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p-Coumaroyl Anthocyanins from the Tuber Epidermis of a Colored Potato Solanum tuberosum L. cv Jayoung
p-Coumaroyl Anthocyanins from the Tuber Epidermis of a Colored Potato Solanum tuberosum L. cv Jayoung
Bulletin of the Korean Chemical Society. 2014. Aug, 35(8): 2529-2532
Copyright © 2014, Korea Chemical Society
  • Received : February 26, 2014
  • Accepted : April 02, 2014
  • Published : August 20, 2014
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About the Authors
Hyun Ji Kim
Hye Mi Kim
Kyoung-Goo Lee
Ji-Sun Shin
Hyo-Jin Ahn
College of Oriental Medicine, Sangji University, Wonju-si, Gangwon-do 220-702, Korea
Jin-Cheol Jeong
Highland Agriculture Research Center, NICS, RDA, Pyeongchang 232-955, Korea
Oh-Keun Kwon
Highland Agriculture Research Center, NICS, RDA, Pyeongchang 232-955, Korea
Jung-Hwan Nam
Highland Agriculture Research Center, NICS, RDA, Pyeongchang 232-955, Korea
Kyung-Tae Lee
Dae Sik Jang

Abstract
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Experimental
General Experimental Procedures. 1D and 2D NMR experiments were performed on a Bruker 400 MHz or Verian 500 MHz FT-NMR instrument with tetramethylsilane (TMS) or solvent residues as internal standard. Mass spectra were obtained using an Agilent 1200 series coupled to a 6120 Quadrupole LC/MS system. Silica gel (70-230 mesh and 230-400 mesh, Merck, Germany) was used for column chromatography (CC). Thin-layer chromatographic (TLC) analysis was performed on Kieselgel 60 F 254 plates (silica gel, 0.25 mm layer thickness, Merck, Germany); compounds were visualized by UV light (254 and 365 nm) and 20% (v/v) H 2 SO 4 reagent (Aldrich). All solvents used for the chromatographic separations were distilled before use.
Plant Material. The purple colored potato cultivar, “Jayoung” ( Solanum tuberosum L. cv Jayoung, Solanaceae) was supplied by Highland Agriculture Research Center (HARC), the Korean National Institute of Crop Science, and the Rural Development Administration (RDA), Republic of Korea, in September 2012. A voucher specimen (KHP-2012-SOTU1) was deposited in the Lab. of Natural Product Medicine, College of Pharmacy, Kyung Hee University. The epidermis (< 5 mm thickness) from the fresh tubers of “Jayoung” were cut into small pieces and were freeze-dried.
Extraction and Isolation. The freeze-dried samples (7 kg) were extracted with 30 L of 70% EtOH three times by maceration. The extracts were combined and concentrated in vacuo to give a 70% EtOH extract (642 g). The 70% EtOH extract (641 g) was suspended in distilled water (2 L) and then successively extracted with n -hexane (3 × 2 L), CH 2 Cl 2 (3 × 2 L), EtOAc (3 × 2 L), and n -butanol (3 × 2 L) to give n -hexane- (66.2 g), CH 2 Cl 2 - (5.1 g), EtOAc- (2.3 g), n -butanol- (61.1 g), and water-soluble fractions (506.0 g). The CH 2 Cl 2 - soluble extract was chromatographed over silica gel (230-400 mesh, ϕ 4.2 × 41.5 cm) as stationary phase with a CH 2 Cl 2 -MeOH gradient (from 95:5 to 85:15 v/v; final stage, MeOH 100%) as mobile phase to afford 14 pooled fractions (M1-M14). The fraction M4 (108 mg) was further fractionated using a Sephadex column ( ϕ 2.5 × 75 cm) with CH 2 Cl 2 -MeOH mixture (1:1 v/v), yielding compound 5 (5.0 mg). The fraction M9 (125.7 mg) was subjected to a Sephadex column ( ϕ 3.6 × 73.5 cm) with CH 2 Cl 2 -MeOH mixture (1:1 v/v) to give compound 9 (9.0 mg). Compound 10 (135.1 mg) was purified from the fraction M12 (408 mg) using a reversed phase column chromatography (CC) (YMC gel, ϕ 2.8 × 28.5 cm) with a MeOH-H 2 O gradient (from 1:1 to 1:0 v/v) as mobile phase. A portion of the BuOH-soluble extract (20.2 g) was separated by Diaion HP20 CC ( ϕ 5.0 × 59.0 cm), using gradient mixtures of a MeOH-H 2 O (from 0:1 to 1:0 v/v) as mobile phases, affording 20 fractions (1B1-1B20). Compounds 6 (58.0 mg) and 7 (110.8 mg) were purified from the fraction 1B5 (570 mg) using a flash CC system with Redi Sep-C18 (48 g, MeOH-H 2 O-formic acid = 15:85/1→30/70/1 v/v). Compound 8 (139.8 mg) was obtained from the fraction 1B9 (1.68 g) by using repeated silica gel CC. The fraction 1B12 (310 mg) was subjected to a Sephadex column ( ϕ 3.2 × 37.8 cm) with MeOH to obtain compound 11 (38.8 mg). For the isolation of anthocyanins, a portion of the BuOH-soluble extract (10.26 g) was separated by Diaion HP20 CC ( ϕ 4.4 × 48.8 cm), using gradient mixtures of a MeOH-H 2 O-TFA (from 0:100:0.1 to 100:0:0.1 v/v) as mobile phases, affording five fractions (2B1-2B5). The fraction 2B4 (2.29 g) was further fractionated using a Sephadex column ( ϕ 3.5 × 55.0 cm) with MeOH with 0.1% TFA, yielding seven fractions 2B4-1-2B4-7. An anthocyanin-rich fraction (2B4-4, 245.2 mg) was separated by using preparative HPLC with a gradient of MeCN-H 2 O-TFA (15:85:0.1 to 35:65:0.1), resulting in the isolation of compound 1 (11.0 mg, violet powder) and a mixture of compounds 2-4 (28.0 mg, purple powder).
