Supramolecularly assembled functional nanocages

计划中的研究计划将涉及一些新颖和令人兴奋的化学领域，最终产品可用于从生物医学到材料科学的应用。该项目的总体目标是通过开发新的策略将反应基团束缚在纳米级中空聚合物支架上，从而创造和控制反应基团的性质和局部环境。这些小的离散纳米笼在构造时将含有反应性和离散的官能团，例如在其整个内部壳表面上可用的催化基团。它们也将被定制为尺寸和相响应，以允许改善的吸收/释放的小分子和从solution.These纳米笼容易去除可以设想为三维可剪裁和渗透的支持，提供独特的环境中，选择性的反应和小分子的转化可以发生与控制的组成和产品的性质。有人提出，这些合成结构的催化性能也可以模仿自然界自己的催化剂，酶。这些纳米笼也可以作为反应宿主或容器来运载货物，因为它们具有内部反应功能，使它们成为药物和基因治疗递送载体的理想选择。此外，设想这些功能结构可以表现为病毒胶囊的合成类似物，因此可能在大小、结构和功能上模拟这些生物分子。本计画的研究目标将借由可逆化学在两亲性嵌段共聚物合成中的应用来达成。有人提出，互补的非共价基团被纳入到两个聚合物链端，以允许可逆的嵌段共聚物形成。这些嵌段共聚物的超分子自组装成球形胶束及其稳定化将提供在核-壳界面处具有可裂解基团的聚合物纳米颗粒。通过选择性地裂解这种界面非共价相互作用，可以在温和条件下选择性地去除核心结构域，以提供中空球形笼状结构，其在水性介质中稳定。上述方法允许合成3-D笼状结构，其内表面含有可用于进一步化学反应的多个反应性基团的特定结合。使用这些反应性手柄，纳米笼可以被修饰以允许它们作为递送载体或纳米反应器的特定应用。这些纳米笼作为功能性支架的应用可以通过仔细选择亲水性聚合物链端上的非共价基团来实现。这些纳米笼在形状和大小上与合成囊泡或聚合物囊泡相似，在材料科学、化学生物学和无机化学等领域具有广阔的应用前景。然而，与囊泡或聚合物囊泡不同的是，这些新型纳米结构中的外膜层是完全亲水的，其中中心封装区域被疏水膜包围。这些新材料提供了在改变壳厚度、交联度时的受控渗透性和释放的优点，并且将使这些纳米笼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.