| Because of their highly stable chiral configuration, the 2,2'-substituted 1,1'-binaphthyls have been extensively used to control many asymmetric processes and have demonstrated outstanding chiral discrimination properties. The unique C2 asymmetric binaphthyl structure, the diverse functionalities of the binaphthyl molecules as well as their stable chiral configuration have allowed the construction of molecules and macromolecules with both fascinating structures and properties. Apart from the continuous interest in the design of binaphthyl-based chiral hosts and catalysts for chiral recognition and asymmetric synthesis, the use of binaphthyls in materials science is emerging as a promising field. The rigidity, chirality, and conjugation of such binaphthyl molecules offer great opportunity in the design of new materials with potentially exciting applications.Until these years with the emergence of a new field of nano-technology called molecular architecture, the rigid aromatic macrocycles have began to gain more and more attention as a kind of nano-structural material because of their inherent advantages (a rigid cyclic structure, a rigid nano-scale cavity, good solubility, excellent resistibility for different chemical or physical conditions, etc). Especially compared with the other organic macrocycles such as crown ether, the rigid nano-scale cyclic structure is full of potential application in nano technology, such as acting as aromatic guest molecules or being ordered organized as a template for the growth of nanoparticles in an ordered way with chemical or physical methods.In this dissertation, we introduced the chiral binaphthyl units into poly (ether sulfone) macrocycles and succeeded in synthesis of a series of chiral macrocycles and polymers having functional groups. The organic nano- to submicron-sized solid or hollow spheres of these chiral macrocycles and polymers were prepared through the reprecipitation method. It was found that the size of particles obtained by above methods displayed concentration-dependent behavior; that was, lower concentrations resulted in the formation of smaller spheres while higher concentrations favored the formation of larger ones. As a result, the self-assembled solid and hollow spheres can be endowed with new opportunities in molecular recognition and separation. The main results are summarized as follows:1. We have synthesized novel chiral R- and S-macrocyclic oligomers containing a carboxyl moiety. The products were characterized by FT-IR, 1H-NMR, MALDI-TOF-MS and CD. The recognition capabilities of two molecular receptors R- and S-macrocyclic oligomers toward L-and D-lysine in the water/THF mixture (2:3) were evaluated by UV–vis titration. The binding strength between R- and S-macrocyclic oligomers toward lysine was different: the lysine could be binded into S-macrocyclic oligomer, but not into R-macrocyclic one.2. Some novel aggregating morphologies from R- and S-macrocyclic oligomers containing a carboxyl moiety, i.e. solid spheres, hollow spheres, spherical crown entities, and spherical particles wrapped with thin shell were fabricated by the reprecipitation method. The aggregate morphologies were in strong dependence on the macrocycle cencentration in THF solution. It could be found that the spheres obtained at higher concentration were mostly larger than the ones at lower concentration. The perfect hollow spheres could be formed from the S-macrocycle at a relatively low concentration. This work proved that such general cyclic organic molecule could self-assemble into nano- to micro-structured morphologies and extended the family of source materials for assembly.3. We described the synthesis of comb polymers having rigid racemic or chiral binaphthyl macrocyclic pendant groups via the free radical polymerization. Polymers obtained were well characterizated by MALDI-TOF-MS, 1H NMR, FT-IR, CD and SEC. These comb polymers having macrocyclic pendant groups showed very good solubility in common organic solvents at room temperature.4. The polymers having rigid racemic or chiral binaphthyl macrocyclic pendant groups could self-assemble into different morphologies by dropping their THF solutions of different concentrations on the surface of water. At a relatively low concentration, the polymers self-aggregated into hollow spheres. When the concentration was increased, the aggregates changed into solid spheres. The morphologies of the hollow or solid spheres were observed by TEM and ESEM. The hollow spheres from the chiral polymers were larger than those from the racemic ones, and the shells were also thicker because of the different affinities between the chiral macrocycles and the racemic ones.5. A novel"light-driven"rigid chiral macrocyclic oligomer with one azo group was synthesized successfully and characterized with MALDI-TOF-MS, FT-IR, 1H NMR and CD. Azobenzene moiety in the cyclic chain underwent trans/cis photoisomerization when it was exposed with different wavelength light. The isomerization of azobenzene group could change into the motion of the entire molecule and change the shape of the central cavity. Characterization of the shape, size and properties of nanometer-scale macrocyclic molecules obtained from various amphiphiles is of great importance not only for the study of the structure and function of nanostructured membrane systems, but also for the potential applications, such as drug entrapment and release, and photochemical solar energy conversion.
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