Elucidation of Structure and Function of Photosynthetic Antenna by Model Study

Synthesis of Novel Chlorophyllous PigmentsNovel 3イイD11イエD1-hydroxy-13イイD11イエD1-oxo-chlorins possessing various substituents at 3イイD11イエD1-，7-，8-，13イD12イエD1-，17イD14イエD1-and 20-positions and their metal complexes were prepared by modification of naturally occurring chlorophylls. 2.人造氯细胞组合成金属氯化合物的制备，以自我聚合在非极有机溶剂中给予任何寡聚体。一个有机的解决方案，一个固体薄膜和固体粉末的解决方案。通过几种光谱技术对所得分子的超分子结构进行了调查，并指示在分子轴中沿着羟基、酮组和中心金属的线性取向，需要形成高顺序的超分子分子，以及镁，锌和镉作为中央金属对自我聚合的影响，所有的自我聚合主要由13-C =... H（3-CHR）O... M和π-π染色色素的相互作用，是一种很好的结构模型，用于自然染色体、光合成绿色细菌的外红天线。外围物质对分子的超分子结构产生了轻微的影响，但并没有改变框架。作为一种去除的、合成颜料在微小细胞中自我聚合的羟基球中的一个明确的解决方案。当一个细菌氯林动力学被添加到一个明确的解决方案中，聚体的光激发能量被转移到添加的细菌氯林，指示体外自我聚合是一个很好的功能模型，用于自然氯林组与人工氯林组的自然氯林组的比较自然氯林组与自然氯林组的比较自然氯林组的自然氯林组颜料受到不同同源性的制约。这并不说明自然系统中的同源性是如何自我聚合的。在体外自我聚合的合成颜料的体内自我聚合提供了任何信息，以获得体内自我聚合的机制。

Synthesis of Novel Chlorophyllous PigmentsNovel 3ィイD11ィエD1-hydroxy-13ィイD11ィエD1-oxo-chlorins possessing various substituents at 3ィイD11ィエD1-,7-,8-,13ィイD12ィエD1-,17ィイD14ィエD1-and 20-positions and their metal complexes were prepared by modification of naturally occurring chlorophylls.2. Preparation of Artificial ChlorosomesSynthetic metal-chlorins self-aggregated to give any oligomers in non-polar organic solvents. aqueous organic solution, aqueous solutions of detergents, solid thin films and solid powders. Supramolecular structures of the resulting oligomers were investigated by several spectroscopic techniques, indicating that a linear orientation among the hydroxy, keto groups and central metal along the Qy-axis in the molecule is requisite for formation of highly ordered supramolecules and also that magnesium, zinc and cadmium as the central metal were effective for the self-aggregation.All the self-aggregates were built-up mainly by 13-C=・・・H(3-CHR)O・・・M and π-πinteraction of the chlorin chromophores, which are good structural models for natural chlorosomes, extramembranous antennae of photosynthetic green bacteria. Peripheral substituents affected slightly the supramolecular structures of the oligomers, but did not change the framework.In an aqueous solution of a detergent, synthetic pigments self-aggregated at the hydrophobic sphere in the micelle. When a chromophore of a bacteriochlorin moiety was added to the aqueous solution, photoexcited energy of the oligomers was transferred to the added bacteriochlorin, indicating the in vitro self-aggregates are good functional model for natural chlorosomes.Comparison of Natural Chlorosomes with Artificial ChlorosomesNatural chlorophyllous pigments are consisted of several the homologues. It is not unclear how the homologues self-aggregate in the natural systems. In vitro self-aggregation of synthetic pigments gave any information for the mechanism of in vivo self-aggregation.