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

Commelinin是一种真正的鸭茅蓝色花瓣色素，是一种涉及自缔合和共色的金属络合物。通过对丙二醛(M)、黄连蛋白(F)和镁离子的重组，得到了一种纯色素。通过对类粘连素色素进行组份置换重建实验，确定了金属配位位置。用~1H核磁共振、圆二色谱和原子分析进行了精确的结构分析，并用同步辐射进行了X-射线晶体分析。M和M，F和F在左手螺丝中面对面堆叠，M和F在右手方式下堆叠。大体结构为环-MMFFMMFFMMFF，这种缔合是由于芳香族原子核之间的疏水相互作用造成的。蓝色的显色是由于金属络合产生的花青素核的4‘-酮基阴离子所致。原蓝蛋白是一种来自蓝色玉米花--矢车菊的真正色素。我们首次用电喷雾电喷雾质谱(ESI-MS)测定了花色素的确切相对分子质量，并由琥珀酸蓝蛋白(SC)、丙二酸黄酮组分(MF)、铁组分[SC_6Mf_6Fe；2+&gt；3+&gt；mg^&lt；2+&gt；]等组分重构确定了其组成。

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.