Synthesis of a novel multifunctional stationary phase derived from diethanolamine, HILIC/RPLC/WAX mixed-mode HPLC applications, and investigation of the retention mechanism.

IF 3.8 2区 化学 Q1 BIOCHEMICAL RESEARCH METHODS
Tarık Aral, Meryem Dokdemir, Hayriye Aral, Kübra Tunç, Murat Sunkur, Mehmet Çolak
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Abstract

Mixed-mode chromatography is increasingly valued for retaining analytes with diverse polarity and charge by integrating hydrophilic interaction (HILIC), reversed-phase (RPLC), and ion-exchange mechanisms. However, designing stationary phases that are both easy to synthesize and chromatographically versatile remains challenging. This study presents DEA-Mix-SP, a novel silica-based stationary phase functionalized with diethanolamine via [2-(3,4-epoxycyclohexyl)ethyl]trimethoxysilane, offering a simple synthetic route for broad-spectrum separation. Three variants with different ligand densities were characterized by elemental analysis, FTIR, SEM, and BET. The columns showed excellent separation for various analytes: nine nucleobases/nucleosides were resolved within 13 min, achieving up to 35,000 theoretical plates per meter, and eight benzoic acid derivatives were fully separated in 9 min with efficiencies up to 50,000 N/m. Alkylbenzenes, PAHs, Sudan dyes, phenols, and anilines were also effectively separated. Retention mechanisms were studied using quantitative parameters such as logD, logS, and pKa, confirming significant anion-exchange effects. Performance was compared with ACE C18 (RPLC) and aminopropyl (HILIC) columns: DEA-Mix-SP showed superior separation performance in HILIC over the aminopropyl column and better separation of phenols, benzoic acids, and anilines than ACE C18, while achieving comparable results for fully non-polar analytes like alkylbenzenes, Sudan dyes, and PAHs. DEA-Mix-SP thus combines cost-effectiveness and high mixed-mode selectivity, providing reliable separation for analytes with wide polarity and charge ranges, making it a strong option for pharmaceutical, environmental, and food analyses.

新型二乙醇胺多功能固定相的合成、HILIC/RPLC/WAX混合高效液相色谱应用及保留机理研究。
通过整合亲水相互作用(HILIC)、反相(RPLC)和离子交换机制,混合模式色谱法在保留具有不同极性和电荷的分析物方面越来越受到重视。然而,设计既易于合成又具有色谱通用性的固定相仍然具有挑战性。本研究提出了一种以[2-(3,4-环氧环己基)乙基]三甲氧基硅烷为载体,经二乙醇胺官能化的新型硅基固定相DEA-Mix-SP,为广谱分离提供了一种简单的合成途径。通过元素分析、红外光谱(FTIR)、扫描电镜(SEM)和BET对3种不同配体密度的变异进行了表征。该色谱柱对各种分析物具有良好的分离效果:9个核碱基/核苷在13分钟内被分离,达到每米35000个理论板,8个苯甲酸衍生物在9分钟内被完全分离,效率高达50,000 N/m。烷基苯、多环芳烃、苏丹红染料、酚类和苯胺类也得到了有效的分离。使用定量参数如logD、log和pKa研究了保留机制,证实了显著的阴离子交换效应。比较了ACE C18 (RPLC)和氨基丙基(HILIC)色谱柱的分离性能:DEA-Mix-SP在HILIC色谱柱上的分离性能优于氨基丙基色谱柱,对酚类、苯甲酸和苯胺的分离效果优于ACE C18,同时对烷基苯、苏丹染料和多环芳烃等完全非极性分析物的分离效果也优于ACE C18。因此,DEA-Mix-SP结合了成本效益和高混合模式选择性,为具有宽极性和电荷范围的分析物提供可靠的分离,使其成为制药,环境和食品分析的强大选择。
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来源期刊
CiteScore
8.00
自引率
4.70%
发文量
638
审稿时长
2.1 months
期刊介绍: Analytical and Bioanalytical Chemistry’s mission is the rapid publication of excellent and high-impact research articles on fundamental and applied topics of analytical and bioanalytical measurement science. Its scope is broad, and ranges from novel measurement platforms and their characterization to multidisciplinary approaches that effectively address important scientific problems. The Editors encourage submissions presenting innovative analytical research in concept, instrumentation, methods, and/or applications, including: mass spectrometry, spectroscopy, and electroanalysis; advanced separations; analytical strategies in “-omics” and imaging, bioanalysis, and sampling; miniaturized devices, medical diagnostics, sensors; analytical characterization of nano- and biomaterials; chemometrics and advanced data analysis.
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