UPLC-DAD-QTOF/MS를 이용한 대추나무(Zizyphus jujuba var. inermis (Bunge) Rehder) 잎과 열매의 플라보노이드 배당체 분석

이민기,김헌웅,김영진,이선혜,장환희,정현아,김숙배,이성현,최정숙,김정봉 한국식품저장유통학회 2016 한국식품저장유통학회지 Vol.23 No.7

Flavonoids, non-nutrient secondary metabolites of plants, are widely distributed in commonly consumed agro-food resources. Flavonoids include aglycones, and their glycosides are reported to have potential health-promoting compounds. The aim of this study was to investigate flavonoid glycosides in the fruit and leaves of Zizyphus jujuba var. inermis (Bunge) Rehder (jujube). A total of six flavonoids (five flavonols and one chalcone) were identified in jujube fruit and leaves by using ultra-performance liquid chromatography-diode array detector-quadrupole time of flight mass spectrometry along with chemical library and an internal standard. In positive ion mode, six flavonoids were linked to the C- and O-glycosides which were conjugated with sugar moieties based on kaempferol, quercetin, and phloretin aglycones. Total flavonoid contents of leaves (8,356.5 mg/100 g dry weight (DW)) was approximately 900-fold higher than that of fruit (fresh fruit, 13.6 mg/100 g dry DW; sun-dried fruits, 9.2 mg/100 g dry DW). Quercetin 3-O-rutinoside (rutin) and quercetin 3-O-robinobioside were the predominant flavonols in fruit and leaves of jujube. In particular, rutin had the highest content (6,735.2 mg/100 g DW) in leaves, and rutin is a widely reported bioactive compound. Phloretin 3',5'-di-C-glucoside (chalcone type) was detected only in leaves. The leaves of jujube contain a high content of flavonoids and the results of this study indicate that jujube leaves may be a source of bioactive flavonoids.

Differential Effects of Quercetin and Quercetin Glycosides on Human α7 Nicotinic Acetylcholine Receptor-Mediated Ion Currents

Lee, Byung-Hwan,Choi, Sun-Hye,Kim, Hyeon-Joong,Jung, Seok-Won,Hwang, Sung-Hee,Pyo, Mi-Kyung,Rhim, Hyewhon,Kim, Hyoung-Chun,Kim, Ho-Kyoung,Lee, Sang-Mok,Nah, Seung-Yeol The Korean Society of Applied Pharmacology 2016 Biomolecules & Therapeutics(구 응용약물학회지) Vol.24 No.4

Quercetin is a flavonoid usually found in fruits and vegetables. Aside from its antioxidative effects, quercetin, like other flavonoids, has a various neuropharmacological actions. Quercetin-3-O-rhamnoside (Rham1), quercetin-3-O-rutinoside (Rutin), and quercetin-3-(2(G)-rhamnosylrutinoside (Rham2) are mono-, di-, and tri-glycosylated forms of quercetin, respectively. In a previous study, we showed that quercetin can enhance ${\alpha}7$ nicotinic acetylcholine receptor (${\alpha}7$ nAChR)-mediated ion currents. However, the role of the carbohydrates attached to quercetin in the regulation of ${\alpha}7$ nAChR channel activity has not been determined. In the present study, we investigated the effects of quercetin glycosides on the acetylcholine induced peak inward current ($I_{ACh}$) in Xenopus oocytes expressing the ${\alpha}7$ nAChR. $I_{ACh}$ was measured with a two-electrode voltage clamp technique. In oocytes injected with ${\alpha}7$ nAChR copy RNA, quercetin enhanced $I_{ACh}$, whereas quercetin glycosides inhibited $I_{ACh}$. Quercetin glycosides mediated an inhibition of $I_{ACh}$, which increased when they were pre-applied and the inhibitory effects were concentration dependent. The order of $I_{ACh}$ inhibition by quercetin glycosides was Rutin${\geq}$Rham1>Rham2. Quercetin glycosides-mediated $I_{ACh}$ enhancement was not affected by ACh concentration and appeared voltage-independent. Furthermore, quercetin-mediated $I_{ACh}$ inhibition can be attenuated when quercetin is co-applied with Rham1 and Rutin, indicating that quercetin glycosides could interfere with quercetin-mediated ${\alpha}7$ nAChR regulation and that the number of carbohydrates in the quercetin glycoside plays a key role in the interruption of quercetin action. These results show that quercetin and quercetin glycosides regulate the ${\alpha}7$ nAChR in a differential manner.

