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Identification and characterization of organic and glycosidic acids in crude resin glycoside fraction from Calystegia hederacea

  • Masateru OnoEmail author
  • Yoshino Ichihara
  • Nao Saito
  • Minami Yamada
  • Kana Yuuki
  • Masami Nawata
  • Shuhei Tsutsumi
  • Shin Yasuda
  • Ryota Tsuchihashi
  • Masafumi Okawa
  • Junei Kinjo
  • Hiroyuki Miyashita
  • Hitoshi Yoshimitsu
  • Toshihiro Nohara
Original Paper
  • 27 Downloads

Abstract

Resin glycosides are well known as the purgative ingredients, which are characteristic of convolvulaceous plants. Calystegia hederacea Wall. is a perennial herbaceous vine that is widespread throughout India and East Asia. All parts of this plant are used for the treatment of menoxenia, gonorrhea, etc. Alkaline hydrolysis of the crude resin glycoside fraction of the whole plants of C. hederacea yielded four new glycosidic acids, calyhedic acids A, B, C, and D, along with two known glycosidic acids, calysolic acids A and C, and three known organic acids, 2S-methylbutyric, tiglic, and 2R,3R-nilic acids. Their structures were characterized on the basis of spectroscopic data and chemical evidence. Calyhedic acids A, B, and D were penta-, hexa-, and hepta-glycosides of 12S-hydroxyhexadecanoic acid, respectively, and cayhedic acid C was an isomer of calyhedic acid D, in which the 12S-hydroxyhexadecanoyl residue of calyhedic acid D was replaced by a 11S-hydroxyhexadecanoyl residue. Additionally, cytotoxic activity toward HL-60 human promyelocytic leukemia cells of the crude resin glycoside fraction, the glycosidic acid fraction, calyhedic acid A, and calysolic acid A from C. hederacea was evaluated. Furthermore, to clarify the structure–activity relationship of resin glycosides, the activities of six genuine resin glycosides with calysolic acid A or calysolic acid C as the glycosidic acid, which were isolated from C. soldanella, were examined. Among them, the crude resin glycoside fraction and five genuine resin glycosides with macrolactone structures demonstrated clear cytotoxic activities, while the glycosidic acid fraction, calyhedric acid A, calysolic acid A, and a genuine non-macrolactone-type resin glycoside were either inactive or exhibited weaker activity than the tested macrolactone-type resin glycosides.

Keywords

Resin glycoside Glycosidic acid Calystegia hederacea Convolvulaceae Calyhedic acid Cytotoxic activity 

Notes

Acknowledgements

We express our appreciation to Mr. H. Harazono of Fukuoka University for the measurement of the FAB-MS. This research was supported in part by a Grant-in-Aid for Scientific Research (C) (JPS KAKENHI Grant number JP16K08306) and by the Research and Study Program/Project of Tokai University Educational System General Research Organization (Kanagawa, Japan).

Compliance with ethical standards

Conflict of interest

The authors declare no conflict of interest.

