Assimopoulou A N, Karapanagiotis I, Vasiliou A, Kokkini S, Papageorgiou V P
Organic Chemistry Laboratory, Department of Chemical Engineering, Aristotle University of Thessaloniki, 541 24 Thessaloniki, Greece.
Biomed Chromatogr. 2006 Dec;20(12):1359-74. doi: 10.1002/bmc.705.
Alkannin, shikonin (A/S) and their derivatives are enantiomeric hydroxynaphthoquinone red pigments found in the roots of almost 150 species of the Boraginaceae family. A/S have been shown to exhibit strong wound healing, antimicrobial, anti-inflammatory and antioxidant activities and recent extensive research has well established their antitumor properties. A/S and their derivatives comprise the active ingredients of several pharmaceutical and cosmetic preparations. Although A/S have been efficiently synthesized and have been produced by cell tissue cultures in high yield, most of the pharmaceutical preparations worldwide contain A/S extracted from the roots of Boraginaceous species, found in nature. In the present study, a high-performance liquid chromatography/photodiode array/mass spectrometry (HPLC/PDA/MS) method was established to identify monomeric hydroxynaphthoquinones of the alkannin series and other metabolites from Boraginaceous root extracts. This method can be applied for the identification of alkannin derivatives and other metabolites from Boraginaceous cell cultures, and also to determine active ingredients in pharmaceutical preparations containing A/S derivatives. A phytochemical investigation of the Alkanna genus grown in Greece was also performed. Fifty-three root samples belonging to 10 species of the genus Alkanna (A. calliensis, A. corcyrensis, A. graeca, A. methanaea, A. orientalis, A. pindicola, A. primuliflora, A. sieberi, A. stribrnyi and A. tinctoria) were collected from several regions of the Greek flora and analyzed for their constituent hydroxynaphthoquinones and other metabolites. In most of the above Alkanna samples tested, the main hydroxynaphthoquinones were determined to be beta,beta-dimethylacrylalkannin, isovalerylalkannin + alpha-methyl-n-butylalkannin and acetylalkannin. The hydroxynaphthoquinone constituents and their proportions were found to vary among Alkanna species. Unknown metabolites (not monomeric hydroxynaphthoquinones) were detected by HPLC-PDA-MS, while in several Alkanna species hydroxynaphthoquinones were detected for the first time.
紫朱草素、紫草素（A/S）及其衍生物是对映体羟基萘醌红色素，存在于紫草科近150种植物的根部。已证明A/S具有强大的伤口愈合、抗菌、抗炎和抗氧化活性，最近的广泛研究充分证实了它们的抗肿瘤特性。A/S及其衍生物是几种药物和化妆品制剂的活性成分。尽管A/S已被高效合成并通过细胞组织培养大量生产，但全球大多数药物制剂中的A/S是从自然界中紫草科植物的根部提取的。在本研究中，建立了一种高效液相色谱/光电二极管阵列/质谱（HPLC/PDA/MS）方法，用于鉴定紫朱草素系列的单体羟基萘醌以及紫草科根提取物中的其他代谢物。该方法可用于鉴定紫草科细胞培养物中的紫朱草素衍生物和其他代谢物，还可用于测定含有A/S衍生物的药物制剂中的活性成分。还对生长在希腊的紫朱草属植物进行了植物化学研究。从希腊植物区系的几个地区收集了属于紫朱草属10个物种（卡利紫朱草、科基拉紫朱草、希腊紫朱草、梅塔纳紫朱草、东方紫朱草、品都斯紫朱草、报春紫朱草、西伯紫朱草、斯特里布尔紫朱草和染色紫朱草）的53个根样本，并分析了它们所含的羟基萘醌和其他代谢物。在上述大多数测试的紫朱草样本中，主要的羟基萘醌被确定为β，β-二甲基丙烯酰紫朱草素、异戊酰紫朱草素+α-甲基-n-丁基紫朱草素和乙酰紫朱草素。发现羟基萘醌成分及其比例在紫朱草属物种之间有所不同。通过HPLC-PDA-MS检测到了未知代谢物（不是单体羟基萘醌），同时在几个紫朱草属物种中首次检测到了羟基萘醌。