Flavonoids의 항산화 활성과 미생물 복귀돌연변이에 영향을 미치는 구조적 요인 분석

이진영,김현주,이유영,김미향,한나래,강문석 한국식품과학회 2023 한국식품과학회지 Vol.55 No.4

This study identified the structural flavonoid factors influencing their antioxidant activity and bacterial mutagenicity. The 2,2-diphenyl-1-picrylhydrazyl (DPPH) and 2,2'-azino-bis(3-ethylbenzothiazoline-6-sulphonic acid) (ABTS) radical scavenging activities of the flavonoids were within the ranges of 162.20–917.54 μM and 68.03-2286.04 μM, respectively. Epigallocatechin gallate (EGCg) showed the highest activity in DPPH and ABTS activities, while EGC, quercetin, and myricetin exhibited superior activity to other flavonoids. Quercetin, myricetin, and kaempferol concentrationdependently produced over twice as many revertants as the control. Flavonoid antioxidant activity and mutagenicity commonly increased with B-ring hydroxylation and decreased with C3 glycosylation and B-ring conjugation. Various interacting structures, including C2=C3 double bonds and a 4-oxo structure, influenced the DPPH radical scavenging activity and mutagenicity. In contrast, the ABTS radical scavenging activity was critically influenced by the number of hydroxyl groups in the aglycone.

Differential Effects of Quercetin and Quercetin Glycosides on Human α7 Nicotinic Acetylcholine Receptor-Mediated Ion Currents

이병환,최선혜,김현중,정석원,황성희,표미경,임혜원,김형춘,김호경,이상목,나승열 한국응용약물학회 2016 Biomolecules & Therapeutics(구 응용약물학회지) Vol.24 No.4

Quercetin is a flavonoid usually found in fruits and vegetables. Aside from its antioxidative effects, quercetin, like other flavonoids, has a various neuropharmacological actions. Quercetin-3-O-rhamnoside (Rham1), quercetin-3-O-rutinoside (Rutin), and quercetin- 3-(2(G)-rhamnosylrutinoside (Rham2) are mono-, di-, and tri-glycosylated forms of quercetin, respectively. In a previous study, we showed that quercetin can enhance α7 nicotinic acetylcholine receptor (α7 nAChR)-mediated ion currents. However, the role of the carbohydrates attached to quercetin in the regulation of α7 nAChR channel activity has not been determined. In the present study, we investigated the effects of quercetin glycosides on the acetylcholine induced peak inward current (IACh) in Xenopus oocytes expressing the α7 nAChR. IACh was measured with a two-electrode voltage clamp technique. In oocytes injected with α7 nAChR copy RNA, quercetin enhanced IACh, whereas quercetin glycosides inhibited IACh. Quercetin glycosides mediated an inhibition of IACh, which increased when they were pre-applied and the inhibitory effects were concentration dependent. The order of IACh inhibition by quercetin glycosides was Rutin≥Rham1>Rham2. Quercetin glycosides-mediated IACh enhancement was not affected by ACh concentration and appeared voltage-independent. Furthermore, quercetin-mediated IACh inhibition can be attenuated when quercetin is co-applied with Rham1 and Rutin, indicating that quercetin glycosides could interfere with quercetin-mediated α7 nAChR regulation and that the number of carbohydrates in the quercetin glycoside plays a key role in the interruption of quercetin action. These results show that quercetin and quercetin glycosides regulate the α7 nAChR in a differential manner.

