目的 探究复杂溶液体系中三七皂苷类成分的存在状态，结合超滤膜分离行为分析三七总皂苷胶束的缔合规律。方法 以三七总皂苷溶液为研究对象，选用三七皂苷R₁及人参皂苷Rg₁、Rb₁、Rd为指标成分，选择超滤截留率、透过率和胶束组成比例为考察指标，分析无机盐浓度、温度、皂苷质量浓度等关键参数对皂苷分子存在状态与超滤行为的影响规律。结果 三七总皂苷因其两亲性结构在水溶液中易形成胶束，其超滤分离行为受多种环境因素调控。无机盐通过离子效应及盐析作用影响胶束稳定性：二价阴离子SO₄^2-通过破坏水化层增强疏水作用，促进胶束形成与析出，无机盐盐析效应顺序为Na₂SO₄＞MgSO₄＞KCl；单价盐（如KCl）在低浓度时，可通过屏蔽电荷促进胶束的缔合，而高浓度则会加剧盐析效应。人参二醇型皂苷如人参皂苷Rb₁、Rd，在无机盐诱导缔合的胶束中参与比例更高，体现分子结构驱动的缔合倾向。温度升高加剧分子运动，胶束分子间疏水相互作用减弱，破坏分子间氢键，促进胶束分解，提高超滤透过率、降低截留率。皂苷质量浓度升高增强溶质分子间疏水相互作用和聚集作用，促进胶束缔合。通过拟合不同溶质质量浓度下的超滤截留率和孔径大小的关系，推算出截留率为90%时，各质量浓度的胶束相对分子质量及其特征成分的内部比例。结果表明，溶质质量浓度为10、20 mg/mL时，胶束中主要为人参二醇型皂苷，但胶束缔合程度在低质量浓度下存在局限性；溶质质量浓度为30～60 mg/mL时，胶束相对分子质量明显升高，说明高溶质质量浓度促进杂化胶束的形成。结论 揭示了制药参数对三七总皂苷胶束结构与超滤分离效率的调控机制，为中药制剂中皂苷成分的质量控制及精制工艺优化提供了理论与实践指导。

Objective To investigate the existing states of Panax notoginseng total saponins in complex solution systems and elucidate the micellar association behavior of total saponins based on their ultrafiltration separation characteristics. Methods A total saponins solution of P. notoginseng was used as the research subject, with notoginsenoside R₁ and ginsenoside Rg₁, Rb₁, Rd selected as representative analytes. Ultrafiltration rejection rate, permeation rate, and micellar compositional ratio were employed as evaluation indices to analyze how key parameters—including inorganic salt concentration, temperature, and saponin concentration—affect saponin molecular states and ultrafiltration behavior. Results Owing to their amphiphilic structures, the saponins readily form micelles in aqueous solution, and their ultrafiltration performance is regulated by multiple environmental factors. Inorganic salts modulate micellar stability through ionic effects and salting-out actions: the divalent anion SO₄²⁻ disrupts hydration layers and strengthens hydrophobic interactions, thereby promoting micelle formation and precipitation, with salting-out intensity ranked as Na₂SO₄ > MgSO₄ > KCl. Monovalent salts such as KCl facilitate micellar association at low concentrations via charge shielding, whereas high concentrations intensify salting-out. Dammarane-type saponins, particularly Rb₁ and Rd, showed higher participation in salt-induced micelles, indicating a structure-driven association preference. Increasing temperature enhances molecular motion, weakens hydrophobic interactions and intermolecular hydrogen bonding within micelles, thereby promoting micelle dissociation, increasing permeation rates, and reducing rejection. Elevating saponin concentration strengthens hydrophobic and aggregative interactions among solute molecules, facilitating micelle assembly. By fitting the relationship between ultrafiltration rejection and membrane pore size at different solute concentrations, the molecular weight of micelles at 90% rejection and the internal compositional ratio of characteristic saponins were estimated. The results showed that at 10—20 mg/mL, micelles mainly consisted of diol-type saponins, but their association degree remained limited at low concentrations. At 30—60 mg/mL, the micellar molecular mass increased markedly, indicating that higher solute concentrations promote the formation of hybrid micelles. Conclusion This study elucidates the mechanisms by which pharmaceutical processing parameters regulate the micellar structure and ultrafiltration efficiency of P. notoginseng total saponins, providing theoretical and practical guidance for quality control and purification process optimization in saponin‑based traditional Chinese medicine formulations.

R283.6

国家自然科学基金项目（82274106）；中药制药过程控制与智能制造技术全国重点实验室创新项目（NZYSKL240207）；南京中医药大学中药学一流学科科学研究培育项目（ZYXPY2024-006）