References

  1. 1.
    Ono M (2017) Resin glycosides from Convolvulaceae plants. J Nat Med 71:591–604CrossRefGoogle Scholar
  2. 2.
    Pereda-Miranda R, Rosas-Ramírez D, Castańeda-Gómez J (2010) Resin glycosides from morning glory family. In: Kinghorn AD, Falk H, Kobayashi J (eds) Progress in the chemistry of organic natural products, vol 92. Springer, New York, pp 77–153Google Scholar
  3. 3.
    Yoshikawa K, Yagi C, Hama H, Tanaka M, Arihara S, Hashimoto T (2010) Ipomotaosides A–D, resin glycosides from the aerial parts of Ipomoea batatas and their inhibitory activity against COX-1 and COX-2. J Nat Prod 73:1763–1766CrossRefGoogle Scholar
  4. 4.
    Figueroa-González G, Jacobo-Herrera N, Zentella-Dehesa A, Pereda-Miranda R (2012) Reversal of multidrug resistance by morning glory resin glycosides in human breast cancer cells. J Nat Prod 75:93–97CrossRefGoogle Scholar
  5. 5.
    Ono M, Takigawa A, Kanemaru Y, Kawakami G, Kabata K, Okawa M, Kinjo J, Yokomizo K, Yoshimitsu H, Nohara T (2014) Calysolins V–IX, resin glycosides from Calystegia soldanella and their antiviral activity toward herpes. Chem Pharm Bull 62:97–105CrossRefGoogle Scholar
  6. 6.
    Useful plants of the world (1989) In: Hotta M, Ogata K, Nitta A, Hosikawa K, Yanagi M, Yamazaki K (eds) Heibonsha Ltd., Tokyo, Japan, p 196 (in Japanese plant dictionary)Google Scholar
  7. 7.
    Ono M, Azuchi M, Ichio M, Jiyoubi Y, Tsutsumi S, Yasuda S, Tsuchihasi R, Okawa M, Kinjo J, Yoshimitsu H, Nohara T (2019) Seven new resin glycosides from the seeds of Quamoclit × multifida. J Nat Med 73:11–22CrossRefGoogle Scholar
  8. 8.
    Takigawa A, Setoguchi H, Okawa M, Kinjo J, Miyashita H, Yokomizo K, Yoshimitsu H, Nohara T, Ono M (2011) Identification and characterization of component organic and glycosidic acids of crude resin glycoside fraction from Calystegia soldanella. Chem Pharm Bull 59:1163–1168CrossRefGoogle Scholar
  9. 9.
    Ono M, Takagi-Taki F, Honda-Yamada Y, Noda N, Miyahara K (2010) Components of ether-insoluble resin glycoside (convolvulin) from seeds of Quamoclit pennata. Chem Pharm Bull 58:666–672CrossRefGoogle Scholar
  10. 10.
    Ono M, Takigawa A, Mineno T, Yoshimitsu H, Nohara T, Ikeda T, Fukuda-Teramachi E, Noda N, Miyahara K (2010) Acylated glycosides of hydroxy fatty acid methyl esters generated from the crude resin glycoside (pharbitin) of seeds of Pharbitis nil by treatment with indium(III) chloride in methanol. J Nat Prod 73:1846–1852CrossRefGoogle Scholar
  11. 11.
    Tanaka T, Nakashima T, Ueda T, Tomii K, Kouno I (2007) Facile discrimination of aldose enantiomers by reversed-pase HPLC. Chem Pharm Bull 55:899–901CrossRefGoogle Scholar
  12. 12.
    Ono M, Honda F, Karahashi A, Kawasaki T, Miyahara K (1997) Resin glycosides. XXV. Multifidins I and II, new jalapins, from the seed of Quamoclit × multifida. Chem Pharm Bull 45:1955–1960CrossRefGoogle Scholar
  13. 13.
    Cryle MJ, Matovic NJ, De Voss JJ (2003) Products of cytochrome P450Biol (CYP107H1)-catalyzed oxidation of fatty acids. Org Lett 5:3341–3344 (supporting information) CrossRefGoogle Scholar
  14. 14.
    Ding W, Jiang Z-H, Wu P, Xu L, Wei X (2012) Resin glycosides from the aerial parts of Operculina trupethum. Phytochemistry 81:165–174CrossRefGoogle Scholar
  15. 15.
