Studies on color change of seed coat of edible beans during maturation

• Project/Area Number: 18H02146
• Research Category: Grant-in-Aid for Scientific Research (B)
• Allocation Type: Single-year Grants
• Section: 一般
• Review Section: Basic Section 38040:Bioorganic chemistry-related
• Research Institution: Nagoya University
• Principal Investigator: YOSHIDA Kumi 名古屋大学, 情報学研究科, 教授 (90210690)
• Co-Investigator(Kenkyū-buntansha): 尾山 公一 名古屋大学, 物質科学国際研究センター, 技師 (80402460)
• Project Period (FY): 2018-04-01 – 2022-03-31
• Project Status: Completed (Fiscal Year 2021)
• Budget Amount: ¥17,550,000 (Direct Cost: ¥13,500,000、Indirect Cost: ¥4,050,000); Fiscal Year 2021: ¥2,470,000 (Direct Cost: ¥1,900,000、Indirect Cost: ¥570,000); Fiscal Year 2020: ¥3,250,000 (Direct Cost: ¥2,500,000、Indirect Cost: ¥750,000); Fiscal Year 2019: ¥2,860,000 (Direct Cost: ¥2,200,000、Indirect Cost: ¥660,000); Fiscal Year 2018: ¥8,970,000 (Direct Cost: ¥6,900,000、Indirect Cost: ¥2,070,000)
• Keywords: Vigna angularis / Glycinbe max / Glycine soja / catechinopyranocyanidin / cyanidin 3-glucoside / 2-flavenol / anthocyanin biosynthesis / Glycine max / delphinidin 3-O-glcoside / アントシアニン / 赤小豆 / 黒ダイズ / 色素前駆体 / flav-2-en-3-ol 3-O-glc / anthocyanidin synthase / 黒大豆 / Catehinopyranocyanidin / Photo-degraded compd. / cis-leucocyanidin / 小豆 / シアニジン3-グルコシド / 色素生合成 / Gycine max / catehinopyranocyanidin / purple pigment / seed-coat pigment / 紫色色素

Outline of Final Research Achievements

We conducted a research on the unexplored mechanism of pigmentation in colored edible beans: one was red adzuki beans (Vigna angularis) and the other was black soybeans (Glycine max). Matured small red beans contain almost no anthocyanins, and the chemical structure of the pigment responsible for azuki color in an-paste was unknown. The new pigments, catechinopyranocyanidins A and B, were isolated from the seed coat, and their complete structures, including chiral cetres, were determined. On the other hand, seed coat pigment of the black soybean is cyanidin 3-glucoside (Cy3G), which is the most abundant pigment in plants. Inspired by the phenomenon that the seed coat turns black within a day after the immature green bean is removed from the pod, we found a new biosynthetic pathway for Cy3G. In the immature seed coat, a colorless precursor, glycosylated flavanol compound was already contained and this is rapidly converted to give Cy3G.

Academic Significance and Societal Importance of the Research Achievements

赤小豆の種皮色素は、その赤色から長い間アントシアニンであると誤解されてきた。実際、食品化学の教科書などにもアントシアニンであるとの記載がなされていた。今回、糖を含まない水にほとんど溶けない紫色色素のカテキノピラノシアニジン類が明らかになったことで、その誤解が解かれ、製餡加工工程における餡の紫色着色の科学的解明が進む。
また、黒大豆の種皮色素において、従来教科書に記載されていた生合成経路と異なる新しい生合成経路が見つかり、今後、アントシアニンの生合成研究の不明点などの解明が進む。

Research Products

• [Int'l Joint Research] FCT-UNL(ポルトガル)
• [Int'l Joint Research] Avignon University(フランス)
• [Int'l Joint Research] SISSA(イタリア)
• [Int'l Joint Research] UC Davis/MARS/The Ohio State University(米国)
• [Int'l Joint Research] Institut Ruder Boskovic(クロアチア)
• [Int'l Joint Research] New University of Lisbon/University of Porto(ポルトガル)
• [Int'l Joint Research] New University of Lisbon(ポルトガル)
• [Journal Article] Crystallization of a Membrane Protein from <i>Hydrangea macrophylla</i> Involving in Aluminum Tolerance (2021)
  • Author(s): 伊藤誉明、中林由香里、入江克雅、大嶋篤典、藤吉好則、吉田久美
  • Journal Title: SPring-8/SACLA Research Report Volume: 9 Issue: 6 Pages: 380-382
  • DOI: 10.18957/rr.9.6.380
  • NAID: 130008112299
  • ISSN: 2187-6886
  • Year and Date: 2021-10-29
