Structural and bioactive studies of terpenes and cyclopeptides from the Genus Rubia

Chemistry Central Journal

Kuo Xu¹  Penglong Wang¹  Bin Yuan¹  Yatao Cheng¹  Qiang Li¹  Haimin Lei¹ 

[1] School of Chinese Pharmacy, Beijing University of Chinese Medicine, Beijing, 100102, China

关键词: Bioactivities;    Cyclopeptides;    Terpenes;    Phytochemicals;    Genus Rubia;   

Others  :  787912
DOI  :  10.1186/1752-153X-7-81

 received in 2012-12-28, accepted in 2013-04-11,  发布年份 2013

【 摘 要 】

Genus Rubia fell into about 70 species distributed widely around the world, a total of 36 species and 2 varieties were reported from China. The extracts and phytochemicals of Rubia plants had drawn considerable attention due to their potent bioactivities. As the two major ingredients from these plants, pentacyclic triterpenes and cyclopeptides were becoming a hot topic over the past twenty years for their remarkable anticancer, antioxidant and other effects. This paper compiled all 65 terpenes and 44 cyclopeptides with their distributions, physiological activities and melting points (or optical rotations) as reported in 85 references; besides, structure-activity relationships of these derivatives were briefly discussed. The information involved in this paper was expected to be meaningful for the further studies of the Genus Rubia.