Differential Effects of Quercetin and Quercetin Glycosides on Human α7 Nicotinic Acetylcholine Receptor-Mediated Ion Currents

( Byung Hwan Lee ),( Sun Hye Choi ),( Hyeon Joong Kim ),( Seok Won Jung ),( Sung Hee Hwang ),( Mi Kyung Pyo ),( Hyewhon Rhim ),( Hyoung Chun Kim ),( Ho Kyoung Kim ),( Sang Mok Lee ),( Seung Yeol Nah ) 한국응용약물학회 2016 Biomolecules & Therapeutics(구 응용약물학회지) Vol.24 No.4

Quercetin is a flavonoid usually found in fruits and vegetables. Aside from its antioxidative effects, quercetin, like other flavonoids, has a various neuropharmacological actions. Quercetin-3-O-rhamnoside (Rham1), quercetin-3-O-rutinoside (Rutin), and quercetin- 3-(2(G)-rhamnosylrutinoside (Rham2) are mono-, di-, and tri-glycosylated forms of quercetin, respectively. In a previous study, we showed that quercetin can enhance α7 nicotinic acetylcholine receptor (α7 nAChR)-mediated ion currents. However, the role of the carbohydrates attached to quercetin in the regulation of α7 nAChR channel activity has not been determined. In the present study, we investigated the effects of quercetin glycosides on the acetylcholine induced peak inward current (IACh) in Xenopus oocytes expressing the α7 nAChR. IACh was measured with a two-electrode voltage clamp technique. In oocytes injected with α7 nAChR copy RNA, quercetin enhanced IACh, whereas quercetin glycosides inhibited IACh. Quercetin glycosides mediated an inhibition of IACh, which increased when they were pre-applied and the inhibitory effects were concentration dependent. The order of IACh inhibition by quercetin glycosides was Rutin≥Rham1>Rham2. Quercetin glycosides-mediated IACh enhancement was not affected by ACh concentration and appeared voltage-independent. Furthermore, quercetin-mediated IACh inhibition can be attenuated when quercetin is co-applied with Rham1 and Rutin, indicating that quercetin glycosides could interfere with quercetin-mediated α7 nAChR regulation and that the number of carbohydrates in the quercetin glycoside plays a key role in the interruption of quercetin action. These results show that quercetin and quercetin glycosides regulate the α7 nAChR in a differential manner.

홍차를 첨가하여 제조한 화이트 와인에 함유된 5종 Flavonoid의 분리 및 동정

조정용,손경현,현숙희,마승진,김선재,문제학,박근형 한국차학회 2014 한국차학회지 Vol.20 No.1

홍차를 첨가하여 제조한 홍차 화이트 와인에 catechin류와 theflavin류 외에 유용 화합물을 분자수준에서 구명하였다. 즉 홍차 화이트 와인으로부터 ethanol을 제거한 후의 수용액을 용매분획하여 얻어진 EtOAc층으로부터 ODS opencolumn chromatochraphy와 ODS-HPLC에 의해 5종의 화합물들을 분리하였다. 분리된 화합물들은 NMR 및 MS 분석을 통해 quercetin 3-O-β-D-galactopyranoside (1), quercetin 3-O-β-D-glucopyranoside (2), kaempferol 3-O-β-D-glucopyranoside (3), kaempferol 3-O-β-D-galactopyranoside (4), 2,3-trans-dihydrokaempferol (5)로 동정되었다. 홍차 화이트 와인으로부터 동정된 5종의 flavonoid류는 발효균주를 달리하여 제조한 홍차 화이트 와인 모두에 존재하고 있었으며, 그 중 화합물 2과 3은 비교적 높은 함량을 나타냈다. 홍차 화이트 와인으로부터 동정된 5종 화합물의 함량을 합한 총 flavnoid 함량은 발효균주 간에 통계학적으로 의미있는 차이를 보이지 않았다. 그리고 본 연구를 통해 홍차 화이트 와인에는 catechin류, theaflavin류 외에 5종의 flavonoid류들도 함유되어 있음이 확인되었다. 본 연구 결과는 홍차 및 그 응용제품의 성분 연구에 기초자료로 활용되길 기대한다. Five flavonoids were purified and isolated from white wine prepared with the addition of black tea (BTWW) by octadecylsilane (ODS) open column chromatography and high performance liquid chromatography (HPLC). The compounds were identified as quercetin 3-O-β-D-galactopyranoside (1), quercetin 3-O-β-Dglucopyranoside (2), kaempferol 3-O-β-D-glucopyranoside (3), kaempferol 3-O-β-D-galactopyranoside (4), and 2,3- trans-dihydrokaempferol (5), based on mass spectrometry and nuclear magnetic resonance analysis. The BTWWs were prepared with green grape juice containing 2.5% (w/v) black tea using three Saccharomyces strains and the five flavonoids identified were qualified and quantified by ODS-HPLC analysis. All five flanovoids (1-5) were detected in the BTWWs with compounds 2 and 3 having the highest content among them. The contents of compounds 1 and 2 showed significant differences among the BTWWs prepared by three strains, but the other flavonoids (3-5) and their total flavonoid contents were similar. These results suggest that the 5 flavonoids in BTWWs would be increased by the addition of black tea.

