A self-assembled cylindrical capsule:: New supramolecular phenomena through encapsulation
A self-assembled cylindrical capsule:: New supramolecular phenomena through encapsulation
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DOI：
10.1002/(sici)1521-3765(20000103)6:1
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发表时间：
2000-01-01
影响因子：
4.3
通讯作者：
Rebek, J
中科院分区：
文献类型：
--
作者：
Körner, SK;Tucci, FC;Rebek, J
描述了纳米尺寸的自组装圆柱形胶囊1a. 1a的合成和光谱表征。在[D-12]均三甲苯溶液中，用H-1 NMR谱研究了有机大分子的包封。除了胶囊的形状和几何形状的计算（MacroModel 5.5，琥珀色 * 力场）分析，对内腔尺寸估计的实验方法进行了描述。这涉及使用一系列同源分子“统治者”（例如芳族酰胺5a-i）。利用该技术，胶囊1a 1a内的可用空间可以估计为5.7 × 14.7埃（误差+/-0.2埃）。过氧化二苯甲酰易于包封在[D-12]均三甲苯中，并在70 ℃下在胶囊内至少3天内稳定分解。此外，1a.1a防止包封的过氧化物氧化溶液中存在的Ph 3 P或二苯基卡巴肼。过氧化物的正常化学反应性通过DMF从胶囊中释放而恢复，DMF是一种竞争将胶囊保持在一起的氢键的溶剂。胶囊的保护和释放预示着胶囊在催化和传递中的应用。
The synthesis and spectroscopic characterization of self-assembled cylindrical capsule 1a.1a of nanometer dimensions is described. Encapsulation studies of large organic guest molecules were performed by using H-1 NMR sprectroscopy in [D-12]mesitylene solution. In addition to the computational (MacroModel 5.5, Amber* force field) analysis of the capsule's shape and geometry, an experimental approach towards estimation of the internal cavity dimensions is described. This involves using series of homologous molecular "rulers" (e.g. aromatic amides 5a-i). The available space inside the capsule la la can be estimated as 5.7 x 14.7 Angstrom (error +/- 0.2 Angstrom) with this technique. Dibenzoyl peroxide is readily encapsulated in [D-12]mesitylene and was shown to be stable to decomposition for at least three days at 70 degrees C inside the capsule. Moreover, 1a.1a prevents the encapsulated peroxide from oxidizing Ph3P or diphenyl carbazide present in solution. The normal chemical reactivity of the peroxide is restored by release from the capsule by DMF, a solvent that competes for the hydrogen bonds that hold the capsule together. The protection and release of encapsulated species augurs well for the application of capsules in catalysis and delivery.