Macromolecular semi-rigid nanocavities for cooperative recognition of specific large molecular shapes
Macromolecular semi-rigid nanocavities for cooperative recognition of specific large molecular shapes
复制标题
DOI：
10.1038/ncomms3581
复制
发表时间：
2013-10-01
影响因子：
16.6
通讯作者：
Yamamoto, Kimihisa
中科院分区：
文献类型：
--
作者：
Imaoka, Takane;Kawana, Yuki;Yamamoto, Kimihisa
较大客体分子（通常超过1 nm）的分子形状识别是一项艰巨的任务，因为它需要在宽三维纳米空间内协同探测每个分子方面（大小，轮廓形状，灵活性和特定基团）。虽然蛋白质的智能功能吸引了许多研究人员，但人工分子的复制仍然是一个重大挑战。在这里，我们报告的建设大，明确界定的空腔在大分子主机。通过使用半刚性的树枝状苯基甲亚胺骨干，甚至细微的差异，在大客体分子的形状（高达类似于2纳米）可以区分的合作机制。一个构象固定的复杂的最佳拟合的客户支持的三维模型的基础上的分子模拟。有趣的是，模拟的空腔结构还预测了钌卟啉中心的催化选择性，证明了空腔的高形状持久性和广泛的适用性。
Molecular shape recognition for larger guest molecules (typically over 1 nm) is a difficult task because it requires cooperativity within a wide three-dimensional nanospace coincidentally probing every molecular aspect (size, outline shape, flexibility and specific groups). Although the intelligent functions of proteins have fascinated many researchers, the reproduction by artificial molecules remains a significant challenge. Here we report the construction of large, well-defined cavities in macromolecular hosts. Through the use of semi-rigid dendritic phenylazomethine backbones, even subtle differences in the shapes of large guest molecules (up to similar to 2 nm) may be discriminated by the cooperative mechanism. A conformationally fixed complex with the best-fitting guest is supported by a three-dimensional model based on a molecular simulation. Interestingly, the simulated cavity structure also predicts catalytic selectivity by a ruthenium porphyrin centre, demonstrating the high shape persistence and wide applicability of the cavity.