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Construction of acrylpimaric acid-bonded silica stationary phase and its application in mixed-mode chromatographic separation
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Lei ZENG1, Mengling WEI1, Wei WEI1, Hao LI1, Bo’an SHI1, 2, Fuhou LEI1, *
Chinese Journal of Chromatography | 2025, 43(7) : 744 - 755
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Chinese Journal of Chromatography | 2025, 43(7): 744-755
• Articles •
Construction of acrylpimaric acid-bonded silica stationary phase and its application in mixed-mode chromatographic separation
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Lei ZENG1, Mengling WEI1, Wei WEI1, Hao LI1, Bo’an SHI1, 2, Fuhou LEI1, *
Affiliations
  • 1. Key Laboratory of Chemistry and Engineering of Forest Products of State Ethnic Affairs Commission,Guangxi Key Laboratory of Chemistry and Engineering of Forest Products,Guangxi Collaborative Innovation Center for Chemistry and Engineering of Forest Products,School of Chemistry and Chemical Engineering,Guangxi Minzu University,Nanning 530006,China
  • 2. School of Chemical and Environmental Engineering,Hubei Minzu University,Enshi 445000,China
Published: 2025-07-08 doi: 10.3724/SP.J.1123.2024.10010
Outline
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The development of novel functional materials from renewable biomass resources has garnered widespread attention. This strategy not only effectively reduces the reliance on petrochemical raw materials in the preparation process, thereby reducing carbon emissions and mitigating environmental pollution, but also enhances their added value, promoting the development of related agriculture and forestry industries. In this study, we prepared acrylpimaric acid bonded on silica (Sil-APA) as a new stationary phase by linking the functional ligand to silica using γ-glycidoxypropyltrimethoxysilane as the silane coupling agent. The synthesized stationary phase was characterized by Fourier-transform infrared spectra (FT-IR), elemental analysis (EA), zeta potential analysis, and thermogravimetric analysis (TGA). Acrylpimaric acid was successfully immobilized onto the surface of spherical silica via a ring-opening reaction involving the epoxy and carboxyl groups. Analytes and the stationary phase experience multiple interactions during the separation process owing to the coexistence of functional groups such as hydrogenated phenanthrene rings, as well as hydroxyl, carbonyl, and carboxyl groups on the surface of the Sil-APA stationary phase. Synergy involving multiple interaction mechanisms improves the separability and applicability of the Sil-APA stationary phase. We used hydrophobic, hydrophilic, and ionic compounds to probe the effects of organic-phase content, pH, and buffer-salt concentration in the mobile phase on the chromatographic performance of the Sil-APA column. The logarithm of the retention factor (log k) for alkylbenzenes in the stationary phase was found to decrease with increasing methanol content in the mobile phase during reverse-phase liquid chromatography (RPLC); hence, the Sil-APA stationary phase exhibited typical reverse-phase retention behavior. The Sil-APA column exhibited stronger aromatic selectivity and weaker hydrophobic selectivity compared to a C18 column, which enables polycyclic aromatic hydrocarbons (PAHs) to be more-strongly retained than alkylbenzenes while also separating these hydrophobic compounds in less time. The ln k for nucleosides/bases on the stationary phase decreased with increasing water content in the mobile phase in hydrophilic interaction liquid chromatography (HILIC) mode, confirming that the Sil-APA column has typical hydrophilic retention characteristics for the separation of nucleosides/bases. Furthermore, the relationship between the pH and buffer-salt concentration of the mobile phase and ln k for nucleosides/bases reveals that hydrogen bonding and electrostatic interactions between the stationary phase and the analytes play important roles in addition to hydrophilic interactions. The ln k for ionic compounds was observed to decrease with increasing buffer-salt concentration in the mobile phase in ion-exchange chromatography (IEC) mode, while concurrently increasing with the pH of the mobile phase. These results demonstrate that the Sil-APA column exhibits classical cation-exchange behavior for the separation of cationic compounds. These multiple retention mechanisms render the Sil-APA column suitable for mixed-mode liquid chromatography (MMC). The Sil-APA column exhibits good separation selectivity for different analyte components, further demonstrating its mixed-mode chromatographic performance and potential for complex sample analysis. Furthermore, Sil-APA demonstrated excellent chromatographic repeatability, stability, and reproducibility, as evidenced by low retention-time relative standard deviations (RSDs) of 0.076%–0.356% (n=10), 0.05%–0.193% (n=5), and 0.498%–2.806% (n=4) for inter-day, inter-day, and batch-to-batch precisions, respectively. In summary, we designed and prepared an acrylic-acid-modified silica stationary phase material for use in liquid-chromatography applications. The excellent separation performance observed under mixed-mode conditions demonstrates that acrylpimaric acid can possibly be used a functional stationary-phase monomer, thereby potentially broadening the applications scope of resin acids in separation science. The facile preparation of Sil-APA and its promising applications scope may also provide new concepts for the development of stationary-phase materials based on natural-product-modified silica in the liquid-chromatography field.