【 授权许可】

   
2013 Xu et al.; licensee Chemistry Central Ltd.

【 参考文献 】

• [1]Chen WQ, Luo XR, Gao YZ, Ruan YZ: Flora of China: Rubiaceae. Beijing 1999, 71(1):287-318.
• [2]Xu K, Wang PL, Wang L, Liu CM, Xu SX, Cheng YT, Wang YH, Li Q, Lei HM: Quinone derivatives from Genus Rubia plants and their bioactivities. Chem Biodiversin press
• [3]Zhao SM, Kuang B, Fan JT, Yan H, Xu WY, Tan NH: Antitumor cyclic hexapeptides from Rubia plants: history, chemistry, and mechanism (2005–2011). CHIMIA Int J Chem 2011, 65(12):952-956.
• [4]Chinese Pharmacopoeia Commission: Chinese Pharmacopoeia. Part I. Beijing; 2010:218-219.
• [5]Meena AK, Pal B, Panda P, Sannd R, Rao MM: A review on Rubia cordifolia: its phyto constituents and therapeutic uses. Drug Invention Today 2010, 2(5):244-246.
• [6]RamSingh G, Chauhan SMS: 9, 10-anthraquinones and other biologically active compounds from the Genus Rubia. Chem Biodivers 2004, 1(9):1241-1242.
• [7]Wu LJ, Wang SX, Hua HM, Li X, Zhu TR, Miyase T, Ueno A: 6-methoxygeniposidic acid, an iridoid glycoside from Rubia cordifolia. Phytochemistry 1991, 30(5):1710-1711.
• [8]EI-Emary NA, Backheet EY: Three hydroxymethylanthraquinone glycosides from Rubia tinctorum. Phytochemistry 1998, 49(1):277-279.
• [9]Ozgen U, Kazaz C, Secen H, Calis I, Coskun M, Houghton PJ: A novel naphthoquinone glycoside from Rubia peregrina L. Turk J Chem 2009, 33:561-568.
• [10]Talapatra SK, Sarkar AC, Talapatra B: Two pentacyclic triterpenes from Rubia cordifolia. Phytochemistry 1981, 20(8):1923-1927.
• [11]Itokawa H, Qiao YF , Takeya K : New arborane type triterpenoids from Rubia cordifolia var. pratensis and R. oncotricha. Chem Pharm Bull 1990, 38(5):1435-1437.
• [12]Itokawa H, Qiao YF, Takeya K, Iitaka Y: New triterpenoids from Rubia cordifolia var. pratensis (Rubiaceae). Chem Pharm Bull 1989, 37(6):1670-1672.
• [13]Zou C, Hao XJ, Chen CX, Zhou J: New arborane type triterpenoids from Rubia yunnanensis (I). Acta Botanica Yunnanica 1993, 15(1):89-91.
• [14]Zou C, Hao XJ, Chen CX, Zhou J: Structures of Rubiarbonone B and C. Acta Botanica Yunnanica 1999, 21(2):256-259.
• [15]Liou MJ, Wu TS: Triterpenoids from Rubia yunnanensis. J Nat Prod 2002, 65(9):1283-1287.
• [16]Xu XY, Zhou JY, Fang QC: Chemical constituents of Rubia yunnanensis root. J Chin Pharmaceut Sci 1995, 4(3):157-160.
• [17]Arisawa M, Ueno H, Nimura M, Hayashi T, Morita N: Rubiatriol, a new triterpenoid from the Chinese Drug Qián Cáo Gén. Rubia cordifolia. J Nat Prod 1986, 49(6):1114-1116.
• [18]Xu XY, Zhou JY, Fang QC: Study on the chemical constituents of Rubia Yunnanensis Diels. Acta Pharmaceutica Sinica 1994, 29(3):237-240.
• [19]Morikawa T, Tao J, Ando S, Matsuda H, Yoshikawa M: Absolute stereostructures of new arborinane-type triterpenoids and inhibitors of nitric oxide production from Rubia yunnanensis. J Nat Prod 2003, 66(5):638-645.
• [20]Kuang B, Han J, Zeng GZ, Chen XQ, He WJ, Tan NH: Three new triterpenoids from Rubia schumanniana. Nat Prod Bioprospect 2012, 2:166-169.
• [21]Tao J, Morikawa T, Ando S, Matsuda H, Yoshikawa M: Bioactive constituents from Chinese natural medicines. XI.1) Inhibitors on NO production and degranulation in RBL-2H3 from Rubia yunnanensis: structures of Rubianosides II, III, and IV, Rubianol-g, and Rubianthraquinone. Chem Pharm Bull 2003, 51(6):654-662.
• [22]Fan JT, Kuang B, Zeng GZ, Zhao SM, Ji CJ, Zhang YM, Tan NH: Biologically active arborinane-type triterpenoids and anthraquinones from Rubia yunnanensis. J Nat Prod 2011, 74(10):2069-2080.
• [23]Ibraheim ZZ, Gouda YG: Minor constituents from Rubia Cordifolia L. root. Bull Pharm Sci 2010, 33(2):225-233.
• [24]Son JK, Jung JH, Lee CS, Moon DC, Choi SW, Min BS, Woo MH: DNA Topoisomerases I and II inhibition and cytotoxicity of constituents from the roots of Rubia cordifolia. Bull Korean Chem Soc 2006, 27(8):1231-1234.
