Polymerization of Supramolecular Assemblies for Template-to-Template Synthesis (T2T)

超分子自组装是控制新材料功能纳米结构形成的有力工具。在大分子化学中，人们对超分子组织进行了深入的研究。另一方面，从超分子预先组织的单体形成大分子纳米结构代表了一种不太发达的模板方法。已经证明，纳米对象，如球状和棒状，可以通过双层囊泡的交联和中间相(如倒六方相)中单体的聚合而产生。然而，到目前为止，能够控制分子对象大小的例子很少。在这里，我们研究了楔形磺酸与含有互补碱性基团的聚合物的络合物。我们已经证明，这些络合物在稀溶液中组装成单一的球状和圆柱形的超结构，并根据中和度的不同以片状或六方柱状的形式存在。在超分子圆柱体中，单个聚合物链被楔形分子包围，圆柱体的长度由相应的聚合物主干的轮廓长度定义，类似于烟草花叶病毒的情况，其中蛋白质衣壳组装在RNA周围。本研究项目的目的是利用这种自组织机制来制备具有定义尺寸的功能纳米对象，并完成模板到模板的合成，从而能够复制分子量。为此，将在面向组件外部的楔形分子的较厚端引入可聚合基团。在组装状态下的聚合允许稳定结构。在这种情况下，自组装涉及到楔形分子与线性大分子的络合，可以形成长度由核心大分子控制的圆柱体。在形成涂层的分子聚合后，真正的超分子大分子，其大小以核心分子为模板，其本身可以形成占据单体的功能孔。这样，它就可以作为模板来控制其核心中聚合物的长度。将手性引入侧基或聚合物主链，有望形成具有手性排列的官能团的孔。因此，可以使用这样的模板来合成具有定义的规整度的聚合物。这里的一个关键问题是，是否有可能将聚合限制在复合体内的连接(在单棒内)，即避免复合体间的交联。另一个关键问题是与合适的单体如乙烯基吡啶形成的超分子络合物，它可以在与强酸接触时进行自发聚合。

Supramolecular self-assembly is a powerful tool in the control of nanometer structure formation for new materials functionalities. In macromolecular chemistry supramolecular organization has been studied intensively. On the other hand formation of macromolecular nanostructures from supramolecularly pre-organized monomers represents a less developed template approach. It has been demonstrated that nanoobjects, such as spheres and rods, can result from crosslinking of bilayer vesicles and by polymerization of monomers in mesophases such as an inverted hexagonal phases. So far, however, examples where it has been possible to control the size of the molecular objects, are rare. Here we investigate the complexes of wedge-shaped sulfonic acids with polymers containing complementary basic groups. We have demonstrated that these complexes assemble in dilute solution to single spheres as well as cylindrical superstructure, and lamellar or hexagonal columnar phase in bulk depending on the degree of neutralization. In the supramolecular cylinders, individual polymer chains are enclosed by the wedgeshaped molecules and the length of the cylinders is defined by the contour length of the corresponding polymer backbone similar like in the case of tobacco mosaic virus where a protein capsid is assembled around the RNA. The aim of this research project is to use this self-organization mechanism to prepare functional nanoobjects with defined dimensions and to accomplish a template-to-template synthesis, enabling replication of the molecular weight. For this purpose, polymerizable groups will be introduced at the thicker end of the wedge-shaped molecules that is oriented towards the outside of the assemblies. Polymerization in the assembled state allows to stabilize the structure. In this case self-assembly involves complexation of wedge molecules to a linear macromolecule, cylinders can be formed whose length is controlled by the core macromolecule. After polymerization of the coat forming molecules, a true supramolecular macromolecule whose size is templated from the core molecule and which itself can form a functional pore that takes up monomers. This way it can serve as a template to control the length of the polymer in its core. Chirality will be introduced into either the side groups or the polymer backbone, which will hopefully result in the formation of pores with chiral arrangement of functional groups. Consequently, polymers with defined tacticity can be synthesized using such templates. One key question here is whether it will be possible to confine the polymerization to intra-complex linkages (within the single rods), i.e. to avoid intercomplex cross-linking. Another key question concerns the formation of the supramolecular complex with suitable monomers like vinylpyridine that can undergo spontaneous polymerization in contact with the strong acids.