Flavonoid constituents in the leaves of Myrica rubra sieb. et zucc. with anti-inflammatory activity

김한혁,Dong-Hee Kim,김많흔,오명환,김소라,박광준,이민원 대한약학회 2013 Archives of Pharmacal Research Vol.36 No.12

The leaves of Myrica rubra sieb. et zucc. havebeen used in oriental traditional medicine for the treatmentof burns, skin diseases, and as an antidiarrheal in China,Japan, and Korea. Activity guided isolation of the leaves ofM. rubra has led to the isolation of five flavonoid: myricetin(1), myricitrin (2), myricetin 3-O-(200-O-galloyl)-a-L-rhamnopyranoside (3), myricetin 3-O-(200-O-galloyl)-b-D-galactopyranoside (4), and quercetin 3-O-(200-O-galloyl)-b-D-galactopyranoside (5). All isolates were evaluatedfor their antioxidant potency against the superoxideanion (O2-), and compounds 3–5 showed potent scavengingactivities with 50 % inhibition concentration (IC50)values compared to the positive control, allopurinol. Compounds 1–5 were evaluated as inhibitors of variousmacrophage functions involved in the inflammatory process. These five compounds significantly and dose dependentlyinhibited lipopolysaccharide (LPS)-stimulated nitricoxide (NO), pro-inflammatory cytokines, and the proteinlevels of inducible nitric oxide synthase (iNOS) andcyclooxygenase-2 (COX-2) in LPS-stimulated RAW 264.7macrophages. Our results suggest that galloyl flavonolglycosides (3–5) isolated from M. rubra might be beneficialfor the treatment of inflammation-related diseases.

Flavonoids Glycosides frcm the Fronds of Pyrrosia lingua

Do, Jea Chul,Jung, Keun Young,Son, Kun Ho 영남대학교 약품개발연구소 1993 영남대학교 약품개발연구소 연구업적집 Vol.3 No.-

Two flavonoid glycosides, astragalin(1) and liquiritin(2), were isolated from the fronds of Pyrrosia lingua.

산처리에 의한 적양파 분말의 quercetin 배당체와 aglycone의 농도변화

김미령(Mi-Ryung Kim),임준형(Jun-Hyung Lim),송지수(Ji-Su Song) 한국식품과학회 2022 한국식품과학회지 Vol.54 No.2