• [25]Jeong SY, Zhao BT, Lee CS, Son JK, Min BS, Woo MH: Constituents with DNA Topoisomerases I and II inhibitory activity and cytotoxicity from the roots of Rubia cordifolia. Planta Med 2012, 78(2):177-181.
• [26]Son JK, Jung SJ, Jung JH, Fang Z, Lee CS, Seo CS, Moon DC, Min BS, Kim MR, Woo MH: Anticancer constituents from the roots of Rubia cordifolia L. Chem Pharm Bull 2008, 56(2):213-216.
• [27]Liou MJ, Teng CM, Wu TS: Constituents from Rubia ustulata Diels and R. yunnanensis Diels and their Antiplatelet Aggregation Activity. J Chin Chem Soc 2002, 49(6):1025-1030.
• [28]Chung MI, Jou SJ, Cheng TH, Lin CN, Ko FN, Teng CM: Antiplatelet constituents of formosan Rubia akane. J Nat Prod 1994, 57(2):313-316.
• [29]Khan MA, Rahman A: Karachic acid: A new triterpenoid from Betula utilis. Phytochemistry 1975, 14(3):789-791.
• [30]Zou C, Hao XJ, Chen CX, Zhou J: A new antitumor glycocyclohexapeptide and arborane type new triterpenoids Rubia yunnanensis. Acta Botanica Yunnanica 1992, 14(1):114.
• [31]Melo CL, Queiroz MGR, Fonseca SGC, Bizerra AMC, Lemos TLG, Melo TS, Santos FA, Rao VS: Oleanolic acid, a natural triterpenoid improves blood glucose tolerance in normal mice and ameliorates visceral obesity in mice fed a high-fat diet. Chem-Biol Interact 2010, 185(1):59-65.
• [32]Chen LS, Lv Y, Xu SW, Xin Y: Study on the triterpene acids in fruit of Crataegus pinnatifida. Lishizhen Med Mater Med Res 2008, 19(12):2909-2910.
• [33]Peng JN, Feng XZ, Li GY, Liang XT: Chemical investigation of Genus Hedyotis II. Isolation and identification of iridoids from Hedyotis Chrysotricha. Acta Pharmaceutica Sinica 1997, 32(12):908-913.
• [34]Xie RR, Guo J, Zhang DZ, Yan CY: Study on chemical constituents of compound ZhenzhuTiaozhi. Journal of Guangdong Pharmaceutical College 2010, 26(4):332-333.
• [35]Siddiqui BS, Firdous , Begum S: Two triterpenoids from the leaves of Plumeria obtuse. Phytochemistry 1999, 52(6):1111-1115.
• [36]Kim MR, Lee HH, Hahm KS, Moon YH, Woo ER: Pentacyclic triterpenoids and their cytotoxicity from the stem bark of Styraxjaponica S. et Z. Arch Pharm Res 2004, 27(3):283-286.
• [37]Ngouela S, Nyasse B, Tsamo E, Sondengam BL, Connollya JD: Spathodic acid: a triterpene acid from the stem bark of Spathodea campanulata. Phytochemistry 1990, 29(12):3959-3961.
• [38]Tan NH, Zhou J: Plant cyclopeptides. Chem Rev 2006, 106(3):840-895.
• [39]Zhao SM, Kuang B, Fan JT, Yan H, Xu WY, Tan NH: Antitumor cyclic hexapeptides from Rubia Plants: History, Chemistry, and Mechanism (2005–2011). CHIMIA 2011, 65(12):952-956.
• [40]Itokawa H, Takeya K, Mori N, Sonobe T, Mihashi S, Hamanaka T: Studies on Antitumor cyclic hexapeptides RA obtained from Rubiae Radix Rubiaceae. VI: minor antitumor constituents. Chem Pharm Bull 1986, 34(9):3762-3768.
• [41]Itokawa H, Takeya K, Mihara K, Mori N, Hamanaka T, Sonobe T, Iitaka Y: Studies on the antitumor cyclic hexapeptides obtained from Rubiae Radix. Chem Pharm Bull 1983, 31(4):1424-1427.
• [42]Itokawa H, Morita H, Takeya K, Tomioka N, Itai A, Iitaka Y: New antitumor bicyclic hexapeptides, RA-VI and -VIII from Rubia cordifolia; conformation-activity relationship II. Tetrahedron 1991, 47(34):7007-7020.
• [43]Itokawa H, Yamamiya T, Morita H, Takeya K: New antitumour bicyclic hexapeptides, RA-IX and-X from Rubia cordifolia. Part 3. Conformation–antitumour activity relationship. J Chem Soc, Perkin Trans 1 1992, 4:455-459.
• [44]Itokawa H, Takeya K, Mori N, Hamanaka T, Sonobe T, Mihara K: Isolation and antitumor activity of cyclic hexapeptides isolated from Rubiae Radix. Chem Pharm Bull 1984, 32(1):284-290.
• [45]Morita H, Yamamiya T, Takeya K, Itokawa H: New antitumor bicyclic hexapeptides, RA-XI, -XII, -XIII and -XIV from Rubia cordifolia. Chem Pharm Bull 1992, 40(5):1352-1354.
• [46]Takeya K, Yamamiya T, Morita H, Itokawa H: Two antitumour bicyclic hexapeptides from Rubia cordifolia. Phytochemistry 1993, 33(3):613-615.
