Journal of Applied Biological Chemistry

The Korean Society for Applied Biological Chemistry (한국응용생명화학회)
권호 표지
DOI QR코드

DOI QR Code

Phytochemical constituents of Coix lachryma-jobi var. ma-yuen roots and their tyrosinase inhibitory activity

율무근의 식물화학적 성분 연구 및 Tyrosinase 저해 활성

  • Choi, Yun-Hyeok (Bio-Center, Gyeonggido Business & Science Accelerator) ;
  • Choi, Chun Whan (Bio-Center, Gyeonggido Business & Science Accelerator) ;
  • Lee, Jae Yeon (Bio-Center, Gyeonggido Business & Science Accelerator) ;
  • Ahn, Eun-Kyung (Bio-Center, Gyeonggido Business & Science Accelerator) ;
  • Oh, Joa Sub (College of Pharmacy, Dankook University) ;
  • Hong, Seong Su (Bio-Center, Gyeonggido Business & Science Accelerator)
  • Received : 2016.08.22
  • Accepted : 2016.11.17
  • Published : 2017.03.30
Download PDF
⟨ Previous Next ⟩

Abstract

In the course of screening tyrosinase inhibitory activity, EtOAc-soluble fraction of Coix lachryma-jobi var. mayuen Stapf. (Gramineae) roots showed significant inhibition. Further fractionation of the EtOAc-soluble fraction resulted in six compounds, which were identified as (+)-icariol $A_2$ (1), zhepiresionol (2), 4-hydroxybenzaldehyde (3), trans-${\rho}$-coumaric acid (4), N-(2-hydroxy-4-methoxyphenyl)-2-hydroxyacetamide (5), and coixol (6). The chemical structures of these compounds were identified on the basis of spectroscopic methods (MS, 1D and 2D NMR) and comparison with literature values. Compound 1 was first reported from this plant. Also, this is the first time that the isolation of compound 5 has been reported from nature source. Among the isolated compounds, compounds 4 and 6 showed enzyme inhibitory activity, with $IC_{50}$ values of 6.5 and $62.4{\mu}M$, respectively, in comparison with these of positive control, arbutin.

본 연구는 천연 미백소재 탐색을 위하여 율무(C. lachryma-jobi var. ma-yuen) 부산물 추출물의 tyrosinase 저해활성을 검증하였으며, 그 중에서 뿌리 추출물은 $159.3g/{\mu}mL$의 $IC_{50}$ 값을 나타내었다. 율무 뿌리 추출물의 순차적 용매 분획에 대한 활성 검증 후 가장 활성이 우수한 EtOAc 분획물에 대하여 Diaion HP-20 column chromatography, MPLC및 preparative HPLC를 수행해 율무근으로부터 여섯 개의 화합물을 정제하였고, 이 물질들의 구조 분석은 LC-MS와 NMR 데이터 해석을 바탕으로 진행하여 각각 (+)-icariol $A_2$ (1), zhepiresionol (2), 4-hydroxybenzaldehyde (3), trans-${\rho}$-coumaric acid (4), N-(2-hydroxy-4-methoxyphenyl)-2-hydroxyacetamide (5), coixol (6)로 구조를 규명하였다. 화합물 1은 이 식물에서 처음으로 분리되었으며, 화합물 5는 자연계로부터 처음으로 분리된 화합물로 확인하였다. 이들 화합물 중 4-hydroxybenzaldehyde (3), trans-${\rho}$-coumaric acid (4)와 coixol (6)은 순서대로 707.4, 6.5, $62.4{\mu}M$의 $IC_{50}$ 값을 나타내어 대조군으로 사용한 arbutin ($IC_{50}=618.7{\mu}M$)과 비교시 유사하거나 우수한 활성을 확인하였다. 이로 미루어 보아, 율무근 추출물과 활성물질의 tyrosinase 저해활성을 확인할 수 있었으며, 율무근 추출물의 미백소재로서의 적용 가능성을 확인할 수 있었다.