acrylpimaric acid  /  bonded stationary phase  /  mixed-mode chromatography
曾磊, 韦梦玲, 韦伟, 李浩, 史伯安, 雷福厚. 丙烯海松酸键合硅胶固定相的制备及其在混合模式色谱分离中的应用. 色谱, 2025 , 43 (7) : 744 -755 . DOI: 10.3724/SP.J.1123.2024.10010
Lei ZENG, Mengling WEI, Wei WEI, Hao LI, Bo’an SHI, Fuhou LEI. Construction of acrylpimaric acid-bonded silica stationary phase and its application in mixed-mode chromatographic separation[J]. Chinese Journal of Chromatography, 2025 , 43 (7) : 744 -755 . DOI: 10.3724/SP.J.1123.2024.10010
  • National Natural Science Foundation of China(32460367)
  • Natural Science Foundation of Guangxi Province, China(2024GXNSFAA010378)
  • Innovation Project of Guangxi Graduate Education(YCBZ2024079)
Year 2025 volume 43 Issue 7
26
13
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Article Info
doi: 10.3724/SP.J.1123.2024.10010
  • Receive Date:2024-10-14
  • Online Date:2026-10-30
  • Published:2025-07-08
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History
  • Received:2024-10-14
Funding
National Natural Science Foundation of China(32460367)
Natural Science Foundation of Guangxi Province, China(2024GXNSFAA010378)
Innovation Project of Guangxi Graduate Education(YCBZ2024079)
Affiliations
    1. Key Laboratory of Chemistry and Engineering of Forest Products of State Ethnic Affairs Commission,Guangxi Key Laboratory of Chemistry and Engineering of Forest Products,Guangxi Collaborative Innovation Center for Chemistry and Engineering of Forest Products,School of Chemistry and Chemical Engineering,Guangxi Minzu University,Nanning 530006,China
    2. School of Chemical and Environmental Engineering,Hubei Minzu University,Enshi 445000,China
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表12种不同金属材料的力学参数
科
Family
属数
Number of
genus
种数
Number of
species
占总种数比例
Percentage of
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属
Genus
种数
Number of
species
占总种数比例
Percentage of total
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鹅膏菌科Amanitaceae 2 11 5.26 鹅膏菌属 Amanita 10 4.78
小菇科 Mycenaceae 2 12 5.74 丝盖伞属 Inocybe 5 2.39
多孔菌科 Polyporaceae 8 14 6.70 蜡蘑属 Laccaria 5 2.39
红菇科 Russulaceae 3 23 11.00 小皮伞属 Marasmius 6 2.87
小菇属 Mycena 11 5.26
光柄菇属 Pluteus 5 2.39
红菇属 Russula 17 8.13
栓菌属 Trametes 5 2.39
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