열풍건조로 제조된 껍질을 포함한 적양파 분말은 강력한 항산화제인 플라보노이드 함량이 생양파즙에 비해 약 22배로 고농도로 농축되어 있으며, 60-70% ethanol 농도에서 70℃, 2시간 추출 시 가장 높은 수율을 나타내었다. 이때 추출된 플라보노이드의 함량은 DPPH radical 소거능과 상관계수 0.877의 높은 상관관계를 나타내었다. 적양파 분말의 플라보이드는 주로 quercetin 배당체인 Q3,4G, Q4G와 QA로 이루어져 있으며, 15:39:47의 비율로 구성되어 있었다. 염산, 젖산, 초산 등 다양한 종류의 산처리에 의해 적양파 분말 속 quercetin 배당체는 QA로 전환될 수 있었으며 저농도 초산용액에서 QA로 전환되는 비율이 높았다. 이는 적양파 분말에 포함된 glucosidase가 저농도 산용액에서 활성화되면서 일어나는 반응으로 사료되었다. 초산 처리초기에는 diglycoside인 Q3,4G의 de-glycosylation이 급격히 일어났으며, 초산처리 6시간 이후에는 Q4G의 분해와 함께 QA가 증가하여 24시간 경과 후에 최대 QA의 함량에 도달하였으며, QA의 증가는 DPPH radical 소거능과 유의적인 상관성(r=0.90)을 나타내어 생리활성의 증가를 나타내었다. 본 연구결과, 양파의 주요 플라보노이드인 quercetin 배당체는 저농도 초산 처리로 빠르고 간편하게 QA로 전환이 가능하였으며, 이와 더불어 생리활성의 증가도 도모할 수 있었다. 적양파 분말을 이용하여 저농도 산처리를 통하여 QA로의 전환률을 높이면, 고농도의 quercetin을 함유한 양파 소재의 개발이 가능할 것이며, 이를 통해 기능성 양파 가공품의 개발로 이어질 수 있을 것이다. Flavonoids are bioactive plant metabolites that have a range of beneficial effects on human health. Quercetin 4′-glycoside (Q4′G), quercetin 3,4′-diglycoside (Q3,4′G), and quercetin aglycone (QA) are the main flavonoids found in onions. QA, in particular, is likely to have a greater biological effect than glycosides. To develop an onion extract with high quercetin content, the optimal extraction conditions for red onion powder containing the outer layer of the onion were determined. The effects of acid treatment on the concentration of quercetin glycosides and QA were evaluated. The flavonoids of red onion powder were optimally extracted under 60-70% ethanol at 70℃ for 2 h. The deglycosylation of Q3,4′G and an increase in Q4′G content occurred within 6 h of 0.2% acetic acid treatment. The QA content and deglycosylation of Q4′G eventually peaked at 24 h. In addition, QA content and 2,2-diphenyl-1-picrylhydrazyl (DPPH) radical scavenging activity were highly correlated, with a correlation coefficient of 0.90.

Stepwise Synthesis of Quercetin Bisglycosides Using Engineered Escherichia coli

( Gyu Sik Choi ),( Hyeon Jeong Kim ),( Eun Ji Kim ),( Su Jin Lee ),( Youngshim Lee ),( Joong-hoon Ahn ) 한국미생물생명공학회(구 한국산업미생물학회) 2018 Journal of microbiology and biotechnology Vol.28 No.11

Synthesis of flavonoid glycoside is difficult due to diverse hydroxy groups in flavonoids and sugars. As such, enzymatic synthesis or biotransformation is an approach to solve this problem. In this report, we used stepwise biotransformation to synthesize two quercetin bisglycosides (quercetin 3-O-glucuronic acid 7-O-rhamnoside [Q-GR] and quercetin 3-Oarabinose 7-O-rhamnoside [Q-AR]) because quercetin O-rhamnosides contain antiviral activity. Two sequential enzymatic reactions were required to synthesize these flavonoid glycosides. We first synthesized quercetin 3-O-glucuronic acid [Q-G], and quercetin 3-Oarabinose [Q-A] from quercetin using E. coli harboring specific uridine diphopsphate glycosyltransferase (UGT) and genes for UDP-glucuronic acid and UDP-arabinose, respectively. With each quercetin 3-O-glycoside, rhamnosylation using E. coli harboring UGT and the gene for UDP-rhamnose was conducted. This approach resulted in the production of 44.8 mg/l Q-GR and 45.1 mg/l Q-AR. This stepwise synthesis could be applicable to synthesize various natural product derivatives in case that the final yield of product was low due to the multistep reaction in one cell or when sequential synthesis is necessary in order to reduce the synthesis of byproducts.