Keywords

References

  1. An SM, Lee SI, Choi SW, Moon SW, Boo YC (2008) p-Coumaric acid, a constituent of Sasa quelpaertensis Nakai, inhibits cellular melanogenesis stimulated by alpha-melanocyte stimulating hormone. Br J Dermatol 159: 292-299 https://doi.org/10.1111/j.1365-2133.2008.08653.x
  2. Ando S, Ando O, Suemoto Y, Mishima Y (1993) Tyrosinase gene transcription and its control by melanogenetic inhibitor. J Invest Dermatol 100: 150-155 https://doi.org/10.1038/jid.1993.68
  3. Chang TS (2009) An updated review of tyrosinase inhibitors. Int J Mol Sci 10: 2440-2475 https://doi.org/10.3390/ijms10062440
  4. Chen HH, Chiang W, Chang JY, Chien YL, Lee CK, Liu KJ, Cheng YT, Chen TF, Kuo YH, Kuo CC (2011) Antimutagenic constituents of adlay (Coix lachryma-jobi L. var. ma-yuen Stapf) with potential cancer chemopreventive activity. J Agric Food Chem 59: 6444-6452 https://doi.org/10.1021/jf200539r
  5. Chen WC, Tseng TS, Hsiao NW, Lin YL, Wen ZH, Tsai CC, Lee YC, Lin HH, Tsai KC (2015) Discovery of highly potent tyrosinase inhibitor, T1, with significant anti-melanogenesis ability by zebrafish in vivo assay and computational molecular modeling. Sci Rep 5: 7995 https://doi.org/10.1038/srep07995
  6. Chung CP, Hsia SM, Lee MY, Chen HJ, Cheng F, Chan LC, Kuo YH, Lin YL, Chiang W (2011a) Gastroprotective activities of adlay (Coix lachryma-jobi L. var. ma-yuen Stapf) on the growth of the stomach cancer AGS cell line and indomethacin-induced gastric ulcers. J Agric Food Chem 59: 6025-6033 https://doi.org/10.1021/jf2009556
  7. Chung CP, Hsu CY, Lin JH, Kuo YH, Chiang W, Lin YL (2011b) Antiproliferative lactams and spiroenone from adlay bran in human breast cancer cell lines. J Agric Food Chem 59: 1185-1194 https://doi.org/10.1021/jf104088x
  8. Chung CP, Hsu HY, Huang DW, Hsu HH, Lin JT, Shih CK, Chiang W (2010) Ethyl acetate fraction of adlay bran ethanolic extract inhibits oncogene expression and suppresses DMH-induced preneoplastic lesions of the colon in F344 rats through an anti-inflammatory pathway. J Agric Food Chem 58: 7616-7623 https://doi.org/10.1021/jf101084e
  9. Etzerodt T, Nielsen ST, Mortensen AG, Christophersen C, Fomsgaard IS (2006) Elucidating the transformation pattern of the cereal allelochemical 6-methoxy-2-benzoxazolinone (MBOA) and the trideuteriomethoxy analogue [$D_{3}$]-MBOA in soil. J Agric Food Chem 54: 1075-1085 https://doi.org/10.1021/jf0509052
  10. Han AR, Kang U, Kil YS, Lee J, Seo EK (2015) Identification of Two New Lactams from the Hulled Seeds of Coix lachryma-jobi var. ma-yuen. Bull Korean Chem Soc 36: 2401-2403 https://doi.org/10.1002/bkcs.10456
  11. Han AR, Kil YS, Kang U, Youn IS, Choi G, Lee YJ, Nam JW, Lee JH, Hong J, Lee SK, Seo EK (2013) Identification of a New Fatty Acid from the Seeds of Coix lachryma-jobi var. ma-yuen. Bull Korean Chem Soc 34: 1269-1271 https://doi.org/10.5012/bkcs.2013.34.4.1269
  12. Hill HZ, Li W, Xin P, Mitchell DL (1997) Melanin: a two edged sword? Pigment Cell Res 10: 158-161 https://doi.org/10.1111/j.1600-0749.1997.tb00478.x
  13. Hong SS, Choi CW, Choi YH, Oh JS (2016) Coixlachryside A: A new lignan glycoside from the roots of Coix lachryma-jobi L. var. ma-yuen Stapf. Phytochemistry Lett 17: 152-157 https://doi.org/10.1016/j.phytol.2016.07.004
  14. Hwang JY, Park TS, Son JH (2013) Whitening effect of extracts and fractions from Diospyros kaki calyx. J Life Sci 23: 377-382 https://doi.org/10.5352/JLS.2013.23.3.377
