南、北五味子“辨色论质”机制及其定性识别模型研究(1)
摘 要 目的：探讨南、北五味子药材颜色判断质量(“辨色论质”)的内在机制，构建基于颜色量化值的定性识别模型。方法：采用高效液相色譜法测定39批药材样品中6种有效成分的含量，采用色差仪测定其三色空间值[明暗程度值(ΔL*)、红绿色色调值(Δa*)、黄蓝色色调值(Δb*)]，采用SPSS 24.0软件对6种有效成分含量与三色空间值的相关性进行Pearson分析，采用SIMCA-P14.1软件进行主成分分析。结果：五味子醇甲、五味子醇乙、五味子甲素、五味子乙素、五味子丙素、五味子酯甲检测进样量的线性范围分别为0.204 8～2.560 0、0.049 3～0.616 3、0.098 4～1.230 0、0.046 3～0.578 8、0.010 6～0.132 0、0.100 0～1.500 0 μg(r均大于0.999 0);精密度、稳定性(12 h)、重复性试验的RSD均小于3%，加样回收率分别为98.14%～101.53%(RSD=1.08%，n=6)、97.16%～101.05%(RSD=1.54%，n=6)、98.29%～101.41%(RSD=1.29%，n=6)、97.17%～100.36%(RSD=1.20%，n=6)、97.32%～102.43%(RSD=1.77%，n=6)、98.02%～100.40%(RSD=0.84%，n=6)。39批南、北五味子中上述6种成分的平均含量分别为3.25～7.39、0.96～1.98、0.46～4.74、1.62～2.60、0.06～0.58、0.48～6.11 mg/g。北五味子的平均ΔL*为-80.79～-70.54，平均Δa*为2.54～5.34，平均Δb*为5.20～12.83，平均ΔE*为71.13～81.23;南五味子的平均ΔL*为-75.90～-69.16，平均Δa*为3.77～7.82，平均Δb*为8.59～17.23，平均ΔE*为69.99～77.92。相关性分析结果显示，五味子醇甲、五味子醇乙、五味子甲素、五味子乙素、五味子酯甲的含量与ΔL*、Δa*、ΔE*均呈显著相关性(P<0.01)，与Δb*均不相关(P>0.05);五味子丙素的含量与ΔL*、Δa*呈显著负相关性(P<0.05)，与Δb*、ΔE*不相关(P>0.05)。主成分分析结果显示，前2个主成分的累积方差贡献率为89.8%，且南、北五味子可明显区分。结论：北五味子中五味子醇甲含量较高，南五味子中五味子酯甲含量较高，且南五味子中未检出五味子醇甲、五味子醇乙和五味子乙素。南、北五味子的三色空间值存在差异，即北五味子亮度小，颜色偏黑，南五味子颜色偏红、偏黄。南、北五味子有效成分含量与三色空间值具有相关性，即药材颜色越暗、红色程度越弱，五味子醇甲、五味子醇乙、五味子乙素、五味子丙素的含量越高;药材表面颜色越亮、红色程度越高，五味子甲素、五味子酯甲的含量越高;所建含量测定方法精密度高、稳定性好，可用于测定南、北五味子的含量;所建颜色定性识别模型可用于南、北五味子的鉴别。
关键词 南五味子;北五味子;高效液相色谱法;含量测定;三色空间值;相关性分析;辨色论质;定性识别模型
ABSTRACT OBJECTIVE： To investigate the internal mechanism of Schisandra sphenanthera and Schisandra chinensis in determining quality by color (“color discrimination grading”) of medicinal materials， and to construct a qualitative identification model based on color quantization value. METHODS： HPLC method was used to determine the contents of 6 active components from 39 batches of samples. The colorimeter was used to determine 3-color spatial value [lightness value (ΔL*)， red-green value (Δa*)， yellow-blue value (Δb*)]. SPSS 24.0 statistical software was used to analyze the correlation between the contents of 6 active components and 3-color spatial values. Principal component analysis (PCA) was performed by using SIMCA-P14.1 software. RESULTS： The linear range of schizandrol A， schizandrol B， schisandrin A， schisandrin B， schisandrin C， schisantherin A were 0.204 8-2.560 0， 0.049 3-0.616 3， 0.098 4- 1.230 0， 0.046 3-0.578 8， 0.010 6-0.132 0， 0.100 0-1.500 0 μg (r>0.999 0); RSDs of precision， stability (12 h) and repeatability tests were all less than 3%. The recoveries were 98.14%-101.53%(RSD=1.08%，n=6)， 97.16%-101.05%(RSD=1.54%，n=6)， 98.29%-101.41%(RSD=1.29%，n=6)， 97.17%-100.36%(RSD=1.20%，n=6)， 97.32%-102.43%(RSD=1.77%，n=6)and 98.02%-100.40%(RSD=0.84%，n=6)， respectively. Among 39 batches of S. sphenanthera and S. chinensis， average contents of above 6 components were 3.25-7.39， 0.96-1.98， 0.46-4.74， 1.62-2.60， 0.06-0.58， 0.48-6.11 mg/g， respectively. Average ΔL* of S. chinensis was -80.79--70.54， average Δa* was 2.54-5.34， average Δb* was 5.20-12.83， average ΔE* was 71.13-81.23; average ΔL* of S. sphenanthera was -75.90- -69.16， average Δa* was 3.77-7.82， average Δb* was 8.59-17.23， average ΔE* was 69.99-77.92. The results of relationship analysis showed that the contents of schizandrol A， schizandrol B， schisandrin A， schisandrin B and schisantherin A were significantly correlated with ΔL*， Δa*， ΔE* (P<0.01)， with no significant correlation with Δb*(P>0.05). There was a negative correlation of the content of schisandrin C with ΔL* and Δa* (P<0.05)， and there was no significant correlation with Δb* and ΔE* (P>0.05). Results of PCA showed that accumulative variance contribution rate of primary 2 main components was 89.8%， and S. sphenanthera and S. chinensis could be identified significantly. CONCLUSIONS： The content of schizandrol A in S. chinensis is high relatively， and content of schisantherin A in S. sphenanthera is high relatively. Schizandrol A， schizandrol B and schisandrin B were not detected in S. sphenanthera. The 3-color spatial value of S. sphenanthera and S. chinensis are different， that is， the brightness of S. chinensis is small and the color is slant black， while the color of S. sphenanthera is slant red and yellow. The contents of active components of S. sphenanthera and S. chinensis is related