Effect of C7-Substituent on Self-Assembly of Chlorosomal Chlorophylls
Effect of C7-Substituent on Self-Assembly of Chlorosomal Chlorophylls
复制标题
C7-取代基对叶绿体叶绿素自组装的影响
DOI：
10.1080/10610270108027468
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发表时间：
2001
影响因子：
3.3
通讯作者：
H. Tamiaki
中科院分区：
文献类型：
--
作者：
T. Oba;H. Tamiaki
摘要 合成了在 C71 位上具有一系列大取代基 OMe、OCOMe 和 OCO t Bu 的细菌叶绿素 d 类似物（甲基 71-取代-3-(1-羟基甲基)焦脱镁叶绿酸 a 的锌配合物）。将这些颜料的聚集行为与天然型化合物 (C71-H) 进行比较，以阐明 C71 部分的大小对二氢卟酚自组装的影响。这些 C71 取代的 Zn-二氢卟酚在 1% THF/己烷中形成自聚集体。聚集体给出了几乎相同的可见吸收带，尤其是约。 2000-cm−1 红移 Qy 峰；光谱与天然型二氢锌 (C71-H) 的光谱基本相似。所有C71取代化合物的聚集体在红移Qy区域都显示出相似的激子型CD对，这与C71-H Zn-二氢卟酚聚集体的对的特征不同。这些光谱数据表明，C71 部分并未中断二氢卟酚分子之间的分子间键合，而是改变了影响长程手性的超分子结构。
Abstract Bacteriochlorophyll d analogues that possessed a series of bulky substituents of OMe, OCOMe, and OCO t Bu at the C71-position were synthesized (Zn-complexes of methyl 71-substituted-3-(1-hydroxy-methyl)pyropheophorbide a). Aggregation behavior of these pigments was examined in comparison with a natural-type compound (C71-H) to elucidate the effects of size of the C71-moiety on self-assembly of the chlorins. These C71-substituted Zn-chlorins formed self-aggregates in 1% THF/hexane. The aggregates gave almost the same visible absorption bands, especially a ca. 2000-cm−1 red-shifted Qy peak; the spectra were essentially similar to those of the natural-type Zn-chlorin (C71-H). All the aggregates of the C71-substituted compounds showed similar exciton-type CD couplets in the red-shifted Qy region, which were different from the feature of the couplet of the C71-H Zn-chlorin aggregate. These spectral data suggested that the C71-moiety did not interrupt the intermolecular linkages between chlorin molecules but altered the supramolecular structure which influences the long-range chirality.