Development of Porphyrinoid Materials Aimed at Non-linear Optics and Photodynamic Therapy

用于非线性光学和光动力治疗的类卟啉材料的开发

基本信息

批准号：
20850004
负责人：
SUZUKI Masaaki
金额：
$ 2.1万
依托单位：
Chiba University
依托单位国家：
日本
项目类别：
Grant-in-Aid for Young Scientists (Start-up)
财政年份：
2008
资助国家：
日本
起止时间：
2008 至 2009
项目状态：
已结题

项目摘要

Synthesis of novel porphyrinoids aimed at development of nonlinear optical materials or photodynamic therapy medicines had been started. At first, since unpredictable synthetic problems were found during the synthesis of oligo-pyrrole precursors according to the reported procedure, the reaction conditions were modified so that formation of byproducts was suppressed. In addition, a rare oligo-pyrrole unit bearing a pyridine ring that was difficult to introduce so far was synthesized. The target β-alkyl substituted hexaphyrin (1.1.1.1.1.1) was seemed to be unstable in free base and neutral state, so reproducibility of the reaction was very low and characterization had been carried out only in the protonated form to date. This time, the synthetic method was revised and the reaction intermediate was isolated before oxidized. As aresult, the final step of the purification was dramatically simplified and reproducibility of the reaction was raised. Furthermore, the quick working up made it possible to measure ^1H NMR spectrum of the neutral state of hexaphyrin. This observation revealed that two inner meso-protons of neutral hexaphyrin was pointing inward of the macrocycle in the similar maaner to the protonated form. Moreover, zinc complex of the hexaphyrin was more stable than the free base. This complex showed strong aromaticity and optical property analogous to porphyrin. This is the first example that maintains the inherent aromaticity of the parent molecule among zinc complexes of hexaphyrins (1.1.1.1.1.1) or general metalcomplexes of meso-free hexaphyrins (1.1.1.1.1.1). Good single crystals of the zinc complex suitable for X-ray analysis were obtained, but coordination with the other metals was not achieved. On the other hand, unique bis-BF_2 and bis-Rh(CO)_2 complexes of non-conjugated macrocyclic bis-dipyrrin units were synthesized using the isolated intermediate.

旨在开发非线性光学材料或光动力疗法药物的新型卟啉素的合成。首先，由于根据报告的程序在合成寡中前体的合成过程中发现了不可预测的合成问题，因此对反应条件进行了修改，从而抑制了副产物的形成。此外，合成了一个很难引入吡啶环的罕见的寡吡咯烷基单元。靶标β-烷基取代的六边形蛋白（1.1.1.1.1.1）在自由碱和中性态下似乎是不稳定的，因此反应的可重复性非常低，并且仅在迄今为止以质子化形式进行了表征。这次，修改了合成方法，并在氧化之前将反应中间体分离。纯化的最后一步也大大简化，并提高了反应的可重复性。此外，快速工作使得测量六边形蛋白中性状态的 ^1H NMR光谱是可能的。该观察结果表明，中性六边形蛋白的两个内中核子在与质子化形式相似的大型摩纳犬中指向大环的内部。此外，六边形蛋白的锌综合体比自由碱更稳定。该复合物表现出强烈的芳香性和类似于卟啉的光学特性。这是在六边形蛋白（1.1.1.1.1）锌复合物（1.1.1.1.1）中维持父分子的固有芳香性的第一个示例或无中无六边形蛋白（1.1.1.1.1.1）的一般金属复合物。获得了适合X射线分析的锌复合物的良好单晶，但没有与其他金属进行协调。另一方面，使用分离的中间体合成了独特的BIS-BF_2和BIS-RH（CO）_2非偶联的大环双吡啶单元的复合物。

项目成果

期刊论文数量（0）

专著数量（0）

科研奖励数量（0）

会议论文数量（0）

专利数量（0）

Application of the Perimeter Model to the Assignment of the Electronic Absorption Spectra of Gold(III)Hexaphyrins with[4n+2]and[4n]π-Electron Systems

周长模型在[4n+2]和[4n]π-电子体系金(III)六菲林电子吸收光谱归属中的应用

DOI：
发表时间：
2009
期刊：
Chemistry-A European Journal 15
影响因子：
0
作者：
A.Muranaka;O.Matsushita;K.Yoshida;S.Mori;M.Suzuki;T.Furuyama;M.Uchiyama;A.Osuka;N.Kobayashi
通讯作者：
N.Kobayashi

ヘムタンパク質の電子構造を解明するためのメソ13Cプローブ : ミオグロビンケース

用于阐明血红素蛋白电子结构的 Meso-13C 探针：肌红蛋白案例