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

用于模板到模板合成 (T2T) 的超分子组装体聚合

• 批准号: 157866393
• 负责人: Professor Dr. Martin Möller
• 金额: --
• 依托单位: DWI - Leibniz-Institut für Interaktive Materialien e.V.
• 依托单位国家: 德国
• 项目类别: Research Grants
• 财政年份: 2010
• 资助国家: 德国
• 起止时间: 2009-12-31 至 2013-12-31
• 项目状态: 已结题
• 来源: https://gepris.dfg.de/gepris/projekt/157866393?language=en
• 关键词: Polymerization; Supramolecular; Assemblies; Template; Synthesis

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.

超分子自组装是控制纳米结构形成以实现新材料功能的有力工具。在高分子化学中，超分子结构已被广泛研究。另一方面，由超分子预组织的单体形成大分子纳米结构代表了一种欠发达的模板方法。已经证明，纳米物体，如球体和棒，可以由双层囊泡的交联和通过中间相如倒置六方相中单体的聚合产生。然而，到目前为止，能够控制分子物体大小的例子还很少见。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复合物。我们已经证明，这些配合物组装在稀溶液中的单球以及圆柱形的超结构，和层状或六角柱状相在散装取决于中和度。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聚合物主链的轮廓长度限定，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。该研究项目的目的是使用这种自组织机制来制备具有定义尺寸的功能纳米物体，并完成模板到模板的合成，从而实现分子量的复制。为此目的，可聚合基团将被引入到楔形分子的较厚端，该较厚端朝向组件的外部取向。组装状态下的聚合允许稳定结构。在这种情况下，自组装涉及楔形分子与线性大分子的络合，可以形成其长度由核心大分子控制的圆柱体。在涂层形成分子聚合之后，真正的超分子大分子，其尺寸是从核心分子模板化的，并且其本身可以形成吸收单体的功能孔。通过这种方式，它可以作为模板来控制聚合物在其核心中的长度。手性将被引入到侧基或聚合物主链中，这将有望导致形成具有官能团手性排列的孔。因此，可以使用这样的模板合成具有限定的立构规整度的聚合物。这里的一个关键问题是是否有可能将聚合限制在复合物内的连接（在单杆内），即避免复合物间的交联。另一个关键问题是与合适的单体如乙烯基吡啶形成超分子复合物，这些单体可以在与强酸接触时进行自发聚合。