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.
Soft and flexible two-dimensional (2D) systems, such as liquid interfaces, would have much more potentials in dynamic regulation on nano-macroc onnected functions. In this Minireview article, we focus especially on dynamic motional functions at liquid dynamic interfaces as 2D material systems. Severalr ecent examples are selectedt ob ee xplained for overviewing features and importance of dynamic soft interfaces in aw ide range of action systems. The exemplified research systems are mainly classified into three cate-gories:( i) controlo fm icroobjects with motional regulations; (ii)control of molecular machines with functions of target discriminationa nd optical outputs; (iii)control of living cells including molecular machine functions at cell membranes and cell/biomolecular behaviors at liquid interface. Sciences on soft 2D media with motional freedom and their nanoarchitectonics constructions will have increased importance in future technology in addition to popularr igid solid 2D materials.
An air–water interface enables molecular assemblies and conformations to be controlled according to their intrinsic interactions and anisotropic stimuli. The chirality and conformation of binaphthyl derivatives have been controlled by tuning molecular aggregated states in solution. In this study, we have tuned molecular aggregated states of monobinaphthyldurene (MBD) by applying different mechanical stimuli to control the conformation at the air–water interface. Density functional theory calculations indicate that MBD exists essentially in two conformations, namely, 1-MBD (most stable) and 2-MBD (less stable). MBD was mechanically dissolved in appropriate lipid matrices using the Langmuir–Blodgett (LB) method, while pure MBD was self-assembled at the dynamic air–water interface in the absence of or by applying vortex motions (vortex LB method). In MBD mixed monolayer, surface pressure–molecular area measurements and atomic force microscopy observations suggest that separate lipids and MBD phases transform to mixed phases induced by the dissolution of MBD into the lipid matrices during mechanical compression at the air–water interface. Circular dichroism measurements indicate that molecular conformation changes from 1-MBD to 2-MBD in passing from a separated phase to a mixed MBD/lipid phase. In addition, the molecular aggregated states and conformations of MBD depend on the spreading volume and vortex flow rate when applying the vortex LB method. Molecular conformations and aggregated states of MBD could be controlled continuously by applying a mechanical stimulus at the air–water interface.
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