Helicity Manipulation of a Double-Paddled Binaphthyl in a Two-Dimensional Matrix Field at the Air-Water Interface.
Helicity Manipulation of a Double-Paddled Binaphthyl in a Two-Dimensional Matrix Field at the Air-Water Interface.
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DOI：
10.1021/acsnano.0c05093
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发表时间：
2020-10
期刊：
影响因子：
17.1
通讯作者：
Masaki Ishii;Taizo Mori;Waka Nakanishi;Jonathan P. Hill;H. Sakai;K. Ariga
中科院分区：
文献类型：
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作者：
Masaki Ishii;Taizo Mori;Waka Nakanishi;Jonathan P. Hill;H. Sakai;K. Ariga
分子的行为和功能受到其主要的直接环境的影响。分子机器根据构象变化发挥作用，并且已经在溶液状态下进行了大量研究。为了获得更复杂的功能分子机器，有必要在各种环境中对其进行分析和控制。我们设计并合成了一种双联萘均四甲苯（BBD）分子，它具有两个联萘基团通过一个中心均四甲苯部分连接，允许形成几种构象异构体。在密度泛函理论（DFT）计算中，BBD有五种主要的构象，表示为反1/反2/顺1/顺2/平。它已被证明，BBD在溶液中表现出不同的构象（反-1和syn-1）比在金表面（syn二聚体和平面）。在这项工作中，BBD构象的比例已被控制在混合单分子膜与几种不同的脂质在空气-水界面，以比较不同条件下的构象活性。通过圆二色光谱和密度泛函理论计算，估计了用Langmuir-Blodgett技术得到的转移膜中BBD的构象。研究发现，BBD在混合单分子膜中的构象取决于其聚集态，而聚集态在此受力学性能和结晶性的控制。在具有与BBD具有较低相容性的"硬"脂质的混合单分子膜中以及在流延膜中，BBD是自聚集的，并且主要形成稳定的反-1和syn-1构象，而不稳定的反-2和syn-2构象在涉及"软"脂质的更分散的状态中占主导地位，这显示出与BBD的良好相容性。在BBD的构象变化是由于不同的聚集态的形成在每个混合单分子层根据的可折叠性。总体而言，BBD分子构象（和由此产生的光谱）可以通过控制环境来调整，无论是在溶液中，在固体基质上，或在空气-水界面处与脂质的混合物中。
Molecular behavior and functionality are affected by their prevailing immediate environment. Molecular machines function according to conformational variations and have been studied largely in solution states. In order to access more highly complex functional molecular machines, it is necessary to analyze and control them in various environments. We have designed and synthesized a bisbinaphthyldurene (BBD) molecule that has two binaphthyl groups connected through a central durene moiety, allowing for the formation of several conformers. In density functional theory (DFT) calculations, BBD has five major conformers, denoted anti-1/anti-2/syn-1/syn-2/flat. It has been demonstrated that BBD exhibits different conformations in solution (anti-1 and syn-1) than on a gold surface (syn dimer and flat). In this work, the ratio of BBD conformations has been controlled in mixed monolayers with several different lipids at an air-water interface in order to compare conformational activity under different conditions. The conformations of BBD in transferred films obtained by using Langmuir-Blodgett techniques were estimated from circular dichroism spectra and DFT calculations. It has been found that the conformation of BBD in the mixed monolayer depends on its aggregated state, which has been controlled here by the mechanical properties and miscibility. In mixed monolayers with "hard" lipids having less miscibility with BBD as well as in cast film, BBD is self-aggregated and mostly forms stable anti-1 and syn-1 conformations, while unstable anti-2 and syn-2 conformers dominated in the more dispersed states involving "soft" lipids, which show good miscibility with BBD. Conformational changes in BBD are due to the formation of different aggregated states in each mixed monolayer according to the miscibility. Overall, BBD molecular conformations (and the resulting spectra) could be tuned by controlling the environment whether in solution, on a solid substrate, or in an admixture with lipids at the air-water interface.