to the surface 3-color spatial values， that is， the darker the color is， the weaker the red degree is， and the higher the contents of schizandrol A， schizandrol B， schisandrin B and schisandrin C are; the brighter the surface color is， the stronger the red degree is， and the higher the contents of schisandrin A and schisantherin A are. The established content determination method is precise and stable， and can be used for the content determination of S. sphenanthera and S. chinensis. The color qualitative identification model can be used for the identification of S. sphenanthera and S. chinensis., http://www.100md.com(焦美钰 佟月 吴浩善 康廷国 张慧)
关键词 南五味子;北五味子;高效液相色谱法;含量测定;三色空间值;相关性分析;辨色论质;定性识别模型
ABSTRACT OBJECTIVE： To investigate the internal mechanism of Schisandra sphenanthera and Schisandra chinensis in determining quality by color (“color discrimination grading”) of medicinal materials， and to construct a qualitative identification model based on color quantization value. METHODS： HPLC method was used to determine the contents of 6 active components from 39 batches of samples. The colorimeter was used to determine 3-color spatial value [lightness value (ΔL*)， red-green value (Δa*)， yellow-blue value (Δb*)]. SPSS 24.0 statistical software was used to analyze the correlation between the contents of 6 active components and 3-color spatial values. Principal component analysis (PCA) was performed by using SIMCA-P14.1 software. RESULTS： The linear range of schizandrol A， schizandrol B， schisandrin A， schisandrin B， schisandrin C， schisantherin A were 0.204 8-2.560 0， 0.049 3-0.616 3， 0.098 4- 1.230 0， 0.046 3-0.578 8， 0.010 6-0.132 0， 0.100 0-1.500 0 μg (r>0.999 0); RSDs of precision， stability (12 h) and repeatability tests were all less than 3%. The recoveries were 98.14%-101.53%(RSD=1.08%，n=6)， 97.16%-101.05%(RSD=1.54%，n=6)， 98.29%-101.41%(RSD=1.29%，n=6)， 97.17%-100.36%(RSD=1.20%，n=6)， 97.32%-102.43%(RSD=1.77%，n=6)and 98.02%-100.40%(RSD=0.84%，n=6)， respectively. Among 39 batches of S. sphenanthera and S. chinensis， average contents of above 6 components were 3.25-7.39， 0.96-1.98， 0.46-4.74， 1.62-2.60， 0.06-0.58， 0.48-6.11 mg/g， respectively. Average ΔL* of S. chinensis was -80.79--70.54， average Δa* was 2.54-5.34， average Δb* was 5.20-12.83， average ΔE* was 71.13-81.23; average ΔL* of S. sphenanthera was -75.90- -69.16， average Δa* was 3.77-7.82， average Δb* was 8.59-17.23， average ΔE* was 69.99-77.92. The results of relationship analysis showed that the contents of schizandrol A， schizandrol B， schisandrin A， schisandrin B and schisantherin A were significantly correlated with ΔL*， Δa*， ΔE* (P<0.01)， with no significant correlation with Δb*(P>0.05). There was a negative correlation of the content of schisandrin C with ΔL* and Δa* (P<0.05)， and there was no significant correlation with Δb* and ΔE* (P>0.05). Results of PCA showed that accumulative variance contribution rate of primary 2 main components was 89.8%， and S. sphenanthera and S. chinensis could be identified significantly. CONCLUSIONS： The content of schizandrol A in S. chinensis is high relatively， and content of schisantherin A in S. sphenanthera is high relatively. Schizandrol A， schizandrol B and schisandrin B were not detected in S. sphenanthera. The 3-color spatial value of S. sphenanthera and S. chinensis are different， that is， the brightness of S. chinensis is small and the color is slant black， while the color of S. sphenanthera is slant red and yellow. The contents of active components of S. sphenanthera and S. chinensis is related to the surface 3-color spatial values， that is， the darker the color is， the weaker the red degree is， and the higher the contents of schizandrol A， schizandrol B， schisandrin B and schisandrin C are; the brighter the surface color is， the stronger the red degree is， and the higher the contents of schisandrin A and schisantherin A are. The established content determination method is precise and stable， and can be used for the content determination of S. sphenanthera and S. chinensis. The color qualitative identification model can be used for the identification of S. sphenanthera and S. chinensis., http://www.100md.com(焦美钰 佟月 吴浩善 康廷国 张慧)