基于化学计量学的枸杞多糖部分酸水解产物PMP-HPLC指纹图谱

本文通过构建枸杞多糖的部分酸水解产物指纹图谱，结合多种化学计量学方法评价不同产地枸杞多糖的差异并用于市售样品的真伪鉴别。采用水提醇沉法提取16批不同产地的枸杞多糖，采用三氟乙酸部分水解，将水解产物中的单糖和寡糖采用1-苯基-3-甲基-5-吡唑啉酮（PMP）柱前衍生化HPLC分析，通过中药色谱指纹图谱软件评估不同产地样品的相似性，采用聚类分析（HCA）、主成分分析（PCA）和偏最小二乘判别分析（PLS-DA）对指纹图谱进行综合评价。结果表明，不同产地枸杞多糖部分酸水解产物中均含有7种单糖、聚合度（DP 2~4）的半乳糖醛酸聚糖和3种其他类型的二糖。16批产地的枸杞多糖相似度在0.911~0.997，HCA、PCA和PLS-DA将不同产地的枸杞多糖分为3类，分类结果与产地有一定的相关性，并且筛选出3个影响产地间差异的标志性成分，分别为葡萄糖（Glc）、阿拉伯糖（Ara）和半乳糖（Gal）。本文建立的指纹图谱可用于枸杞多糖的质量控制。

PMP-HPLC Fingerprint of Partial Acid Hydrolysate of Lycium barbarum Polysaccharides Based on the Chemometric Methods

In this paper, the fingerprints of partial acid hydrolysates of Lycium barbarum polysaccharides (LBPs) were constructed, combined with a variety of chemometric methods, to evaluate the differences of LBPs from different origins and identify the authenticity of commercial samples. Sixteen batches of Lycium barbarum polysaccharides (LBPs) from different areas were obtained by the method of water extraction and alcohol precipitation, which were partially hydrolyzed by trifluoroacetic acid. The PMP pre-column derivatization-HPLC method was applied to analyse the monosaccharides and oligosaccharides in the partial hydrolysates of LBPs. The similarity of samples of different origins was calculated by the “similarity Evaluation System for Chromatographic Fingerprint of Traditional Chinese Medicine(TCM)”software. And the fingerprints were further evaluated by chemometric methods including cluster analysis (HCA), principal component analysis (PCA) and partial least squares discriminant analysis (PLS-DA). The results showed that the partial acid hydrolysis products of LBPs contained seven monosaccharides, galacturonic acid glycans of DP 2~4 and three kinds of disaccharides. The similarities of 16 batches of LBPs of different origins were high ranging from 0.911 to 0.997. HCA, PCA and PLS-DA all divided LBPs from different origins into three categories, and the classification results had certain correlation with the origins. The three iconic components that influenced the differences between origins were screened out by PLS-DA, which were glucose (Glc), arabinose (Ara) and galactose (Gal), respectively. The established fingerprint in this paper could be used for the quality control of LBPs.