石菖蒲中核苷类成分的分离鉴定及转化途径分析  

Nucleosides from Acorus tatarinowii and Their Transformation Pathway

作　　者：焦森 毛淑杰[2] 梁曜华[2] 陈两绵[2] 闫利华[2] 王智民[2] JIAO Sen;MAO Shu-jie;LIANG Yao-hua;CHEN Liang-mian;YAN Li-hua;WANG Zhi-min(Henan University of Chinese Medicine,Zhengzhou 450000,China;National Engineering Laboratory for Quality Control Technology of Chinese Herbal Medicines,Institute of Chinese Materia Medica,China Academy of Chinese Medical Sciences,Beijing 100700,China)

机构地区：[1]河南中医药大学,郑州450000 [2]中国中医科学院中药研究所,中药质量控制技术国家工程实验室,北京100700

出　　处：《中国实验方剂学杂志》2020年第12期145-153,共9页Chinese Journal of Experimental Traditional Medical Formulae

基　　金：国家“重大新药创制”科技重大专项(2018ZX09721-004)。

摘　　要：目的:研究石菖蒲(Acorus tatarinowii)根茎的水溶性化学成分及核苷类成分在水提过程中的转化途径。方法:采用大孔树脂,LH-20型羟丙基葡聚糖凝胶(Sephadex LH-20),ODS柱色谱及制备HPLC等方法进行分离纯化,根据理化性质和波谱数据鉴定化合物结构。采用HPLC指认石菖蒲水提液中的核苷类化学成分并考察其稳定性,通过核苷酸添加试验,研究石菖蒲水提过程中核苷类成分可能存在的转化途径。结果:从石菖蒲根茎中分离鉴定了11个化合物,包括4个核苷或碱基类化合物,4个苯丙素类化合物,2个生物碱类化合物,1个糠醛类化合物,分别鉴定为尿苷(1),腺嘌呤(2),鸟苷(3),腺苷(4),5-羟甲基糠醛(5),5-(羟基甲基)-1H-吡咯-2-甲醛(6),(threo)1’,2’-dihydroxyasarone(7),(erythro)1’,2’-dihydroxyasarone(8),acoraminol A(9),acoraminol B(10),菖蒲碱丙(11)。化合物1~4及胞苷可从石菖蒲水提液的HPLC色谱图中指认出来。石菖蒲超声提取0.5 h水溶液中核苷类成分稳定性较差,超声提取3 h和回流提取0.5 h水溶液中核苷类成分稳定性较好。石菖蒲在水提过程中,可能存在5’-胞苷酸向胞苷转化;单磷酸尿苷向尿苷转化;鸟苷酸向鸟苷转化;单磷酸腺苷、二磷酸腺苷、三磷酸腺苷均可以向腺苷转化,腺苷进而向腺嘌呤转化。结论:化合物1~4和6为首次从菖蒲属植物中分离得到,进一步丰富了石菖蒲的化学成分组成。石菖蒲中核苷类成分的稳定性及转化途径研究为石菖蒲及其他含核苷类成分中药的分析评价提供了参考依据。Objective:To study the water soluble chemical constituents in rhizoma of Acorus tatarinowii and transformation pathway of nucleosides in the process of water extraction.Method:Compounds were isolated and purified by column chromatography on macroporous resin,Sephadex LH-20,ODS and preparative HPLC.Their structures were identified on the basis of physicochemical properties and spectral data.Nucleosides were identified from aqueous extract of A.tatarinowii,and their stability was investigated by HPLC.The possible transformation pathways of nucleosides in aqueous extract of A.tatarinowii were studied by nucleotide addition test.Result:Eleven compounds including four nucleosides,four phenylpropanoids,two alkaloids and a furfural were isolated,and identified as uridine(1),adenine(2),guanosine(3),adenosine(4),5-hydroxymethylfurfural(5),5-(hydroxymethyl)-1 H-pyrrole-2-carboxaldehyde(6),(threo)1’,2’-dihydroxyasarone(7),(erythro)1’,2’-dihydroxyasarone(8),acoraminol A(9),acoraminol B(10),and tatarine A(11).The chromatographic peaks of compounds 1-4 and cytidine were identified from aqueous extract of A.tatarinowii by HPLC.After ultrasonic extraction for 0.5 h,the stability of nucleosides in water was poor.After ultrasonic extraction for 3 h or refluxing extraction for 0.5 h,the stability of nucleosides in water was good.Four transformation pathways including 5’-cytidylic acid→cytidine,uridine monophosphate→uridine,guanosine monophosphate,guanosine and adenosine-5’-monophosphate,adenosine 5’-diphosphate,adenosine 5’-triphosphorate,adenosine,adenine might exist in water extract of A.tatarinowii.Conclusion:Compounds 1-4 and 6 were isolated from the genus Acorus for the first time.These compounds further enriched the chemical constituents of A.tatarinowii.The stability and transformation pathway of nucleosides in A.tatarinowii provides reference data for the analysis of nucleosides in A.tatarinowii and other traditional Chinese medicine.

关 键 词：石菖蒲 水提液 苯丙素 核苷 核苷酸 转化途径 

分 类 号：R284.2[医药卫生—中药学] R22[医药卫生—中医学]