Supramolecularly assembled functional nanocages

计划中的研究计划将涉及一些新的和令人兴奋的化学领域，最终的产品将在从生物医学到材料科学的各种应用中有用。该项目的总体目标是通过开发新的策略将活性基团连接到纳米级的中空聚合物支架上，来创建和控制活性基团的性质和局部环境。当这些小的离散纳米笼构建时，将包含活性和离散功能，例如整个内壳表面都有催化基团。它们还将被定制成尺寸和相响应的，以允许更好地吸收/释放小分子并容易地从溶液中去除纳米笼。这些纳米笼可以被设想为三维可定制和可渗透的载体，提供了独特的环境，在其中可以通过控制产品的组成和性质来发生小分子的选择性反应和转化。有人认为，这些合成结构的催化性能也可以模拟自然界自身的催化剂，酶。这些纳米笼还可以作为反应性宿主或运载货物的容器，因为它们具有内部反应性功能，使它们成为药物和基因治疗输送载体的理想选择。此外，据设想，这些功能结构可以作为病毒胶囊的合成类似物，从而可能在大小、结构和功能上模仿这些生物分子。通过可逆化学反应在两亲性嵌段共聚物合成中的应用，实现项目研究目标。建议将互补的非共价基引入到聚合物链的两端，以允许形成可逆的嵌段共聚物。这些嵌段共聚物的超分子自组装成球形胶束及其稳定性将提供在核-壳界面具有可切割基团的聚合物纳米颗粒。通过选择性地切割这种界面非共价相互作用，可以在温和的条件下选择性地去除核心区，得到在水介质中稳定的中空球形笼状结构。上述方法允许合成3-D笼状结构，其内表面包含多种活性基团的特定结合，可用于进一步的化学反应。使用这些反应性手柄，纳米笼可以被修饰，以允许它们作为输送载体或纳米反应器的特定应用。这些纳米笼作为功能支架的应用可以通过仔细选择亲水性聚合物链端的非共价基来实现。提出了这些材料在材料科学、化学生物学和无机化学中有很大的应用前景，这些纳米笼在形状和大小上类似于合成的囊泡或聚合体。然而，与囊泡或多聚体不同的是，在这些新型纳米结构中，中央被包裹的区域被疏水膜包围，而外膜层是完全亲水的。这些新材料在改变壳层厚度和交联度时具有可控的渗透性和释放的优点，并将使这些纳米笼子能够适应更广泛的应用。

The intended research program will address some novel and exciting areas of chemistry, with the eventual products being useful in applications ranging from biomedicine to material science. The overall goal of the project is to create and control the properties and local environment of reactive groups by developing new strategies to tether them to nanoscale hollow polymeric scaffolds. These small discrete nanocages when constructed, will contain reactive and discrete functionality such as catalytic groups available throughout their interior shell surface. They will also be tailored to be size and phase responsive to allow for improved uptake/release of small molecules and facile removal of the nanocages from solution.These nanocages can be envisaged as 3-dimensional tailorable and permeable supports that afford unique environments in which the selective reaction and transformation of small molecules can occur with control of the composition and nature of products. It is proposed that the catalytic properties of these synthetic structures could also mimic natures' own catalysts, enzymes. These nanocages could also behave as reactive hosts or vessels to carry cargo, given their interior reactive functionality, making them ideal for uses as drug and gene therapy delivery vehicles. In addition, it is envisaged that these functional structures could behave as synthetic analogues to virus capsules and thus perhaps mimic these biomolecules in size, structure and function. The project research goals will be achieved using the application of reversible chemistries in the synthesis of the amphiphilic block copolymers. It is proposed that complementary non-covalent groups be incorporated into the two polymer chain ends to allow for reversible block copolymer formation. The supramolecular self-assembly of these block copolymers into spherical micelles and their stabilisation will afford polymeric nanoparticles with a cleavable group in place at the core-shell interface. By selectively cleaving this interfacial non-covalent interaction the core domain can be selectively removed under mild conditions to afford a hollow spherical cage-like structure, which is stable in aqueous media. These water-soluble, flexible yet robust spherical shell layers can be described as nanocages or nanocapsules.The methodlogy described above allows for the synthesis of 3-D cage structures whose interior surface contains the specific incorporation of multiple reactive groups which are available for further chemistries. Using these reactive handles the nanocages can be modified to allow for their specific application as delivery vehicles or nanoreactors. The application of these nanocages as functional scaffolds can be achieved by careful choice of the non-covalent groups on the hydrophilic polymer chain end. It is proposed that there is great scope for the application of these materials in material science, chemical biology and inorganic chemistry.These nanocages are similar in shape and size to synthetic vesicles or polymersomes. However, unlike vesicles or polymersomes were the central encapsulated region is surrounded by a hydrophobic membrane, the outer membrane layer in these novel nanostructures is completely hydrophilic. These new materials afford the advantage of controlled permeability and release upon altering the shell thickness, degree of cross-linking and will enable the tailoring of these nanocages to a wider range of applications.