  • Peer Reviewed
• [Journal Article] Insight into chemical mechanisms of sepal color development and variation in hydrangea (2021)
  • Author(s): YOSHIDA Kumi、OYAMA Kin-ichi、KONDO Tadao
  • Journal Title: Proceedings of the Japan Academy, Series B Volume: 97 Issue: 2 Pages: 51-68
  • DOI: 10.2183/pjab.97.003
  • NAID: 130007983360
  • ISSN: 0386-2208, 1349-2896
  • Year and Date: 2021-02-10
  • Peer Reviewed / Open Access
• [Journal Article] Discovery of a natural cyan blue: A unique food-sourced anthocyanin ccould replace synthetic brilliant blue. (2021)
  • Author(s): Denish, P. R., Fenger, J-A., Powers, R., Sigurdson, G. T., Grisanti, L., Guggenheim, K. G., Laporte, S., Li, J., Kondo, T., Magistrato, A., Moloney, M. P., Riley, M., Rusishvili, M., Ahmadiani, N., Baroni, S., Dangles, O., Giusti, M., Collins, T. M., Didzbalis, J., Yoshida, K., Siegel, J. B., Robbins, R. J.
  • Journal Title: Sci. Advances Volume: 7 Issue: 15
  • DOI: 10.1126/sciadv.abe7871
  • Peer Reviewed / Open Access / Int'l Joint Research
• [Journal Article] Polyacylated anthocyanins in bluish-purple petals of Chinese bellflower, Platycodon grandiflorum. (2021)
  • Author(s): Kondo, T., Hagihara, S., Takaya, Y., Yoshida, K.
  • Journal Title: Int. J. Mol. Sci. Volume: 22 Issue: 8 Pages: 4044-4044
  • DOI: 10.3390/ijms22084044
  • Peer Reviewed / Open Access
• [Journal Article] Protecting group-free method for synthesis of N-glycosyl carbamates and an assessment of the anomeric effect of nitrogen in the carbamate group (2021)
  • Author(s): Ichikawa Yoshiyasu、Kaneno Daisuke、Saeki Nobuyoshi、Minami Takahiro、Masuda Toshiya、Yoshida Kumi、Kondo Tadao、Ochi Rika
  • Journal Title: Carbohydrate Research Volume: － Pages: 108280-108280
  • DOI: 10.1016/j.carres.2021.108280
  • Peer Reviewed
• [Journal Article] アジサイの花色の謎を解く、ようやく明らかになった青色色素の構造と色の変わるしくみ (2021)
  • Author(s): 吉田久美
  • Journal Title: 月刊化学 Volume: 76 Pages: 23-28
  • NAID: 40022592207
• [Journal Article] フラボノイド系植物色素の化学ー最近の話題を中心に (2021)
  • Author(s): 吉田久美
  • Journal Title: 色材誌 Volume: 94 Pages: 263-269
  • NAID: 130008107248
  • Peer Reviewed
• [Journal Article] Blue flower coloration of Corydalis ambigua requires ferric ion and kaempferol glycoside (2021)
  • Author(s): Yoshida Kumi、Oniduka Takeya、Oyama Kin-ichi、Kondo Tadao
  • Journal Title: Bioscience, Biotechnology, and Biochemistry Volume: 85 Issue: 1 Pages: 61-68
  • DOI: 10.1093/bbb/zbaa022
  • Peer Reviewed / Int'l Joint Research
• [Journal Article] Determination of absolute configuration of photo‐degraded catechinopyranocyanidin A by modified Mosher's method (2020)
  • Author(s): Oyama Kin‐ichi、Kondo Tadao、Shimizu Toshimichi、Yoshida Kumi
  • Journal Title: Chirality Volume: 32 Issue: 5 Pages: 556-563
  • DOI: 10.1002/chir.23202
  • NAID: 120006869623
  • Peer Reviewed / Open Access
• [Journal Article] The peculiarity of malvidin 3-O-(6-O-p-coumaroyl) glucoside aggregation. Intra and intermolecular interactions (2020)
  • Author(s): Mendoza Johan、Oliveira Joana、Ara?jo Paula、Bas?lio Nuno、Teixeira Nat?rcia、Br?s Nat?rcia F.、Pina Fernando、Yoshida Kumi、de Freitas Victor
  • Journal Title: Dyes and Pigments Volume: 179 Pages: 108382-108382
  • DOI: 10.1016/j.dyepig.2020.108382
  • Peer Reviewed / Open Access / Int'l Joint Research
• [Journal Article] Determination of anthocyanins and antioxidants in ‘Titanbiscus’ edible flosers in vitro and in vivo. (2020)
  • Author(s): Chensom, S., Shimada, Y., Nakayama, H., Yoshida, K., Kondo, T., Kasuzaki, H., Hasegawa, S., Mishima,T.
