Selecting of the stationary phase aromatic selector for the implementation of mixed mode liquid chromatography using the Welch mode
Despite the variety of the chromatographic modes, laboratory-synthesized and commercially available stationary phases, the reversed-phase liquid chromatography with spectrophotometric detection remains the most popular and widespread liquid chromatography mode, especially in the pharmaceutical industry, food industry and forensic chemistry. This is due to the fact that the vast majority of known organic compounds, including physiologically active, toxic and endogenous substances, contain an aromatic functional group. The aromatic group, as a rule, absorbs radiation in the ultraviolet region, allowing the use of a simple, cheap and sensitive method of UV detection. The hydrophobic nature of the aromatic group allows the implementation of a well-studied and handling separation mechanism based on the hydrophobic effect and dispersion interactions. In this case, the most popular are hydrophobic stationary phases, such as octylsilyl (C8) and octadecylsilyl (C18) stationary phases. One of the effective ways to solve this issue is to use multimodal stationary phases containing several functional groups to combine retention mechanisms and selectivity of several chromatographic modes. One of the types of multimodal stationary phases are phases containing aromatic groups. However, the most commonly used stationary phases with aromatic groups (phenyl, pentafluorophenyl) do not provide sufficiently strong π-interactions. According to the literature review, electron-deficient aromatic groups containing electron-withdrawing substituents, as a rule, provide stronger π-interactions than electron-saturated aromatic groups. In this work, using the Welch "immobilized guest" approach, the structure of the aromatic selector providing strong π-interactions in the mixed reversed-phase liquid chromatography mode was selected. During the experiment, it was found that dinitroaromatic groups demonstrate strong retention in a wide range. The highest retention was demonstrated by N-alkyl-substituted 2,4-dinitroaniline, which was chosen as an aromatic selector. The obtained stationary phase containing V-propyl-substituted 2,4-dinitroaniline group demonstrated the possibility of stronger retention and selective determination for polar substances using novocaine as an example compared to commercially available C8 and C18 stationary phases. Advanced retention was demonstrated for ketoprofen and naproxen compared to the commercially available pentafluorophenyl stationary phase due to the implementation of π-interactions. The possibility of practical application of the developed stationary phase for the determination of active pharmaceutical ingredients and related impurities in the combination drug "Askofen-P" was demonstrated. The developed stationary phase provides higher selectivity and retention for polar compounds such as caffeine, theophylline and paracetamol compared to the commercially available C8 stationary phase. Contribution of the authors: the authors contributed equally to this article. The authors declare no conflicts of interests.
Keywords
high performance liquid chromatography,
multimodal liquid chromatography,
reversed-phase liquid chromatography,
π-interactions,
dinitroaromatic groups,
Welch “immobilized guest”Authors
| Upyrenko Evgeny V. | Tomsk State University | eugeniy.upyrenko@gmail.com |
| Kurgachev Dmitry A. | Tomsk State University | kurgachev.tsu@gmail.com |
| Bakibaev Abdigali A. | Tomsk State University | bakibaev@mail.ru |
Всего: 3
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