Development of three-dimensional boronate affinity dendritic mesoporous silica coupled with HPLC-CAD for selective
Weiman Zhao1, Wenxiang Fan1, Longchan Liu1
1State Key Laboratory of Discovery and Utilization of Functional Components in Traditional Chinese Medicine, The MOE Key Laboratory of Standardization of Chinese Medicines, The SATCM Key Laboratory of New Resources and Quality Evaluation of Chinese Medicines, The Shanghai Key Laboratory for Compound Chinese Medicines, Institute of Chinese Materia Medica, Shanghai University of Traditional Chinese Medicine, Shanghai, 201203, China.
Abstract:
The precise and selective determination of ginsenosides, pharmacologically diverse saponins abundant in Panax species, is crucial for their therapeutic development and stringent quality control. However, inherent challenges, including their weak ultraviolet absorption and the high polarity imparted by sugar moieties, complicate their determination. Addressing these limitations, this study introduces the first-time construction and application of a boronate affinity dendritic mesoporous silica nanomaterial (BA-DMSN) as a highly efficient adsorbent for ginsenoside pretreatment. The synthesized BA-DMSN was comprehensively characterized, confirming a unique three-dimensional open dendritic framework, high specific surface area, and exceptional inner surface accessibility. These attributes facilitate rapid analyte adsorption and release, enabling a solid-phase extraction (SPE) process completed within approximately 10 min. Critically, the strategic incorporation of boronic acid groups conferred specific selectivity towards the cis-diol structures present in ginsenosides, allowing for their highly effective enrichment from complex matrices. Integrating this novel adsorbent with charged aerosol detection (CAD), a boronate affinity chromatography strategy was successfully developed and validated for the quantitative determination of nine key ginsenosides (notoginsenosides Fa, Fc, FP2, Fe, and ginsenosides Rc, Rd, Rb1, Rb2, Rb3) in stem-leaf extracts of Panax notoginseng. Methodological investigations demonstrated that this approach offers significant advantages over existing techniques, including operational simplicity, outstanding selectivity, and enhanced sensitivity, particularly for ginsenosides lacking strong chromophores. The successful analysis of actual Panax notoginseng samples underscores the robust applicability and promising prospects of the BA-DMSN-based SPE-CAD methodology for the quality control and further research of ginsenoside-based natural products.
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