  • Journal Title: Plant Food Human Nutr. Volume: 75 Issue: 2 Pages: 265-271
  • DOI: 10.1007/s11130-020-00813-3
  • Peer Reviewed / Open Access
• [Journal Article] 5,7,3’,4’-Tetrahydroxyflav-2-en-3-ol 3-O-glucoside, a new biosynthetic precursor of cyanidin 3-O-glucoside in the seed coat of black soybean, Glycine max (2020)
  • Author(s): Yoshida Kumi、Teppabut Yada、Sawaguchi Reo、Nakane Yuhsuke、Hayashi Emi、Oyama Kin-ichi、Nishizaki Yuzo、Goda Yukihiro、Kondo Tadao
  • Journal Title: Scientific Reports Volume: 10 Issue: 1 Pages: 17184-17184
  • DOI: 10.1038/s41598-020-74098-6
  • Peer Reviewed / Open Access / Int'l Joint Research
• [Journal Article] Conversion of flavonol glycoside to anthocyanin: an interpretation of the oxidation?reduction relationship of biosynthetic flavonoid-intermediates (2019)
  • Author(s): Oyama Kin-ichi、Kimura Yuki、Iuchi Satoru、Koga Nobuaki、Yoshida Kumi、Kondo Tadao
  • Journal Title: RSC Advances Volume: 9 Issue: 54 Pages: 31435-31439
  • DOI: 10.1039/c9ra06986k
  • Peer Reviewed / Open Access
• [Journal Article] Formation of an Aluminum Complex of 5-O-Caffeoylquinic Acid with Chiral Molecular Stacking under Vacuolar Condition (2019)
  • Author(s): Yoshida Kumi、Ito Daisuke、Kondo Tadao
  • Journal Title: HETEROCYCLES Volume: 99 Issue: 2 Pages: 1322-1322
  • DOI: 10.3987/com-18-s(f)47
  • Peer Reviewed / Open Access
• [Journal Article] Direct mapping of hydrangea blue-complex in sepal tissues of Hydrangea macrophylla (2019)
  • Author(s): T. Ito, D. Aoki, K. Fukushima, K. Yoshida
  • Journal Title: Scientific Reports Volume: 9 Issue: 1 Pages: 5450-5450
  • DOI: 10.1038/s41598-019-41968-7
  • Peer Reviewed / Open Access
• [Journal Article] 小豆の赤色はアントシアニンではない！？種皮から餡の紫色を担う新規の色素を発見 (2019)
  • Author(s): 吉田久美
  • Journal Title: 化学74 Volume: 74 Pages: 24-28
• [Journal Article] Structure of two purple pigments, catechiopyranocyanidins A and B from the seed-coat of the small red bean, Vigna angularis (2019)
  • Author(s): Yoshida Kumi、Nagai Nobukazu、Ichikawa Yoshiki、Goto Miki、Kazuma Kohei、Oyama Kin-ichi、Koga Kazushi、Hashimoto Masaru、Iuchi Satoru、Takaya Yoshiaki、Kondo Tadao
  • Journal Title: Scientific Reports Volume: 9 Issue: 1 Pages: 1484-1484
  • DOI: 10.1038/s41598-018-37641-0
  • Peer Reviewed / Open Access
• [Journal Article] Red cabbage anthocyanins: The influence of d-glucose acylation by hydroxycinnamic acids on their structural transformations in acidic to mildly alkaline conditions and on the resulting color (2018)
  • Author(s): Moloney Micheal、Robbins Rebecca J.、Collins Tom M.、Kondo Tadao、Yoshida Kumi、Dangles Olivier
  • Journal Title: Dyes and Pigments Volume: 158 Pages: 342-352
  • DOI: 10.1016/j.dyepig.2018.05.057
  • Peer Reviewed
• [Journal Article] Direct Observation of Hydrangea Blue-Complex Composed of 3-O-Glucosyldelphinidin, Al3+ and 5-O-Acylquinic Acid by ESI-Mass Spectrometry (2018)
  • Author(s): Ito Takaaki、Oyama Kin-ichi、Yoshida Kumi
  • Journal Title: Molecules Volume: 23 Issue: 6 Pages: 1424-1424
  • DOI: 10.3390/molecules23061424
  • Peer Reviewed / Open Access
• [Journal Article] Change of Petals′ Color and Chemical Components in Oenothera Flowers during Senescence (2018)
  • Author(s): Teppabut Yada、Oyama Kin-ichi、Kondo Tadao、Yoshida Kumi
  • Journal Title: Molecules Volume: 23 Issue: 7 Pages: 1698-1698
  • DOI: 10.3390/molecules23071698
  • Peer Reviewed / Open Access
• [Journal Article] DFT/TD-DFT calculations of the electronic and optical properties of bis-N,N-dimethylaniline-based dyes for use in dye-sensitized solar cells (2018)
  • Author(s): El-Meligy Asmaa B.、Koga Nobuaki、Iuchi Satoru、Yoshida Kumi、Hirao Kimihiko、Mangood Ahmed H.、El-Nahas Ahmed M.
