Synthesis of polyacylated anthocyanins and functional analysis of supramolecular metal-complexes involved in blue flower color development

• Project/Area Number: 18K05457
• Research Category: Grant-in-Aid for Scientific Research (C)
• Allocation Type: Multi-year Fund
• Section: 一般
• Review Section: Basic Section 38040:Bioorganic chemistry-related
• Research Institution: Nagoya University
• Principal Investigator: Oyama Kin-ichi 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: ¥4,420,000 (Direct Cost: ¥3,400,000、Indirect Cost: ¥1,020,000); Fiscal Year 2021: ¥650,000 (Direct Cost: ¥500,000、Indirect Cost: ¥150,000); Fiscal Year 2020: ¥1,300,000 (Direct Cost: ¥1,000,000、Indirect Cost: ¥300,000); Fiscal Year 2019: ¥910,000 (Direct Cost: ¥700,000、Indirect Cost: ¥210,000); Fiscal Year 2018: ¥1,560,000 (Direct Cost: ¥1,200,000、Indirect Cost: ¥360,000)
• Keywords: 多アシル化アントシアニン / 青色超分子金属錯体色素 / 配糖化フラボノール / グルコシル化反応 / ESI-MS / 酸化反応 / ミリセチン / 質量分析 / 青色花色発現 / 超分子金属錯体 / ケルセチン / 相関移動触媒 / フラボノイド / 超分子 / 分子認識

Outline of Final Research Achievements

Synthetic method of flavonol glycosides as a precursor of polyacylated anthocyanin was investigated and then the myricetin glycoside of the precursor of platyconin was synthesized. Syntheses of anthocyanins from flavonol glycosides and acylated flavonol glycosides using Zn reduction and air oxidation method were conducted. In addition, ESI-MS analysis of a variety of blue supramolecular metal-complexes from flowers and synthetic pigments were performed. First observation of hydrangea blue-complex using ESI-MS was achieved.

Academic Significance and Societal Importance of the Research Achievements

多アシル化アントシアニンは、天然にありふれた植物色素であり、ヒトの生活に深く関与しているにもかかわらず、確立した合成方法がない。植物中の複雑な混合物から純粋なサンプルを得ることは極めて困難であり、合成によるサンプル供給が強く求められている。本研究では、多アシル化アントシアニンの自在合成法の確立を目指して合成研究を行った。また、多アシル化アントシアニンが関与する生物有機化学的研究として、質量分析を用いた青い花の超分子金属錯体色素の構造の詳細や安定性の解明の研究も行った。

Research Products

• [Journal Article] Synthesis and characterization of methoxybenzene-linked polyimides formed by 1,4-addition to bismaleimides (2022)
  • Author(s): Hor Seanghai、Oyama Kin-ichi、Koga Nobuaki、Tsukamoto Masaki
  • Journal Title: Polymer Volume: 238 Pages: 124326-124326
  • DOI: 10.1016/j.polymer.2021.124326
  • 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] Bronsted acid-catalyzed 1,4-addition of 1,3,5-trimethoxybenzene to maleimides and acrylates (2021)
  • Author(s): Hor Seanghai、Oyama Kin-ichi、Koga Nobuaki、Tsukamoto Masaki
  • Journal Title: Tetrahedron Letters Volume: 74 Pages: 153100-153100
  • DOI: 10.1016/j.tetlet.2021.153100
  • 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] 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] 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] 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] 植物ポリフェノール有機合成研究の今と昔 -革新的反応が生み出す新しい合成戦略- (2019)
  • Author(s): 尾山公一
  • Journal Title: 化学と生物 Volume: 57 Pages: 463-471
  • NAID: 130007883279
  • Peer Reviewed
• [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] 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] アジサイの花色変異の謎を解く (2018)
  • Author(s): 吉田久美, 伊藤誉明, 尾山公一
  • Journal Title: Foods & Food Ingredients J. Jpn. Volume: 223 Pages: 231-240
  • NAID: 40021670176
• [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] 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] エゾエンゴサクの青色花弁に含まれる鉄錯体アントシアニンの化学研究 (2020)
  • Author(s): 吉田 久美, 鬼塚 丈矢, 尾山 公一, 近藤 忠雄
  • Organizer: 日本農芸化学会2020年度 (令和2年度)
• [Presentation] キキョウ花弁に含まれる多アシル化アントシアニン, プラチコニンの全合成研究 (2020)
  • Author(s): 尾山公一, 清水 俊順, 柴 康太, 近藤忠雄, 吉田久美
  • Organizer: 日本農芸化学会2020年度 (令和2年度)
• [Presentation] フラボノールの還元反応を用いた多アシル化アントシアニンの合成研究 (2019)
  • Author(s): 柴康太・尾山公一・近藤忠雄・吉田久美
  • Organizer: 日本化学会第99春季年会(2019)
• [Presentation] アントシアニン-フラボン連結型色素の合成と色素増感太陽電池への応用研究 (2019)
  • Author(s): 酒井勇輔・尾山公一・若宮淳志・近藤忠雄・吉田久美
  • Organizer: 日本化学会第99春季年会(2019)
• [Presentation] アジサイの花色を担う青色超分子錯体の組成と構造 (2018)
  • Author(s): 伊藤誉明、尾山公一、青木弾、福島和彦、吉田久美
  • Organizer: 第60回天然有機化合物討論会