• [47]Hitotsuyanagi Y, Ishikawa H, Hasuda T, Takeya K: Isolation, structural elucidation, and synthesis of RA-XVII, a novel bicyclic hexapeptide from Rubia cordifolia, and the effect of side chain at residue 1 upon the conformation and cytotoxic activity. Tetrahedron Lett 2004, 45(5):935-938.
• [48]Itokawa H, Morita H, Takeya K, Tomioka N, Itai A: RAI-III and VI, conformational isomers of antitumor cyclic hexapeptides, RA-III and VI from Rubia cordifolia. Chemistry Lett 1991, 20(12):2217-2220.
• [49]Morita H, Yamamiya T, Takeya K, Itokawa H, Sakuma C, Yamada J, Suga T: Conformational recognition of RA-XII by 80S Ribosomes: a differential line broadening study in 1H NMR spectroscopy. Chem Pharm Bull 1993, 41(4):781-783.
• [50]Itokawa H, Morita H, Kondo K, Hitotsuyanagi Y, Takeya K, Iitaka Y: Isomerization of antitumour bicyclic hexapeptide, RA-VII from Rubia cordifolia. Part 4. conformation– antitumour activity relationship. J Chem Soc, Perkin Trans 2 1992, 9:1635-1642.
• [51]Lee JE, Hitotsuyanagi Y, Kim IH, Hasuda T, Takeya K: A novel bicyclic hexapeptide, RA-XVIII, from Rubia cordifolia: structure, semi-synthesis, and cytotoxicity. Bioorg Med Chem Lett 2008, 18(2):808-811.
• [52]Lee JE, Hitotsuyanagi Y, Takeya K: Structures of cytotoxic bicyclic hexapeptides, RA-XIX, -XX, -XXI, and -XXII, from Rubia cordifolia L. Tetrahedron 2008, 64(18):4117-4125.
• [53]Lee JE, Hitotsuyanagi Y, Fukaya H, Kondo K, Takeya K: New cytotoxic bicyclic hexapeptides, RA-XXIII and RA-XXIV, from Rubia cordifolia L. Chem Pharm Bull 2008, 56(5):730-733.
• [54]Fan JT, Chen YS, Xu WY, Du LC, Zeng GZ, Zhang YM, Su J, Li Y, Tan NH: Rubiyunnanins A and B, two novel cyclic hexapeptides from Rubia yunnanensis. Tetrahedron Lett 2010, 51(52):6810-6813.
• [55]Fan JT, Su J, Peng YM, Li Y, Li J, Zhou YB, Zeng GZ, Yan H, Tan NH: Rubiyunnanins C–H, cytotoxic cyclic hexapeptides from Rubia yunnanensis inhibiting nitric oxide production and NF-κB activation. Bioorg Med Chem 2010, 18(23):8226-8234.
• [56]Zou C, Hao XJ, Zhou J: Antitumor glycocyclohexapeptide from Rubia yunnanensis. Acta Botanica Yunnanica 1993, 15(4):399-402.
• [57]He M, Zou C, Hao XJ, Zhou J: A new antitumor cyclic hexapeptide glycoside from Rubia yunnanensis. Acta Botanica Yunnanica 1993, 15(4):408.
• [58]He M, Zou C, Hao XJ, Zhou J: New antitumor glycocyclohexapeptide from Rubia yunnanensis. Chinese Chem Lett 1993, 4:1065.
• [59]Hitotsuyanagi Y, Aihara T, Takeya K: RA-dimer A, a novel dimeric antitumor bicyclic hexapeptide from Rubia cordifolia L. Tetrahedron Lett 2000, 41(32):6127-6130.
• [60]Hamanaka T, Ohgoshi M, Kawahara K, Yamakawa K, Tsuruo T, Tsukagoshi S: A novel antitumor cyclic hexapeptide (RA-700) obtained from Rubiae radix. Pharmaceutical Society of Japan 1987, 10(11):616-623.
• [61]Adwankar MK, Chitnis MP: In vivo anti-Cancer activity of RC-18. Chemotherapy 1982, 28(4):291-293.
• [62]Hitotsuyanagi Y, Odagiri M, Kato S, Kusano JI, Hasuda T, Fukaya H, Takeya K: Isolation, structure determination, and synthesis of Allo-RA-V and Neo-RA-V, RA-Series bicyclic peptides from Rubia cordifolia L. Chem Eur J 2012, 18(10):2839-2846.
• [63]Hitotsuyanagi Y, Kusano JI, Kim IH, Hasuda T, Fukaya H, Takeya K: O-Seco-RA-XXIV, a possible precursor of an antitumor peptide RA-XXIV, from Rubia cordifolia L. Phytochem Lett 2012, 5(2):335-339.
• [64]Krishnaiah VC, Ishaq BM, Kumar CH, Kumar JGS: Antidiarrhoeal activity of root extracts of Rubia cordifolia Linn. JGTPS 2011, 2(4):476-488.
• [65]Patel PR, Raval BP, Karanth HA, Patel VR: Potent antitumor activity of Rubia cordifolia. International Journal of Phytomedicine 2011, 2(1):44-46.
• [66]Joharapurkar AA, Zambad SP, Wanjari MM, Umathe SN: In vivo evaluation of antioxidant activity of alcoholic extract of Rubia cordifolia Linn. and its influence on ethanol-induced immunosuppression. Indian J Pharmacol 2003, 35(4):232-236.
• [67]Baskar R, Bhakshu LM, Bharathi GV, Reddy SS, Karuna R, Reddy GK, Saralakumari D: Antihyperglycemic activity of aqueous root extract of Rubia cordifolia in streptozotocin- induced diabetic rats. Pharm Biol 2006, 44(6):475-479.
