase
Base nucleoside
Aniline
