Studies on Structural Analysis of Molecular Association of Flower Pigments, Anthocyanins

花色素、花青素分子缔合结构分析研究

• 批准号: 04640525
• 负责人: KONDO Tadao
• 金额: $ 1.41万
• 依托单位: Nagoya University
• 依托单位国家: 日本
• 项目类别: Grant-in-Aid for General Scientific Research (C)
• 财政年份: 1992
• 资助国家: 日本
• 起止时间: 1992 至 1993
• 项目状态: 已结题
• 来源: https://kaken.nii.ac.jp/en/grant/KAKENHI-PROJECT-04640525/
• 关键词: anthocyanin; molecular association; strucutral analysis; color variation; stability; commelinin; protocyanin; X-ray crystallography; 金属錯体; 構造決定; 再合成; 発色発現

Commelinin is a real pigment of blue petals of Commelina communis and a metal-complex involving self-association and copigmentation. We obtained it as a pure pigment by reconstruction from the components, malonylawobanin (M), flavocommelin (F) and magnesium ion. By reconstruction experiments of the commelinin-like pigments by replacement of the components the metal-coordination position was determined. The exact structural analysis was succeeded by ^1H NMR,CD and atomic analyzes followed by X-ray crystallographic analysis using synchrotoron radiation. M and M,and F and F are stacking each other in face-to-face in left-handed screw and M and F is in right-handed manner. The gross strucutre is cyclo-MMFFMMFFMMFF.The association is due to hydrophobic interaction of the aromatic nuclei. The blue color development is due to the 4'-keto anhydrobase anion of the anthocyanidin nucleus arising from metal chelation.Protocyanin is a real pigment from blue corn flower, Centaurea cyanus. We first detrmined the exact molecular weight by ESI-mass, and established the composition by reconstruction from components, succinylcyanin (Sc), malonylflavone (Mf), Fe^<3+> and Mg^<2+> tobe [Sc_6Mf_6Fe^<3+>Mg^<2+>].We first succeeded in exact structural elucidation of real flower pigment and put a period of controversy of metal-complex theory during 70 years.

Commelinin是Commelina communis蓝色花瓣中的一种真实色素，是一种涉及自结合和共色素的金属络合物。由丙二酰洛巴宁(M)、黄科美林(F)和镁离子组成，重组得到纯色素。通过置换组分对类石粉颜料进行重构实验，确定了金属配位位置。精确的结构分析是继1H核磁共振、CD和原子分析之后，再用同步辐射进行x射线晶体学分析。M和M， F和F以左旋方式面对面堆叠，M和F以右旋方式堆叠。总结构是环- mmffmmffmmff。这种结合是由芳香核的疏水相互作用引起的。由于金属螯合作用，花青素核的4′-酮型无氢阴离子形成蓝色。原花青素是一种真正的色素，来自蓝色玉米花Centaurea cyanus。我们首先用ESI-mass法确定了其确切的分子量，并通过对三种组分（Sc）、丙二醇黄酮（Mf）、Fe^<3+>和Mg^<2+>)的重构确定了其组成[Sc_6Mf_6Fe^<3+>Mg^<2+>]。我们首次成功地对真正的花色素进行了精确的结构解析，使金属配合物理论陷入了长达70年的争论。

项目成果

Tsukasa Mori, Miei Sakurai, Jun-ichi Shigeta, Kumi Yoshida, Tadao Kondo: "Formation of Anthocyanins from Cells Cultured from Different Parts of Strawberry Plants" Journal of Food Science. 58. 788-792 (1993)

Tsukasa Mori、Miei Sakurai、Jun-ichi Shigeta、Kumi Yoshida、Tadao Kondo：“从草莓植物不同部位培养的细胞中形成花青素”食品科学杂志。

Kumi Yoshida, Kiyoshi Kameda, Tadao Kondo: "Diglucuronoflavones from Purple Leaves of Perilla ocimodes" Phytochemistry. 33. 917-919 (1993)

Kumi Yoshida、Kiyoshi Kameda、Tadao Kondo：“紫苏紫叶中的二葡萄糖醛酸黄酮”植物化学。

Tadao Kondo, Kumi Yoshida, Atsushi Nakagawa Takatoshi Kawai, Hirotoshi Tamura, Toshio Goto: "Structural Basis of Blue-Color Development in Flower Petals from Commelina communis" Nature. 358. 515-518 (1992)

Tadao Kondo、Kumi Yoshida、Atsushi Nakakawa Takatoshi Kawai、Hirotoshi Tamura、Toshio Goto：“鸭跖草花瓣蓝色发育的结构基础”自然。

Tsukasa Mori: "Fromation of Anthocyanins from Cells Cultured from Different Parts of Strawberry Plants" Journal of Food Science. 58. 788-792 (1993)

Tsukasa Mori：“草莓植物不同部分培养的细胞中花青素的形成”食品科学杂志。

Tadao Kondo, Kumi Yoshida: "Mechanism for Blue Flower-Color Development : Structural Determination of commelinin from Blue Petals of Commerina communis" Polyphenols Actualites. 10. 2-21 (1994)

Tadao Kondo、Kumi Yoshida：“蓝花颜色形成机制：鸭跖草蓝色花瓣中鸭跖草素的结构测定”多酚现状。