Supramolecular Structure of Self-assembled Synthetic Zinc-131-oxo-chlorins Possessing a Primary, Secondary or Tertiary Alcoholic 31-Hydroxyl Group: Visible Spectroscopic and Molecular Modeling Studies¶
Supramolecular Structure of Self-assembled Synthetic Zinc-131-oxo-chlorins Possessing a Primary, Secondary or Tertiary Alcoholic 31-Hydroxyl Group: Visible Spectroscopic and Molecular Modeling Studies¶
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具有伯、仲或叔醇31-羟基基团的自组装合成锌-131-氧代-二氢卟酚的超分子结构：可见光谱和分子模型研究¶
DOI：
10.1562/0031-8655(2001)073
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发表时间：
2001
影响因子：
3.2
通讯作者：
H. Tamiaki
中科院分区：
文献类型：
--
作者：
S. Yagai;Tomohiro Miyatake;Yoshiyuki Shimono;H. Tamiaki
合成了含有31-叔羟基和13-酮基的锌-氯3（见图2），作为绿细菌天线叶绿素的模型。研究了3在非极性有机介质中的自聚集，并将其与1和2分别拥有一个一级和二级31-羟基进行了比较。氯化锌3在1 vol% CH2Cl2 -己烷中自聚集形成低聚物，与单体（CH2Cl2为648 nm）相比，在704 nm处表现出最大的红移Qy。该红移大于2S(648→697 nm)，与2R（648→705 nm）相当，但小于1(648→740 nm)，表明虽然单个31-甲基（prim-OH→秒- oh）抑制了接近和/或更高的聚集，但额外的31-甲基（秒- oh→叔- oh）没有进一步抑制聚集。通过可见光谱分析确定，团聚体的相对稳定性为1 > 2R ~ 3 >2s。对氯锌十二聚体1,2r和3的分子模拟计算得到了相似的有序能量最小化结构，而1比2R和3的堆叠更紧密。而2S则呈现出相对无序（扭曲）的结构。计算的十二元结构可以解释非极性有机介质中1-3的可见光谱数据。
Abstract Zinc-chlorin 3 (see Fig. 2 in text) possessing a tertiary 31-hydroxyl group and a 13-keto group was synthesized as a model for the antenna chlorophylls of green bacteria. Self-aggregation of 3 in nonpolar organic media was examined and compared to 1 and 2 possessing a primary and secondary 31-hydroxyl group, respectively. Zinc-chlorin 3 self-aggregated in 1 vol% CH2Cl2–hexane to form oligomers and showed a red-shifted Qy maximum at 704 nm compared to the monomer (648 nm in CH2Cl2). This red-shift is larger than that of 2S (648 → 697 nm) and comparable to that of 2R (648 → 705 nm), but smaller than that of 1 (648 → 740 nm), indicating that while a single 31-methyl group (prim-OH → sec-OH) suppressed close and/or higher aggregation, the additional 31-methyl group (sec-OH → tert-OH) did not further suppress aggregation. The relative stability of the aggregates was in the order 1 > 2R ∼ 3 > 2S as determined by visible spectral analyses. Molecular modeling calculations on dodecamers of zinc-chlorins 1, 2R and 3 gave similar well-ordered energy-minimized structures, while 1 stacked more tightly than 2R and 3. In contrast, 2S gave a relatively disordered (twisted) structure. The calculated dodecameric structures could explain the visible spectral data of 1–3 in nonpolar organic media.
影响因子：
2.9
作者：
Brune,DC;Nozawa,T;Blankenship,RE
通讯作者：
Blankenship,RE