    Ono M, Yamada F, Noda N, Kawasaki T, Miyahara K (1993) Resin glycosides. XVIII. Determination by Mosher's method of the absolute configurations of mono- and dihydroxyfatty acids originated from resin glycosides. Chem Pharm Bull 41:1023–1026CrossRefGoogle Scholar
  16. 16.
    Dale JA, Mosher HS (1973) Nuclear magnetic resonance enantiomer regents. Configurational correlations via nuclear magnetic resonance chemical shifts of diastereomeric mandelate, O-methylmanndelate, and α-methoxy-α-trifluoromethylphenylacetate (MTPA) esters. J Am Chem Soc 95:512–519CrossRefGoogle Scholar
  17. 17.
    Seo S, Tomita Y, Tori K, Yoshimura Y (1978) Determination of the absolute configuration of a secondary hydroxy group in a chiral secondary alcohol using glycosidation shifts in carbon-13 nuclear magnetic resonance spectroscopy. J Am Chem Soc 100:3331–3339CrossRefGoogle Scholar
  18. 18.
    Kitagawa I, Nishio T, Kobayashi M, Kyogoku Y (1981) Marine natural products. VIII. Bioactive triterpene-oligoglycosides from the sea cucumber Holothuria leucosphilota Brandt. Chem Pharm Bull 29:1951–1956CrossRefGoogle Scholar
  19. 19.
    Kasai R, Suzuo M, Asakawa J, Tanaka O (1977) Carbon-13 chemical shifts of isoprenoid-β-d-glucopyranosides and -β -d-mannopyranosides. Stereochemical influences of aglycone alcohols. Tetrahedron Lett 2:175–178CrossRefGoogle Scholar
  20. 20.
    Tori K, Seo S, Yoshimura Y, Arita H, Tomita Y (1977) Glycosidation shifts in carbon-13 NMR spectroscopy: carbon-13 signal shifts from aglycone and glucose to glucoside. Tetrhedron Lett 2:179–182CrossRefGoogle Scholar
  21. 21.
    Yu B, Luo J, Wang J, Zhang D, Yu S, Kong L (2013) Pentasaccharide resin glycosides from Ipomoea cairica and their cytotoxic activities. Phytochemistry 95:421–427CrossRefGoogle Scholar
  22. 22.
    Fan BY, Gu YC, He Y, Li ZR, Luo JG, Kong LY (2014) Cytotoxic resin glycosides from Ipomoea aquatica and their effects on intracellular Ca2+ concentrations. J Nat Prod 77:2264–2272CrossRefGoogle Scholar
  23. 23.
    Takigawa A, Muto H, Kabata K, Okawa M, Kinjo J, Yoshimitsu H, Nohara T, Ono M (2011) Calysolins I–IV, resin glycosides from Calystegia soldanella. J Nat Prod 74:2414–2419CrossRefGoogle Scholar
  24. 24.
    Ono M, Takigawa A, Muto H, Kabata K, Okawa M, Kinjo J, Yokomizo K, Yoshimitsu H, Nohara T (2015) Antiviral activity of four new resin glycosides calysolins XIV–XVII from Calystegia soldanella against herpes simplex virus. Chem Pharm Bull 63:641–648CrossRefGoogle Scholar
  25. 25.
    Fan BY, Lu Y, Yin H, He Y, Li JL, Chen GT (2018) Arvensic acids A-D, novel heptasaccharide glycosidic acids as the alkaline hydrolysis products of crude resin glycosides from Convolvulus arvensis. Fitoterapia 131:209–214CrossRefGoogle Scholar

Copyright information

© The Japanese Society of Pharmacognosy 2019

Authors and Affiliations

  • Masateru Ono
    • 1
    Email author
  • Yoshino Ichihara
    • 1
  • Nao Saito
    • 1
  • Minami Yamada
    • 1
  • Kana Yuuki
    • 1
  • Masami Nawata
    • 1
  • Shuhei Tsutsumi
    • 1
  • Shin Yasuda
    • 1
  • Ryota Tsuchihashi
    • 2
  • Masafumi Okawa
    • 2
  • Junei Kinjo
    • 2
  • Hiroyuki Miyashita
    • 3
  • Hitoshi Yoshimitsu
    • 3
  • Toshihiro Nohara
    • 3
  1. 1.School of AgricultureTokai UniversityKumamotoJapan
  2. 2.Faculty of Pharmaceutical SciencesFukuoka UniversityFukuokaJapan
  3. 3.Faculty of Pharmaceutical SciencesSojo UniversityKumamotoJapan

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