• [68]Charde RM, Charde MS, Fulzele SV, Satturwar PM, Joshi SB: Wound healing activity of ethanolic extract of Rubia Cordifolia roots. J Pharm Res 2010, 3(12):3070-3071.
• [69]Deoda RS, Kumar D, Bhujbal SS: Gastroprotective effect of Rubia cordifolia Linn. on aspirin plus pylorus-ligated ulcer. Evid base Compl Alternative Med 2011, 2011(Article ID 541624):5. http://www.hindawi.com/journals/ecam/2011/541624/abs/ webcite
• [70]Cheng XH, Xiong YQ: Advances in studies on pharmacological activities of pentacyclic triterpenoid saponins. Chinese Traditional and Herbal Drugs 2007, 38(5):792-795.
• [71]Hasuda T, Hitotsuyanagi Y, Takeya K: Production of monoclonal antibodies against antitumor cyclohexapeptide RA-VII from Rubia cordifolia and their characterization. J Nat Med 2011, 65(3):588-593.
• [72]Koizumi T, Abe M, Yamakuni T, Ohizumi Y, Hitotsuyanagi Y, Takeya K, Sato Y: Metronomic scheduling of a cyclic hexapeptide Ra-VII for anti-angiogenesis, tumor vessel maturation and anti-tumor activity. Cancer Sci 2006, 97(7):665-674.
• [73]Reyes-Zurita FJ, Rufino-Palomares EE, Lupianez JA, Cascante : Maslinic acid, a natural triterpene from Olea europaea L., induces apoptosis in HT29 human colon-cancer cells via the mitochondrial apoptotic pathway. Cancer Lett 2009, 273(1):44-54.
• [74]Juan ME, Planas JM, RuizGutierrez V, Daniel H, Wenzel U: Antiproliferative and apoptosis inducing effects of maslinic and oleanolic acids, two pentacyclic triterpenes from olives, on HT29 colon cancer cells. Brit J Nutr 2008, 100(1):36-43.
• [75]Li CH, Yang ZF, Zhai CY, Qiu WW, Li DL, Yi ZF, Wang L, Tang J, Qian M, Luo J, Liu MY: Maslinic acid potentiates the anti-tumor activity of tumor necrosis factor a by inhibiting NF-κB signaling pathway. Mol Cancer 2010, 9:73-85. BioMed Central Full Text
• [76]Mooi LY, Yew WT, Hsum YW, Soo KK, Hoon LS, Chieng YC: Suppressive effect of maslinic acid on PMA-induced Protein Kinase C in Human B-Lymphoblastoid Cells. Asian Pac J Cancer P 2012, 13:1177-1182.
• [77]Prasad S, Yadav VR, Kannappan R, Aggarwal BB: Ursolic Acid, a pentacyclic triterpene, potentiates TRAIL-induced apoptosis through p53-independent up-regulation of death receptors. J Biol Chem 2011, 286(7):5546-5557.
• [78]Pathak AK, Bhutani M, Nair AS, Ahn KS, Chakraborty A, Kadara H, Guha S, Sethi G, Aggarwal BB: Ursolic acid inhibits STAT3 activation pathway leading to suppression of proliferation and chemosensitization of human multiple myeloma cells. Mol Cancer Res 2007, 5(9):943-955.
• [79]Yan SL, Huang CY, Wu ST, Yin MC: Oleanolic acid and ursolic acid induce apoptosis in four human liver cancer cell lines. Toxicol in Vitro 2010, 24(3):842-848.
• [80]Yue GGL, Fan JT, Lee JKM, Zeng GZ, Ho TWF, Fung KP, Leung PC, Tan NH, Lau CBS: Cyclopeptide RA-V inhibits angiogenesis by down-regulating ERK1/2 phosphorylation in HUVEC and HMEC-1 endothelial cells. Brit J Pharmacol 2011, 164(7):1883-1898.
• [81]Horiuchi K, Shiota S, Hatano T, Yoshida T, Kuroda T, Tsuchiya T: Antimicrobial activity of oleanolic acid from Salvia officinalis and related compounds on Vancomycin-Resistant Enterococci (VRE). Biol Pharm Bull 2007, 30(6):1147-1149.
• [82]Jayaprakasam B, Olson LK, Schutzki RE, Tai MH, Nair MG: Amelioration of obesity and glucose intolerance in High-Fat-Fed C57BL/6 mice by anthocyanins and ursolic acid in Cornelian Cherry (Cornus mas). J Agric Food Chem 2006, 54(1):243-248.
• [83]Liu J, Sun HB, Duan WG, Mu DY, Zhang LY: Maslinic acid reduces blood glucose in KK-Ay mice. Biol Pharm Bull 2007, 30(11):2075-2078.
• [84]Wang ZH, Hsu CC, Huang CN, Yin MC: Anti-glycative effects of oleanolic acid and ursolic acid in kidney of diabetic mice. Eur J Pharmacol 2010, 628(1–3):255-260.
• [85]Xu HX, Zeng FQ, Wan M, Sim KY: Anti-HIV triterpene acids from Geum japonicum. J Nat Prod 1996, 59(7):643-645.