Petanin (1): Amorphous violet powder; UV (On-line HPLC-DAD) λ max nm: 532; 1 H-NMR (0.1% CF 3 COOD in CD 3 OD, 400 MHz), see Table 1 ; 13 C-NMR (0.1% CF 3 COOD in CD 3 OD, 100 MHz), aglycone: see Table 2 , 3-O-β-Glu : δ 101.3 (C-1''), 73.3 (C-2''), 76.8 (C-3''), 69.9 (C-4''), 76.5 (C-5''), 65.9 (C-6''), 5-O-β-Glu : δ 101.4 (C-1'''), 73.4 (C-2'''), 76.2 (C-3'''), 69.6 (C-4'''), 77.3 (C-5'''), 60.8 (C-6'''), 6''-O-α-Rha : δ 100.7 (C-1''''), 70.7 (C-2''''), 68.9 (C-3''''), 73.9 (C-4''''), 66.4 (C-5''''), 16.5 (C-6''''), 4''''-E-p-Cou : δ 125.7 (C-1), 129.9 (C-2/C-6), 115.5 (C-3/C-5), 159.9 (C-4), 145.6 (C-7), 113.6 (C-8), 167.6 (C-9); APT-ES-MS (positive mode) m/z = 933 [M] + .
Peonanin (2): Amorphous purple powder; UV (On-line HPLC-DAD) λ max nm: 520; 1 H-NMR (0.1% CF 3 COOD in CD 3 OD, 500 MHz), see Table 1 ; 13 C-NMR (0.1% CF 3 COOD in CD 3 OD, 125 MHz), aglycone: see Table 2 , 3-O-β-Glu : δ 101.4 (C-1''), 73.3 (C-2''), 76.8 (C-3''), 69.8 (C-4''), 76.5 (C-5''), 65.9 (C-6''), 5-O-β-Glu : δ 101.3 (C-1'''), 73.4 (C-2'''), 76.2 (C-3'''), 69.6 (C-4'''), 77.3 (C-5'''), 60.7 (C-6'''), 6''-O-α-Rha : δ 100.7 (C-1''''), 70.7 (C-2''''), 68.9 (C-3''''), 73.9 (C-4''), 66.4 (C-5''), 16.5 (C-6''), 4''''-E-p-Cou : δ 125.7 (C-1), 129.8 (C-2/C-6), 115.4 (C-3/C-5), 159.9 (C-4), 145.6 (C-7), 113.6 (C-8), 167.5 (C-9); APT-ES-MS (positive mode) m/z = 917 [M] +
Malvanin (3): 1 H-NMR (0.1% CF 3 COOD in CD 3 OD, 500 MHz): δ 9.00 (1H, s, H-4), 7.98 (2H, s, H-2'/H-6'); 13 C-NMR (0.1% CF 3 COOD in CD 3 OD, 125 MHz), aglycone: see Table 2 ; APT-ES-MS (positive mode) m/z = 947 [M] + .
Pelanin (4): 1 H-NMR (0.1% CF 3 COOD in CD 3 OD, 500 MHz): δ 9.00 (1H, s, H-4), 8.59 (2H, d, J = 9.0 Hz, H-2'/H-6'), 7.06 (2H, d, J = 9.0 Hz, H-3'/H-5'); 13 C-NMR (0.1% CF 3 COOD in CD 3 OD, 125 MHz), aglycone: see Table 2 ; APT-ES-MS (positive mode) m/z = 887 [M] + .
Acknowledgements
Supporting Information.The NMR spectra of1-4are available on request from the correspondence author.
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