Kinetic and HPLC-MS analyses revealed the catalysis behavior of total saponins from MOF-based solid acids

IF 5.3 2区化学 Q2 CHEMISTRY, PHYSICAL

Journal of Molecular Liquids Pub Date : 2025-04-21 DOI:10.1016/j.molliq.2025.127635

YanXiao Zhang , XiaoNing Gao , Juan Xu , Lu Feng

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Abstract

Diosgenin is an influential intermediate for the preparation of various steroidal drugs, and has the reputation of “mother of hormones” and “medicinal gold”. In this work, UiO-66-NH₂ is quaternary ammoniated by functional modification of 3,5-diamino-1,2,4-triazole and then ion-exchanged with different concentrations of CF₃SO₃H to produce ionic liquids grafted MOF-based solid acids, namely UNS-0.96 and UNS-1.28, where 0.96 and 1.28 represent the volume (mL) of CF₃SO₃H consumed. They were used to extract diosgenin from total saponins, suggesting that UNS-1.28 can achieve high diosgenin extraction with a shorter time (2.5 h) and a lower addition amount (0.15 g) and the optimum diosgenin yield of 22.5 % was obtained. The extraction efficiency is higher than that obtained by hydrolysis of 2 M H₂SO₄ and commercial ion exchange resins. Kinetic studies have shown that the catalytic of total saponins by UNS-1.28 is in perfect agreement with the pseudo-first-order kinetic model, and that the activation energy required for extraction is low, only 2.83 × 10⁴ J/mol. In addition, HPLC-MS was used to analyze the total saponins and products at different extraction times. The fragmentation peak types and relative abundances of the different extracted products are compared to reveal the cleavage pathways of the total saponins and the optimal period of diosgenin production, and to suggest the mechanism of action of the solid acid on the total saponins.

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动力学和HPLC-MS分析揭示了mof基固体酸对总皂苷的催化行为

薯蓣皂苷元是制备各种甾体药物的重要中间体，被誉为“激素之母”和“药用黄金”。本研究通过对3,5-二胺-1,2,4-三唑进行官能团修饰，将uiu -66- nh2进行季铵化处理，然后与不同浓度的CF3SO3H进行离子交换，得到接枝mof基固体酸的离子液体，即uns0.96和uns1.28，其中0.96和1.28分别表示CF3SO3H消耗的体积（mL）。通过对总皂苷中薯蓣皂苷元的提取，结果表明，在较短的提取时间（2.5 h）和较低的添加量（0.15 g）下，UNS-1.28可获得较高的薯蓣皂苷元提取率，最佳的薯蓣皂苷元得率为22.5%。萃取效率高于用2 M H2SO4和商用离子交换树脂水解得到的萃取效率。动力学研究表明，UNS-1.28对总皂苷的催化作用完全符合准一级动力学模型，提取所需活化能较低，仅为2.83 × 104 J/mol。采用高效液相色谱-质谱法对不同提取时间的总皂苷及其产物进行分析。通过对不同提取产物的断裂峰类型和相对丰度的比较，揭示了薯蓣皂苷元的裂解途径和生产薯蓣皂苷元的最佳时期，并对固体酸对薯蓣皂苷元的作用机制进行了探讨。

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来源期刊

Journal of Molecular Liquids 化学-物理：原子、分子和化学物理

CiteScore

10.30

自引率

16.70%

发文量

2597

审稿时长

78 days

期刊介绍： The journal includes papers in the following areas: – Simple organic liquids and mixtures – Ionic liquids – Surfactant solutions (including micelles and vesicles) and liquid interfaces – Colloidal solutions and nanoparticles – Thermotropic and lyotropic liquid crystals – Ferrofluids – Water, aqueous solutions and other hydrogen-bonded liquids – Lubricants, polymer solutions and melts – Molten metals and salts – Phase transitions and critical phenomena in liquids and confined fluids – Self assembly in complex liquids.– Biomolecules in solution The emphasis is on the molecular (or microscopic) understanding of particular liquids or liquid systems, especially concerning structure, dynamics and intermolecular forces. The experimental techniques used may include: – Conventional spectroscopy (mid-IR and far-IR, Raman, NMR, etc.) – Non-linear optics and time resolved spectroscopy (psec, fsec, asec, ISRS, etc.) – Light scattering (Rayleigh, Brillouin, PCS, etc.) – Dielectric relaxation – X-ray and neutron scattering and diffraction. Experimental studies, computer simulations (MD or MC) and analytical theory will be considered for publication; papers just reporting experimental results that do not contribute to the understanding of the fundamentals of molecular and ionic liquids will not be accepted. Only papers of a non-routine nature and advancing the field will be considered for publication.