| 高碳含量新型亚微米无孔二氧化硅材料的修饰方法及其在反相加压毛细管电色谱平台上的应用 |
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| 引用本文： | 夏子航,Soumia CHEDDAH,王薇薇,王彦,阎超. 高碳含量新型亚微米无孔二氧化硅材料的修饰方法及其在反相加压毛细管电色谱平台上的应用[J]. 色谱, 2022, 40(1): 88-99. DOI: 10.3724/SP.J.1123.2021.03042 |
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| 作者姓名： | 夏子航 Soumia CHEDDAH 王薇薇 王彦 阎超 |
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| 作者单位： | 上海交通大学药学院, 上海 200240 |
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| 基金项目： | 国家自然科学基金项目(81874307,21874088);上海市科委“科技创新行动计划”(18142200700,19142203100,20142200400,18490731500);细胞工程及抗体药物教育部工程研究中心开放课题(19X110020009-005);上海交通大学“新进青年教师启动计划”(19X100040029). |
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| 摘 要： | 亚微米无孔二氧化硅(NPS)材料具有小粒径及表面光滑形状规整等特点,是一种性能优异的色谱材料,但其存在比表面积小、修饰效率低的问题.针对此设计了一种具有高碳含量的修饰方法:以3-缩水甘油基氧基丙基三甲氧基硅烷(GPTS)作为硅烷偶联剂,聚乙烯亚胺(PEI)作为聚合物包覆层,并以硬脂酰氯修饰得到一种氨基包覆的具有C18碳...
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| 关 键 词： | 加压毛细管电色谱 亚微米无孔二氧化硅微球 高碳含量 硅羟基 电渗流 |
| 收稿时间： | 2021-03-29 |
Novel submicron nonporous silica material modification with high carbon content and its application in reversed-phase pressurized capillary electrochromatography |
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| XIA Zihang,Soumia CHEDDAH,WANG Weiwei,WANG Yan,YAN Chao. Novel submicron nonporous silica material modification with high carbon content and its application in reversed-phase pressurized capillary electrochromatography[J]. Chinese journal of chromatography, 2022, 40(1): 88-99. DOI: 10.3724/SP.J.1123.2021.03042 |
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| Authors: | XIA Zihang Soumia CHEDDAH WANG Weiwei WANG Yan YAN Chao |
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| Affiliation: | School of Pharmacy, Shanghai Jiao Tong University, Shanghai 200240, China |
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| Abstract: | Submicron nonporous silica(NPS) materials feature small particle sizes, smooth surfaces, and regular shapes. They also exhibit excellent performance as a stationary phase;however, their use is limited by their low specific surface area and low phase ratio. Therefore, a novel surface modification strategy tailored for NPS microspheres was designed, involving a multi-step reaction. 3-Glycidyloxypropyltrimethoxysilane(GPTS) was first grafted onto NPS particles as a silane coupling agent. Polyethyleneimine(PEI), a high-molecular-weight polymer, was then coated onto the particles, providing numerous amino reaction sites. In the final step, an acylation reaction was initiated between stearoyl chloride and the amino groups to obtain the final product, designated as C18-NH2-GPTS-SiO2. Elemental analysis, FT-IR spectroscopy, Zeta potential analysis, thermogravimetric analysis(TGA), and scanning electron microscopy(SEM) were employed to investigate the success of the chemical modifications at each step. The carbon content increased from 0.55% to higher than 8.29%. Thus, it solved the low carbon loading capacity problem when modifying NPS microspheres with traditional C18 reversed phase(e. g., octadecyl chlorosilane modification). Meanwhile, the reasons for the considerable differences between NPS and porous silica(PS) microspheres in terms of the reactivity to surface modification were investigated in detail. The BET method was employed to compare the pore structures. FT-IR and 29Si solid-state NMR spectroscopy were employed to analyze the differences in the structure and quantity of silanol groups on the surfaces of the NPS and PS microspheres. Differences were observed not only in the pore size and surface area, but also in the types of silanol groups. FT-IR analysis indicated that the NPS and PS microspheres had different υSi-OH band positions, which shifted from 955 to 975 cm-1, respectively. 29Si solid-state NMR analysis further highlighted the differences in structural information for Si atom environments. Results revealed that 16% of silicon atoms in the PS microspheres had one hydroxyl group(isolated silanols, Q3, δ 100), while 19% had two hydroxyl groups(geminal silanols, Q2, δ 90). On the other hand, the NPS microspheres possessed no geminal silanols, and only 30% of the Si atoms were in the Q3 state. Therefore, the NPS microspheres had a lower density of silanol groups and lacked geminal silanol groups, compared to the PS microspheres. Geminal silanol groups have already been confirmed in previous studies to offer far higher reactivity than isolated silanols. These factors together explained the low reactivity of NPS microspheres toward surface modification. Further, the low specific surface area of the microspheres arising from their nonporous nature made it challenging to obtain a high carbon content through a simple one-step reaction.Hydrophobic substances such as hydrocarbons from the benzene series and polycyclic aromatic hydrocarbons(PAHs) were selected to study the chromatographic performance. The hydrophobic mechanism was revealed by the separation of PAHs using different ratios of acetonitrile. Separation was achieved with a C18-NH2-GPTS-SiO2 column,following which a hydrophobic phenomenon occurred. The presence of the amino coating led to the inversion of the electroosmotic flow(EOF)of the silica microspheres on the pressurized capillary electrochromatography(pCEC)platform. It also enhanced the linear velocity in the pCEC platform when the pH was selected to be low. The effects of the applied voltage on the separation ability of the720 nm C18-NH2-GPTS-SiO2 column were examined to determine optimal conditions. Rapid and effective separation was achieved in a relatively short time. Therefore,the C18-NH2-GPTS-SiO2 stationary phase is promising for practical use with a higher phase ratio,demonstrating superiority for use in reversed-phase pCEC separation,and thus,providing a new strategy and valuable reference for the future application of submicron NPS microspheres. |
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| Keywords: | pressurized capillary electrochromatography(pCEC) submicron nonporous silica microsphere high carbon content silanol groups electroosmotic flow(EOF) |
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