不同产地姜黄甲醇和石油醚部位化学成分的比较分析

Comparative Analysis of Chemical Composition in Methanol and Petroleum Ether Fractions from Curcuma longa of Different Habitats

目的:比较不同产地姜黄甲醇和石油醚部位化学成分的差异。方法:采用超声法提取7个不同产地(S1~S7)姜黄并萃取得甲醇和石油醚部位,计算其得率。采用液质联用法测定甲醇部位中的姜黄素类化合物;采用气质联用法分析石油醚部位中的化学成分,通过与NIST 2005、Wiley275标准质谱图进行对比确定其结构,采用峰面积归一化法测定其相对百分含量;采用SPSS 25.0软件对不同产地姜黄石油醚部位中共有成分的相对百分含量进行主成分分析和聚类分析,同时分析不同产地所在纬度对总姜黄酮(以芳香-姜黄酮和姜黄酮计)含量的影响。结果:7个不同产地姜黄中甲醇部位的得率为1.35%~8.90%,石油醚部位的得率为0.81%~4.90%,最高均为福建龙岩。S1、S3~S7等地姜黄中姜黄素类化合物含量(参考峰面积)无显著差异,且含量均为姜黄素>去甲氧基姜黄>双去甲氧基姜黄素;S2产姜黄中姜黄素类化合物略有不同,主要表现为双去甲氧基姜黄素的含量比其他产地更高。不同产地姜黄石油醚部位共鉴定出47种化学成分,主要为倍半萜和单萜类化合物,其中S1~S7姜黄中分别鉴定出23、10、15、18、11、14、15种,总相对百分含量分别为94.49%、96.09%、95.66%、98.98%、99.24%、89.05%、97.27%;不同产地有4种共有成分,为姜黄酮(17.90%~43.07%)、芳香-姜黄酮(6.97%~33.66%)、(6R,7R)-红没药烯(1.60%~4.28%)、姜黄新酮(6.80%~20.63%);主成分分析结果显示,姜黄中前6个主成分的累计方差贡献率为100%;聚类分析结果显示,S1、S2、S6各聚为一类,其他聚为一类。总姜黄酮含量随着纬度的升高呈先下降后升高的趋势且以四川绵阳最高(64.28%)、福建漳州最低(26.92%)。结论:不同产地姜黄甲醇部位姜黄素类成分及含量、石油醚部位成分及含量存在差异。

OBJECTIVE:To compare the chemical composition difference in methanol and petroleum ether fraction from Curcuma longa of different habitats.METHODS:The ultrasonic method was used to extract C.longa from 7 defferent producingareas(S1-S7),and methanol and petroleum ether fraction were obtained and calculated yield.The curcumin compounds in methanol fraction were determined by LC-MS;The chemical components in petroleum ether fraction were analyzed by GC-MS,and the relative percentage content was determined by peak area normalization method after determining its structure by comparing NIST 2005 standard mass spectra and Wiley 275 standard mass spectra.SPSS 25.0 software was used for principle component analysis(PCA)and cluster analysis of relative percentage content of common components in petroleum ether fraction from C.longa of different habitats.At the same time,the influence of latitude of the habitats on the content of total tumerone(by tumerone and ar-tumerone)was analyzed.RESULTS:The yield of methanol fraction were 1.35%-8.90%from C.longa of 7 habitats;the yield of petroleum ether fraction were 0.81%-4.90%,which were the highest in C.longa from Longyan of Fujian Province.There was no significant difference in the relative content of curcumin compounds(reference peak area)from S1,S3-S7,which was in descending order as follows as curcumin>desmethoxycurcumin>bisdemethoxycurcumin.There was slightly different in curcumin compounds of C.longa from S2,mainly manifesting as the content of bisdemethoxycurcumin was higher than that from other producing areas.Totally 48 chemical compositions were identified from petroleum ether fraction in C.longa from different habitats,mainly being sesquiterpenoids and monoterpenoids.23,10,15,18,11,14,15 chemical compositions were identified from S1-S7,accounting for 94.49%,96.09%,95.66%,98.98%,99.24%,89.05%and 97.27%.There were 4 common compositions in C.longa from different habitats,which were tumerone(17.90%-43.07%),ar-tumerone(6.97%-33.66%),(6 R,7 R)-bisabolone(1.60%-4.28%),curlone(6.80%-20.63%).PCA analysis showed that accumulative contribution rate of former 6 principle components was 100%.Cluster analysis showed that S1,S2,S6 was clustered into a category,respecrively;and others into a category.Total content of total tumerone decreased first and then increased as the increase of latitude,which was the highest in Mianyang of Sichuan province(64.28%)and the lowest in Zhangzhou of Fujian province(26.92%).CONCLUSIONS:There are difference in composition and content of methanol and petroleum ether fractions in C.longa from different habitats.