Collaborative Research: Exotic Block Copolymer Nanoparticles through Hierarchical Solution Construction

技术概述：该项目是特拉华大学和德克萨斯农工大学之间的合作项目，旨在建立新的实验范例，以构建新颖的外来纳米颗粒。通过对动力学和热力学控制的微调阶段迭代以及在所需阶段应用化学修饰，将开发直接嵌段共聚物溶液行为的协议。此外，一个新的嵌段共聚物功能工具箱将制定的纳米粒子的溶液结构。新的嵌段共聚物化学将允许a)壳交联，b)核交联，c)壳降解，d)核降解，e)从聚合物纳米颗粒的壳中显示配体功能，f)在动力学控制的组装过程中扩展到多碱基作为与多酸分子络合的亲水性嵌段，g)由于动力学控制的分层组装而被捕获在纳米颗粒内部区域内的新的疏水嵌段用于相分离。新的溶剂混合途径将用于开发动力学控制的组装过程，以将两种或多种不同的嵌段共聚物捕获到同一纳米颗粒中，用于局部相分离和多室颗粒结构。由此产生的多室粒子可以在分层构建过程中进行额外的组装和/或合成步骤，以实现任意，不对称结构和未来功能。非技术总结：这项研究将发展科学家创造结构和功能空前复杂的纳米级粒子的能力。自然界中有很多复杂纳米结构的例子，它们显示出华丽的形状和功能，既有有益的（如细胞、细胞膜内的微管），也有有害的（如病毒）。合成大分子聚合物的新方法，结合迫使这些分子在一起产生纳米结构的新方法，将被寻求和结合，以制造非凡的合成纳米结构。经过努力，制造这些纳米材料的构造方法将像光刻技术制造现代电子产品的微处理器和存储器一样常规。理想情况下，最终的纳米结构在结构上是任意的，并且在未来会像光刻技术生产的设备一样有用。从事这项跨学科研究的学生将获得纳米材料科学和聚合物化学的广泛而深入的知识。所有参与的学生将通过K-12活动将这些知识传播给大学预科学生，这些活动利用研究来开发有趣的话题，以促进他们对科学和技术的兴趣。

TECHNICAL SUMMARY:This project is a collaboration between the University of Delaware and Texas A&M which aims to establish new experimental paradigms for the construction of novel, exotic nanoparticles. Protocols will be developed that direct block copolymer solution behavior through fine-tuning stagewise iterations of kinetic vs. thermodynamic control and the application of chemical modifications at desired stages. In addition, a new toolbox of block copolymer functionality will be formulated for solution construction of nanoparticles. New block copolymer chemistries will allow a) shell crosslinking, b) core crosslinking, c) shell degradation, d) core degradation, e) display of ligand functionality from shell of polymer nanoparticle, f) extension to polybases as hydrophilic blocks for complexation with multiacid molecules during kinetically controlled assembly, and g) new hydrophobic blocks for phase separation once trapped within internal domains of the nanoparticles due to kinetically controlled hierarchical assembly. New solvent mixing pathways will be used to develop kinetically-controlled assembly processes for trapping two or more different block copolymers into the same nanoparticle for local phase separation and multicompartment particle construction. Resultant multicompartment particles can then undergo additional assembly and/or synthetic steps in a hierarchical construction process towards arbitrary, asymmetric structure and future function.NON-TECHNICAL SUMMARY: This research will develop the ability of scientists to create particles on the nanoscale with unprecedented complexity in structure and function. Nature contains plenty of examples of complex nanostructures that display ornate shape and function, both beneficial (e.g. microtubules within cells, cell membranes) and deleterious (e.g. viruses). New methods of synthesizing large polymer molecules, combined with new methods for forcing these molecules together to produce nanostructures, will be sought and combined to make extraordinary synthetic nanostructures. With effort, the construction method to make these nanomaterials will be as routine as lithography is in making microprocessors and memories for modern electronics. Ideally, the final nanostructures will be as arbitrary in structure and useful as lithographically produced devices in the future. The students who perform this interdisciplinary research will gain a broad and deep knowledge of nanomaterials science and polymer chemistry. All students involved will spread this knowledge to pre-college students through K-12 activities that use the research to develop fun, interesting topics to promote their interest in science and technology.