色谱

色谱 ›› 2013, Vol. 31 ›› Issue (4): 342-347.DOI: 10.3724/SP.J.1123.2012.11032

• 特别策划：色谱固定相专栏 • 上一篇    下一篇

氮氧化硅反相色谱固定相材料的制备及色谱分离性能评价

钟虹敏1,张华1,万慧慧1,2*   

  1. 1. 大连理工大学化工与环境生命学部化学分析测试中心, 辽宁 大连 116024;
    2. 中国科学院大连化学物理研究所, 中国科学院分离分析化学重点实验室, 辽宁 大连 116023
  • 收稿日期:2012-11-30 出版日期:2013-04-22 发布日期:2013-04-24
  • 通讯作者: E-mail:wanhuihui@dlut.edu.cn
  • 基金资助:

    大连理工大学引进人才科研专题(DUT12RC(3)93).

Synthesis of porous spherical silicon oxynitride material and evaluation of its properties in reversed-phase chromatographic separation

ZHONG Hongmin1, ZHANG Hua1, WAN Huihui1,2*   

  1. 1. Analytical Center, Faculty of Chemical, Environmental and Biological Science and Technology, Dalian University of Technology, Dalian 116024, China;2. CAS Key Laboratory of Separation Science for Analytical Chemistry, Dalian Institute of Chemical Physics, Chinese Academy of Sciences, Dalian 116023, China
  • Received:2012-11-30 Online:2013-04-22 Published:2013-04-24

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摘要：

硅胶是目前高效液相色谱(HPLC)固定相中应用最为广泛的基质材料,其流动相的最佳使用范围为pH 2～8。在高pH(pH＞8)的流动相条件下,流动相中的氢氧根会进攻硅胶基质表面残余的硅醇基,导致硅胶基质固定相骨架溶解。在前期的研究中,我们将高温氨气处理多孔硅胶微球得到的氮氧化硅材料用作HPLC固定相,氮氧化硅在高pH流动相条件下表现出了较硅胶更高的稳定性。本文利用元素分析对氮氧化硅材料的氮化程度及含氮量进行系统的表征,并考察了氮氧化硅材料在不同pH条件下的静态稳定性。利用十八烷基二甲基氯硅烷试剂对氮氧化硅材料表面进行疏水性修饰,并以元素分析和核磁共振波谱对表面键合氮氧化硅材料进行了表征。考察了不同碳链的烷基苯、酸性化合物、碱性化合物在疏水改性的C18氮氧化硅反相色谱固定相上的色谱分离性能。进一步分别以酸、碱和中性化合物为分析对象,比较了C18-SiON1050(10)与C18-SiO2色谱保留的差异。

关键词: 氮氧化硅, 反相色谱, 硅胶, 液相色谱固定相, 元素分析

Abstract:

Silica has been widely used as HPLC column packing material. However, the fact that base can attack the silanol and dissolve the silica embarrasses the utilization of silica stationary phase in high pH mobile phases (pH＞8). In our previous research, the use of porous spherical silicon oxynitride (sph-SiON) material from high temperature nitridation of silica microspheres as stationary phase for HPLC has been explored, and the sph-SiON is stable to alkaline mobile phases and demonstrates excellent separation of a variety of polar compounds in hydrophilic interaction liquid chromatography (HILIC) mode. Herein, the degree of nitridation was studied as a function of temperature of nitridation at 750-1050 ℃, yielding the silicon oxynitride with 0.40%-12.0% (mass fraction) nitrogen from elemental analysis. At the temperature of 1050 ℃, the nitrogen content increased from 12.0% to 24.5% with the nitridation time increasing from 20 h to 120 h. The sph-SiON is stable when disposed in different pH aqueous solutions for one week. The sph-SiON material can be modified to give hydrophobic surface through the reaction of surface Si-NHx with dimethyloctadecylchlorosilane. Elemental analysis and 13C cross-polarization magic-angle spinning (CP/MAS) NMR spectrum of C18-sph-SiON prove the integration of C18 alkyl groups attached onto the sph-SiON surface. The chromatographic evaluation of C18-sph-SiON in reversed-phase separation mode was performed with alkylbenzenes as hydrophobic probes. Three alkylbenzene compounds can be separated and retained well on C18-sph-SiON even in the mobile phase of methanol/H2O (70/30, v/v) with 78507 plates/m, and an excellent tailing factor (0.95) can be obtained for ethylbenzene. In comparison with C18-SiO2, C18-sph-SiON shows distinct differences with respect to different classes of analytes, i.e. neutral analyte naphthalene, acidic analyte ibuprofen, and basic analyte amitriptyline.

Key words: elemental analysis, liquid chromatographic stationary phase, reversed-phase chromatography, silica, silicon oxynitride

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