  • Journal Title: Journal of Photochemistry and Photobiology A: Chemistry Volume: 367 Pages: 332-346
  • DOI: 10.1016/j.jphotochem.2018.08.036
  • Peer Reviewed
• [Presentation] 様々な品種のアズキ種皮に含まれる色素の分析． (2022)
  • Author(s): 吉田久美、高山陽子、浅野友世、萩原星児
  • Organizer: 日本農芸化学会2022年度大会
• [Presentation] ツルマメの登熟過程における種皮成分の変化の分析 (2022)
  • Author(s): 仁瓶栞里、杉田千恵子、吉野奈津子、近藤忠雄、吉田久美
  • Organizer: 日本農芸化学会2022年度大会
• [Presentation] 外部標準法定量NMR（EC-qNMR）によるアントシアニン市販試薬の純度測定 (2022)
  • Author(s): 西﨑雄三、建部千絵、吉田久美、杉本直樹、佐藤恭子
  • Organizer: 日本農芸化学会2022年度大会
• [Presentation] A new biosynthetic intermediate of cyanidin 3-O-glucoside in black soybean seed coat (2021)
  • Author(s): Kumi Yoshida, Yada Teppabut, Reo Sawaguchi, Kin-ichi Oyama, Tadao Kondo
  • Organizer: ICP2020 Turk
  • Int'l Joint Research
• [Presentation] アントシアニンを用いた食品着色料の可能性 (2021)
  • Author(s): 吉田久美
  • Organizer: ifia JAPAN2021 (第26回国際食品素材/添加物展・会議)／HFE JAPAN2021(第19回ヘルスフードエキスポ)
  • Invited
• [Presentation] アントシアニンを用いた青色着色料の可能性 (2021)
  • Author(s): 吉田久美
  • Organizer: 愛知県立明和高等学校SSH理科特別講座
  • Invited
• [Presentation] フラボノイド系色素の化学と生物学 (2021)
  • Author(s): 吉田久美
  • Organizer: 理化学研究所 環境資源科学研究センター－千葉大学植物分子科学研究センター植物科学ジョイントセミナー
  • Invited
• [Presentation] 黒ダイズ種皮におけるシアニジン 3-O -グルコシドの新規生合成経路 (2021)
  • Author(s): 澤口 玲央、古川 楓、和氣 駿之、テッパブット ヤダー、中根 悠輔、林 英美、尾山 公一、杉田 千恵子、近藤 忠雄、中山 亨、吉田 久美
  • Organizer: 第63回天然有機化合物討論会
• [Presentation] 赤小豆中のカテキノピラノシアニジンA,Bの定量分析 (2021)
  • Author(s): 高山 陽子、数馬 恒平、吉田 久美
  • Organizer: 日本農芸化学会2021年度大会
• [Presentation] 鉄イオンとフラボノールが関与するエゾエンゴサク青色花弁の発色機構 (2020)
  • Author(s): 吉田久美、鬼塚丈矢、尾山公一、近藤忠雄
  • Organizer: 第62回天然有機化合物討論会
• [Presentation] キキョウ花弁に含まれる青紫色素の単離と構造決定 (2020)
  • Author(s): 萩原星児、近藤忠雄、吉田久美
  • Organizer: 日本農芸化学会2021年度大会
• [Presentation] Chemical studies on pigments in various colored beans’ seed-coat (2019)
  • Author(s): Yoshida, K.
