Formation of Porphyrin Fiber and Control of Its Electronic Process by Photon Injection

卟啉纤维的形成及其电子过程的光子注入控制

基本信息

批准号：
11650935
负责人：
KOMATSU Teruyuki
金额：
$ 1.41万
依托单位：
Waseda University
依托单位国家：
日本
项目类别：
Grant-in-Aid for Scientific Research (C)
财政年份：
1999
资助国家：
日本
起止时间：
1999 至 2000
项目状态：
已结题

项目摘要

In order to revive the dioxygen-coordination ability of the self-organized lipidporphyrinatoiron assemblies, two non-enzymatic systems to reduce the oxidized ferric metal centers have been constructed, and their mechanisms were studied.First, a new lipidporphyrin with a covalently bound axial imidazole has been synthesized. It was self-organized in aqueous media to give fibrous aggregate (10 nm width). The AFM measurement in liquid phase revealed that four porphyrin molecules continuously aligned at the fiber's core, which can reversibly bind and release dioxygen under physiological conditions. The resonance Raman spectroscopy showed the coordination structure of the dioxygen, and the dioxygen-binding affinity and dioxygen association and dissociation rate constants were also measured.Photoirradiation of phospholipid vesicle embedding lipidporphyrinatoiron(III) and lipidporphyrinato-zinc(II) (30-40 nmφ) induced electron transfer from the excited zinc(II) center to the Fe(III) complex. Under the coexistence of triethanolamine, the ratio of the ferrous complex increased and it can bind dioxygen.On the other hand, saline solution of lipidporphyrinatoiron(III) showed a ligand-to-metal charge transfer (LMCT) absorption band at 362 nm. Under the presence of small amount of saccharides (hyaluronic acid, glucose, etc.), LMCT irradiation (365 nm) led to reduction of the central ferric iron(III), giving ferrous high-spin complex. This photoreduction involves fast intramolecular electron transfer, and the saccharide itself is oxidized to prevent the back electron transfer reaction. The result of the laser-flash photolysis showed that the formation of the ferrous high-spin complex occurred within 100 ns. The obtained Fe(II) complex formed a stable dioxygen adduct complex.Furthermore, this photoreduction system could be applied to the albumin-porphyrinatoiron(III) hybrid, in which albumin played the role of the electron donner.

为了恢复自组织的脂磷脂铁组装的二氧化量配合能力，已经构建了两个非酶系统以减少氧化的铁金属中心，它们的机制是研究的。首先是一种新的脂肪蛋白，并具有轴向型的新型型纤维蛋白，并具有轴向的膜源。聚集体（10 nm宽）。液相的AFM测量表明，四个卟啉分子继续在纤维的核心处排列，在生理条件下可以可逆地结合并释放二氧化物。共振拉曼光谱法显示了二恶英的配位结构，还测量了二氧结合亲和力和二恶英的关联和解离速率常数。磷脂囊泡嵌入脂源性孢子虫（III II）和lipidporpphyrinphyrinato-Zinc（II III）（III）（III）（II）（III）（II）（III）（II）（III）（II）（II）（II）（II）（II）（III）（II）（激发锌（ii）中心至Fe（III）复合物。在三乙醇胺的共存下，亚铁络合物的比率增加，另一方面可以结合二恶英。脂源性孢子虫（III）的盐溶液显示出362 Nm处的配体和金属电荷转移（LMCT）吸收带。在存在少量糖（透明质酸，葡萄糖等）的存在下，LMCT辐射（365 nm）导致中央铁（III）的减少，从而使黑色的高旋转络合物复合物。该光电传递涉及快速分子内电子转移，糖本身被氧化以防止后电子转移反应。激光闪烁光解的结果表明，亚铁高旋转络合物的形成发生在100 ns之内。获得的Fe（II）配合物形成了稳定的二氧化加合成络合物。曲线，该光塑性系统可以应用于专辑por-porphyrinatoiron（III）混合动力，在该专辑中，专辑中发挥了Electronic Donner的作用。