  15. Jin KS, Oh YN, Park JA, Lee JY, Jin S, Hyun SK, Hwang HJ, Kwon HJ, Kim BW (2012) Anti-oxidant, anti-melanogenic, and anti-inflammatory activities of Zanthoxylum schinifolium Extract and its Solvent Fractions. Korean J Microbiol Biotechnol 40: 371-379 https://doi.org/10.4014/kjmb.1207.07023
  16. Kamperdick C, Lien TP, Sung TV, Adam G (1997) 2-hydroxy-2H-1,4-benzoxazin-3-one from Scoparia dulcis. Pharmazie 52: 965-966
  17. Kim JD (2012) Literature on the Quality and Effect of Job's Tears. Korean Journal of Agricultural History 11: 89-122
  18. Kim KH, Kim HK, Choi SU, Moon E, Kim SY, Lee KR (2011) Bioactive lignans from the rhizomes of Acorus gramineus. J Nat Prod 74: 2187-2192 https://doi.org/10.1021/np200541m
  19. Kim SY, Choi CW, Hong SS, Shin H, Oh JS (2016) A new neolignan from Coix lachryma-jobi var. mayuen. Nat Prod Commun 11: 229-231
  20. Kobayashi T, Urabe K, Winder AJ, Jimenez-Cervantes C, Imokawa G, Brewington T, Solano F, Garcia-Borron JC, Hearing VJ (1994) Tyrosinase related protein-1 (TRP-1) function as a DHICA oxidase in melanin biosynthesis. EMBO J 3: 5818-5825
  21. Kuo CC, Chen HH, Chiang W (2012) Adlay (薏苡 yi yi ; "soft-shelled job's tears"; the seeds of Coix lachryma-jobi L. var. ma-yuen Stapf) is a potential cancer chemopreventive agent toward multistage carcinogenesis processes. J Tradit Complement Med 2: 267-275 https://doi.org/10.1016/S2225-4110(16)30112-2
  22. Lee MY, Lin HY, Cheng F, Chiang W, Kuo YH (2008) Isolation and characterization of new lactam compounds that inhibit lung and colon cancer cells from adlay (Coix lachryma-jobi L. var. ma-yuen Stapf) bran. Food Chem Toxicol 46: 1933-1939 https://doi.org/10.1016/j.fct.2008.01.033
  23. Lee SY, Choi SU, Lee JH, Lee DU, Lee KR (2010) A new phenylpropane glycoside from the rhizome of Sparganium stoloniferum. Arch Pharm Res 33: 515-521 https://doi.org/10.1007/s12272-010-0404-1
  24. Nagao T, Otsuka H, Kohda H, Sato T, Yamasaki K (1985) Benzoxazinones from Coix lachryma-jobi var. ma-yuen. Phytochemistry 26: 2959-2962
  25. Otsuka H, Hirai Y, Nagao T, Yamasaki K (1988) Anti-inflammatory activity of benzoxazinoids from roots of Coix lachryma-jobi var. ma-yuen. J Nat Prod 51: 74-79 https://doi.org/10.1021/np50055a009
  26. Otsuka H, Takeuchi M, Inoshiri S, Sato T, Yamasaki K (1989) Phenolic compounds from Coix lachryma-jobi var. ma-yuen. Phytochemistry 28: 883-886 https://doi.org/10.1016/0031-9422(89)80136-0
  27. Prota G (1988) Progress in the chemistry of melanins and related metabolites. Med Res Rev 8: 525-556 https://doi.org/10.1002/med.2610080405
  28. Song MY, Jung HW, Park YK (2016) Antiobesity effect of water extract of Coix lachrymajobi var. mayuen in high fat fed C5BL/6 Mice. J Korean Med Obes Res 16: 27-35 https://doi.org/10.15429/jkomor.2016.16.1.27
  29. Takahashi M, Konno C, Hikino H (1986) Isolation and hypoglycemic activity of coixans A, B and C, glycans of Coix lachryma-jobi var. ma-yuen seeds. Planta Med 52: 64-65 https://doi.org/10.1055/s-2007-969074
  30. Wang L, Chen C, Su A, Zhang Y, Yuan J, Ju X (2016) Structural characterization of phenolic compounds and antioxidant activity of the phenolic-rich fraction from defatted adlay (Coix lachryma-jobi L. var. ma-yuen Stapf) seed meal. Food Chem 196: 509-517 https://doi.org/10.1016/j.foodchem.2015.09.083
  31. Yi B, Hu L, Mei W, Zhou K, Wang H, Luo Y, Wei X, Dai H (2011) Antioxidant phenolic compounds of cassava (Manihot esculenta) from Hainan. Molecules 16: 10157-10167 https://doi.org/10.3390/molecules161210157