  • Organizer: 2019年度中日小豆学術交流会
  • Int'l Joint Research / Invited
• [Presentation] MS analysis of hydrangea blue-complex pigment and its direct mapping in sepals of Hydrangea macrophylla. (2019)
  • Author(s): Ito, T., Aoki, D., Fukushima, K., Kondo, T., Yoshida, K.
  • Organizer: International Workshop on Anthocyanins
  • Int'l Joint Research
• [Presentation] Anthocyanin and non-anthocyanin pigments from colored seed coat of edible beans. (2019)
  • Author(s): Yoshida, K.
  • Organizer: The 9th International Conference on Polyphenols and Health
  • Int'l Joint Research / Invited
• [Presentation] フラブ-2-エン-3-オール 3-O-グルコシドの合成とアントシアニンの生合成解明を目指した分析法の研究 (2019)
  • Author(s): 澤口怜央、中根悠輔、林英美、近藤忠雄、吉田久美
  • Organizer: 日本農芸化学会関西・中部支部2019年度合同神戸大会
• [Presentation] 赤アズキ種皮色素、カテキノピラノシアニジンA光分解物の新モッシャー法による絶対立体配置の確認 (2019)
  • Author(s): 清水俊順、尾山公一、近藤忠雄、吉田久美
  • Organizer: 日本農芸化学会関西・中部支部2019年度合同神戸大会
• [Presentation] 赤アズキ種皮に含まれ餡に移行する紫色色素の絶対立体配置の決定． (2019)
  • Author(s): 吉田久美, 井内哲, 橋本勝, 清水俊順,永井伸和,近藤忠雄
  • Organizer: 日本農芸化学会2019年度大会
• [Presentation] Two Novel purple pigments, catechinopyranocyanidin A and B, from red adzuki bean, Vigna angularis. (2018)
  • Author(s): Yoshida, K.,;Nagai, N.,;Ichikawa, Y.,;Kazuma, K.,;Koga, K.,;Kondo, T.
  • Organizer: XXIX International Conference on Polyphenols
  • Int'l Joint Research
• [Presentation] Chemical analysis on blue supramolecular metal-complex composed with delphinidin-3-O-glucoside in hydrangea sepal. (2018)
  • Author(s): Ito, T., Oyama, K-I., Yoshida, K.
  • Organizer: XXIX International Conference on Polyphenols
  • Int'l Joint Research
• [Presentation] Mechanism of petal color change of Oenothera flowers during secescence by chemical analysis of flavonoid content. (2018)
  • Author(s): Teppabut, Y., Oyama, K-I., Kondo, T., Yoshida, K.
  • Organizer: XXIX International Conference on Polyphenols
  • Int'l Joint Research
• [Remarks] Yoshida Laboratory
  • URL: http://www.info.human.nagoya-u.ac.jp/lab/yoshida/index.html
• [Remarks] アントシアニンの新規生合成経路を黒豆で発見 黒大豆の枝豆は、莢から出すと１日で真っ黒になる
  • URL: https://www.nagoya-u.ac.jp/about-nu/public-relations/researchinfo/upload_images/20201015_i1.pdf
• [Remarks] Peeking into the pods of black soybeans
  • URL: https://en.nagoya-u.ac.jp/research/activities/news/2020/12/peeking-into-the-pods-of-black-soybeans.html
• [Remarks] 黒大豆種皮のシアニジン3-グルコシドの新しい生合成経路を見つけました
  • URL: http://www.info.human.nagoya-u.ac.jp/lab/yoshida/index.html
• [Remarks] 小豆の色素について月刊化学に寄稿しました
  • URL: http://www.info.human.nagoya-u.ac.jp/lab/yoshida/index.html
• [Remarks] 小豆の赤色の正体とは？&#8212;新たな色素「カテキノピラノシアニジン」の化学構造
  • URL: https://academist-cf.com/journal/?p=10616
• [Remarks] 赤小豆種皮に含まれる紫色色素の論文が公開されました
  • URL: http://www.info.human.nagoya-u.ac.jp/lab/yoshida/index.html
• [Patent(Industrial Property Rights)] 小豆餡の製造方法 (2020)
  • Inventor(s): 吉田久美、川原美香
  • Industrial Property Rights Holder: 名古屋大学、とかち財団
  • Industrial Property Rights Type: 特許
  • Filing Date: 2020