Multifunctional Hybrid Nanomaterials: Development to Biomedical Applications

在聚合物和树枝状大分子化学的总主题下，这项研究计划的目标是创造在纳米医学中融合使用的新类别的大分子。基础科学研究是开发用于现实世界的材料的基础。通过这项研究计划，我们的短期目标是合理地设计新的结构并研究其独特的性能，长期而言，将它们作为构建块来制造用于生物医学应用的新型纳米材料。第一个项目旨在创造一种新的定义明确的金属聚合物。虽然已经报道了多种金属聚合物，但基于N-杂环克拉宾(NHCs)的金属聚合物非常少见。这与NHC已被证明与许多金属离子形成强键的事实形成鲜明对比。在我们的方法中，我们将合成各种基于NHC金属络合物的金属聚合物，如Au和Ag。然后，我们将使用这些新材料作为新的前驱体来合成尺寸和组成可控的纳米颗粒，从而实现微调的光电性能，用于干法输送应用。在第二个项目中，我们将引入结晶型线状-树枝状嵌段共聚物(BCP)作为新的自组装构建块，用于纳米材料工程。尽管在一定程度上报道了无定形线状树枝状BCP的合成和自组装，但还没有具有结晶链段的线状树枝状BCP的例子。利用这类新开发的BCP，我们将形成具有长血液循环时间的纳米材料，同时能够与生物系统有效地相互作用。第三个项目的重点将是设计和合成基于高氟化树枝状大分子的纳米材料。与含氟的线性聚合物不同，文献中只有少数几篇报告展示了含氟的树枝状大分子。使用我们的新型含氟树枝状大分子，其深入的自组装研究可以为纳米医学带来令人兴奋的机会。除了用作药物输送载体外，我们还将在19F磁共振成像中研究这些材料作为固有的活性纳米结构。拟议的研究计划处于功能聚合物、树枝状大分子和纳米材料领域的前沿。这一创新计划的成果将对国内和国际上高度增长的材料化学领域做出重大贡献。通过该计划，高素质的人员将接受在有机、无机和材料合成与表征技术方面的广泛培训，并将获得与生物和计算化学人员的广泛合作机会，所有这些都将对他们未来职业生涯发展必要的技能至关重要。

Under the general theme of polymer and dendrimer chemistry, the objective of this research program, consisting of three projects, is to create new classes of macromolecules that converge in their use in nanomedicine. Research in fundamental science is the basis for development of materials for real world applications. Through this research program, our short-term goal is to rationally design new structures and study their unique resulting properties, and, in the long-term, use them as building blocks to fabricate novel nanomaterials for biomedical applications. The first project aims to create a new class of well-defined metallopolymers. Although a wide variety of metallopolymers have been reported, those based on N-heterocyclic crabenes (NHCs) are very rare. This is in sharp contrast with the fact that NHCs have been shown to form strong bonds to many metal ions. In our approach, we will synthesize a variety of metallopolymers based on NHCmetal complexes with metals such as Au and Ag. We will then use these new materials as novel precursors for the synthesis of nanoparticles with controlled dimensions and compositions and, hence, fine-tuned optoelectronic properties for dry delivery applications.In the second project, we will introduce crystalline linear-dendritic block copolymers (BCPs) as new self-assembling building blocks for nanomaterial engineering. Although the synthesis and self-assembly of amorphous linear-dendritic BCPs is reported to some extent, there are no examples of linear-dendritic BCPs with crystalline segments. Using this newly-developed class of BCPs, we will form nanomaterials that have long blood circulation times while, at the same time, are capable of effectively interacting with biological systems. The focus of the third project will be the design and synthesis of nanomaterials based on highly-fluorinated dendrimers. Unlike fluorinated linear polymers, there are only handful reports showcasing fluorinated dendrimers in the literature. Using our new fluorinated dendrimers, their in-depth self-assembly study can open exciting opportunities in nanomedicine. Besides their use as drug delivery vehicles, we will also investigate these materials as inherently-active nanostrutures in 19F magnetic resonance imaging. The proposed research program is at the cutting edge of functional polymer-, dendrimer-, and nanomaterials fields. Outcomes of this innovative program will make high-impact contributions to the highly-growing field of materials chemistry, nationally and internationally. Through this program, highly qualified personnel will receive extensive training in organic, inorganic, and materials synthesis and characterization techniques, and will be exposed to extensive collaboration opportunities with bio- and computational chemists, all of which will be essential to develop necessary skillset for their future careers.