天然色素アントシアニンの合成とその機能の解明

花色苷是一种天然色素，它的合成及其生物学功能的阐明花色苷是一种主要的花卉色素，可能具有多种生物学功能，如基因保护、防晒、杀虫、清除自由基等。我们以黄酮醇糖苷为原料合成了新的酰化花色苷(1)，并证明了其对DNA的保护作用(2)利用太阳光、UV-A和B对DNA进行了酰化花色苷(HBA)的保护。(1)通过金属还原反应，实现了芦丁及其衍生物直接转化为花色苷。采用不同的反应条件进行还原。芦丁用锌汞在3%的盐酸-甲醇中于0℃反应制得花青素3-芦丁糖苷，产率为24%。同时，以Ox(3E)5%的产率合成了相应的花色苷。用锌粉代替锌汞，以65%的产率合成了黄酮烯3芦丁糖苷。因此，我们找到了合成天然黄素-3-烯的新的有效途径。(2)我们提供了化学证据，证明三色通蓝花青素(HBA)具有紫外线A和B的遮光作用来保护DNA。用纤维素酶处理花瓣组织后分离的蓝色原生质体进行显微光度测定，证实HBA存在于花瓣上皮细胞的10-2M。我们建立了花瓣保护DNA免受紫外光照射的模型系统。用抗胸腺嘧啶核苷二聚体抗体用ELISA法分析DNA损伤情况。AQ的浓度(10-3M)。与活细胞相同的HBA溶液完全阻断了紫外光照射下的DNA损伤，表明开放花中的花青素具有保护基因免受日光照射的作用。

Synthesis of anthocyanin, a natural pigment, and clarification of its biological functionAnthocyanin is major flower pigment and might play role of amount biological functions such as gene protection form sunlight, entomophily, and radical scavenger. It is used for a food colorant and eye therapeutic medicine.We developed the new synthesis (1) of acylated anthocyanins from flavonol glycoside and proven protection (2) of DNA by acylated anthocyanin (HBA) from sunlight, UV-A and B.(1) We realized the direct transformation to anthocyanin from rutin and its derivatives, a flavonol glycoside by using metal reduction reaction. Various reaction conditions were applied to the reduction. Rutin was treated with Zn-Hg in absolute 3% HCl-methanol at 0℃ to give cyanidin 3-rutinoside in 24% yield. And also, perbenzoylrutins were reduced to afford the corresponding anthocyanin in Ox(3E)5% yield. Zn powder in replacing of Zn-Hg gave flav-3-ene 3-rutinoside in 65% yield. Therefore, we found the new efficient synthetic route to a natural flav-3-ene.(2) We provided chemical evidence that heavenly blue anthocyanin (HBA), a pigment of blue petal of Ipomoea tricolor, has a light shielding effect of UV-A and B to protect the DNA. That HBA exists at 10-2M in epidermis cell of the petal, was clarified by micro-photometery of a blue protoplast, which was isolated after treatment of the tissue with cellulase. We built up a model system of the petal for protection of DNA from UV-light exposure. The DNA damage was analyzed by ELISA method using antibody of thymidine dimers. The concentration (10-3M) of an aq. HBA solution just as that of living cell completely blocked the DNA damage under UV-irradiation, indicating that the anthocyanin pigment in open flower has a function of protection of the gene from sun-light.