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    无机元素图谱结合化学计量学在枸杞子产地溯源的应用

    Application of Inorganic Element Chart Combined with Chemometrics in Tracing the Region of Goji Fruit

    • 摘要: 采用电感耦合等离子体质谱法(ICP-MS)测定不同产地枸杞子中38种无机元素的含量,包括21种常规元素(Na、Mg、Al、K、Ca、Cr、Mn、Fe、Co、Ni、Cu、Zn、As、Se、Ag、Cd、Ba、Li、Pb、Sr、U)和17种稀土元素(Sc、Y、La、Ce、Pr、Nd、Sm、Eu、Gd、Tb、Dy、Ho、Er、Tm、Yb、Lu、Th),建立了枸杞子中无机元素含量的特征图谱,并结合化学计量学方法主成分分析、聚类分析、判别分析对测定结果进行系统分析。结果表明,不同产地枸杞子的无机元素特征图谱均呈现出比较有规律的分布特征。4个不同产地中38种元素质量分数最高的均是K,其次是Na、Mg、Ca、Fe、Al、Zn、Mn、Cu、Sr,而17种稀土元素质量分数均较低。采用IBM SPSS 24.0软件的单因素方差分析可知,甘肃玉门产地枸杞子中17种稀土元素、Mg、Al、K、Mn、Fe、Co、Ni、Cu、Cd、Ba、Pb的质量分数与靖远产地的存在显著性差异(p<0.05),宁夏中宁与青海产地枸杞子中Na、Mg、Ca、Co、Ni、Cu、Zn、Ag、Cd、Pb、Li、U的质量分数也存在显著性差异(p<0.05)。经主成分分析可知,Al、Fe、Ni、Cu、Zn、Ca、Li、As、Sc、Y、La、Ce、Pr、Nd、Sm、Eu、Gd、Tb、Dy、Ho、Er、Tm、Yb、Lu、Th是枸杞子的特征无机元素。通过聚类与判别分析,筛选出有效指标为Na、Al、K、Cr、Co、Ni、Cu、Zn、Cd、Pb、Sc,判别结果的方差分析表明,类间差异显著(p<0.01),说明判别结果有效。采用正交验证法对判别模型进行验证,61批次枸杞子样品的回判正确率为100%,交叉验证成功率为98.4%,说明得到的判别方程较为理想有效,为枸杞子道地药材的产地溯源研究提供了方法和依据。

       

      Abstract: A method was used for determination of 38 inorganic elements in goji fruit from different regions, including 21 conventional elements (Na, Mg, Al, K, Ca, Cr, Mn, Fe, Co, Ni, Cu, Zn, As, Se, Ag, Cd, Ba, Li, Pb, Sr, and U) and 17 rare earth elements (Sc, Y, La, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu, and Th), by inductively coupled plasma mass spectrometry (ICP-MS). A characteristic chart of inorganic element content in goji fruit was established, and the determination results were systematically analyzed by chemometric methods of principal component analysis, cluster analysis, and discriminant analysis. As shown by the results, the inorganic element characteristic chart of goji fruit from different regions exhibited a relatively regular distribution pattern. Among the 4 different regions, K had the highest mass fraction of 38 elements, followed by Na, Mg, Ca, Fe, Al, Zn, Mn, Cu, and Sr, while mass fractions of 17 rare earth elements were all lower. There were significant differences (p<0.05) in mass fractions of 17 rare earth elements, Mg, Al, K, Mn, Fe, Co, Ni, Cu, Cd, Ba, and Pb, in goji fruit from Yumen region in Gansu Province compared to Jingyuan region, and there were also significant differences (p<0.05) in mass fractions of Na, Mg, Ca, Co, Ni, Cu, Zn, Ag, Cd, Pb, Li, and U in goji fruit from Zhongning region in Ningxia Province compared to Qinghai Province region by one-way analysis of variance using IBM SPSS 24.0 software. According to principal component analysis, Al, Fe, Ni, Cu, Zn, Ca, Li, As, Sc, Y, La, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu, and Th were the characteristic inorganic elements of goji fruit. Through cluster analysis and discriminant analysis, the effective indicators including Na, Al, K, Cr, Co, Ni, Cu, Zn, Cd, Pb, and Sc were selected. The variance analysis of the discriminant results showed significant inter-class differences (p<0.01), indicating the validity of the discriminant results. The orthogonal validation method was used for verification of the discriminant model, and the accuracy of the regression for 61 batches of goji fruit samples was 100%, with a cross validation success rate of 98.4%, indicating that the obtained discriminant equation was ideal and effective, to provide a method and basis for tracing the region of genuine goji fruit medicinal materials.

       

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