반하(Pinellia ternata)에서의 [6]-gingerol 함량과 멜라닌 저해 활성에 영향을 미치는 원산지 판별 마커로의 활용 = Utilization of [6]-gingerol as an origin discriminant marker influencing melanin inhibitory activity relative to its content in Pinellia ternata

국문 초록 (Abstract)

반하(Pinellia ternata Breitenbach)는 천남성과(Araceae)의 약용식물로 동아시아 일대가 원산지이며, 유럽과 북아메리카 일부지역에도 널리 분포하고 있는 식물이다. 반하의 괴경(tuber)은 약재로 사용되어 구토, 염증, 외상을 치료하는 목적으로 사용되고 있다. 보고된 약리학적 작용으로는 항경련, 항종양, 살충, 세포독성 등이 있는 것으로 알려져 있다. 반하는 약리학적으로 유용한 약용식물로 잘 알려져 있음에도 불구하고, 원산지를 판별할 수 있는 신뢰성이 있고 표준화된 방법이 없는 실정이다. 이를 위한 한국산과 중국산 반하를 판별할 수 있는 유의적인 화합물을 탐색하기 위해 UPLC-PDA와 QTof-MS에 기반을 둔 대사체 표지법을 이용하였다. 한국산으로부터 원산지 판별 화합물로 예상되는 화합물을 반복적인 역상 칼럼크로마토그래피에 기반을 둔 활성유도 분획법을 통해 분리하였다. 그리고, NMR과 MS를 포함한 물리화학적, 분광학적 정보의 결과를 토대로 [6]- gingerol이라는 화합물의 구조를 동정하였다. [6]-gingerol은 원산지를 판별할 수 있는 능력과 melanin 생합성 저해 활성을 지닌 기능성 화장품 소재로서 가치가 있다고 판단되어짐에 따라 유효성분 원산지 판별 화합물로 Fingerprint법에 의해 선정되었다. 더욱이, 한국산과 중국산 반하 유래 [6]-gingerol의 함량 비교를 위해, 유효성이 검증된 분석법을 이용하여 이에 대한 검량곡선을 작성하여 그 함량을 비교하였다. 이것은 한국산 반하판별을 위한 화합물 선정과 성공적인 유효성 검증을 다룬 최초의 보고이다.

다국어 초록 (Multilingual Abstract)

Pinellia ternata Breitenbach, the natural medicinal plant of the Araceae family, is a perennial plant originated from the East Asia, but also widely distributed in Europe and North America. Its tuber is used as traditional medicine for treatment of various diseases such as vomiting, inflammation, and traumatic injury. Pharmacological studies revealed that P. ternata possesses anticonvulsant, anti-tumor, insecticidal, and cytotoxic activities. Despite being well-known as the useful medicinal plant, there is no reliable, standardized method for origin discrimination. Ultra performance liquid chromatography-photodiode array detector and quadrupole time of flight-mass spectrometry based metaboliteprofiling was applied to explore significant metabolite for origin discrimination between Korean and Chinese P. ternata. One compound was isolated from Korean P. ternata using repeated ODS column chromatography by bioactivity guided fractionation, and determined as [6]-gingerol according to the results of spectroscopic data including nuclear magnetic resonance and MS. This compound was selected as cosmeceutical biomarker by fingerprints, and it was associated to melanin inhibitory effect determining its origin authenticity. Furthermore, the calibration curve of biomarker was prepared using validated method for the comparison of content between Korean and Chinese P. ternata. This is the report to address the selection and successful validation of the discriminant metabolite for confirmation of Korean P. ternata.

참고문헌 (Reference)

1 전명제, "톳(Hizikia fusiformis) 에탄올 추출물 및 분획물의 미백활성" 한국생명과학회 22 (22): 889-896, 2012

2 김기옥, "우슬의 뿌리로부터 Phytoecdysones의 분리와 항 아토피 효과" 한국응용생명화학회 58 (58): 13-19, 2015

3 Ji X, "The ethnobotanical, phytochemical and pharmacological profile of the genus Pinellia" 93 : 1-17, 2014

4 Ali BH, "Some phytochemical, pharmacological and toxicological properties of ginger (Zingiber officinale Roscoe): a review of recent research" 46 : 409-420, 2008

5 Peng ZS, "Rapid propagation of the medicinal plant Pinellia ternata by in vitro leaves culture" 13 : 1-6, 2007

6 Zuo Z, "Purification and characterization of a novel plant lectin from Pinellia ternata with antineoplastic activity" 16 : 1-, 2012

7 Chen JH, "Pinelloside, an antimicrobial cerebroside from Pinellia ternata" 64 : 903-906, 2003

8 Nagai T, "Oral adjuvant activity for nasal influenza vaccines caused by combination of two trihydroxy fatty acid stereoisomers from the tuber of Pinellia ternata" 10 : 655-661, 2010

9 Zhang ZH, "Metabonomic study of biochemical changes in the rat urine induced by Pinellia ternata (Thunb.) Berit" 85 : 186-193, 2013

10 Huang HC, "Inhibitory effect of [6]-gingerol on melanogenesis in B16F10 melanoma cells and a possible mechanism of action" 75 : 1067-1072, 2011

11 Kim SH, "Imports & Exports of Biopharmaceuticals & Herbal Medicine, etc., vol 17" Ministry of food and drug safety 380-387, 2015

12 Kim SH, "IgEmediated occupational asthma induced by herbal medicine, banha (Pinellia ternata)" 31 : 779-781, 2001

13 Hyuk-Hwan Song, "Discrimination of white ginseng origins using multivariate statistical analysis of data sets" 고려인삼학회 38 (38): 187-193, 2014

14 Chung HS, "Determination of the site of origin of Pinellia ternata roots based on RAPD analysis and PCR-RFLP" 136 : 126-129, 2002

15 Ju Sin Kim, "Cytotoxic Components from the Dried Rhizomes of Zingiber officinale Roscoe" 대한약학회 31 (31): 415-418, 2008

16 Iwasa M, "Chemical composition and major odor-active compounds of essential oil from Pinellia tuber (dried rhizome of Pinellia ternata) as crude drug" 63 : 127-135, 2014

17 Jiang H, "Characterization of gingerol-related compounds in ginger rhizome (Zingiber officinale Rosc.)by high-performance liquid chromatography/electrospray ionization mass spectrometry" 19 : 2957-2964, 2005

18 Gonda R, "Characterization of an acidic polysaccharide with immunological activities from the tuber of Pinellia ternata" 17 : 1549-1553, 1994

19 Kim YJ, "Anti-obesity effect of Pinellia ternata extract in zucker rats" 29 : 1278-1281, 2006

20 Ahmed S, "Anti-emetic effects of bioactive natural products" 4 : 390-433, 2013

21 Song HH, "A metabolomics approach to identify factors influencing their activity relative to oleanolic acid contents in Korean mistletoe types" 22 : 64-72, 2016