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，旨在为构建新颖、奇异的纳米颗粒建立新的实验范式。将制定协议，通过微调动力学和热力学控制的阶段性迭代以及在所需阶段应用化学修饰来指导嵌段共聚溶液的行为。此外，还将研制一种新的嵌段共聚功能工具箱，用于纳米颗粒的溶液构建。新的嵌段共聚化学将允许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外壳显示配体功能，f)延伸到多碱作为亲水块用于在动力学控制的组装期间与多酸分子络合，以及g)新的疏水块用于一旦由于动力学控制的分级组装而被捕获在纳米颗粒的内部结构域中用于相分离。新的溶剂混合途径将被用来开发动力学控制的组装工艺，将两种或更多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隔室颗粒构建。然后，得到的多隔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，以获得任意的、不对称的结构和未来的功能。非技术摘要：这项研究将发展科学家在纳米尺度上创造具有前所未有的结构和功能复杂性的粒子的能力。自然界包含了大量复杂纳米结构的例子，它们显示出华丽的形状和功能，既有益(如细胞内的微管、细胞膜)，也有害(如病毒)。人们将寻求合成大分子聚合物的新方法，以及迫使这些分子聚集在一起形成纳米结构的新方法，并将它们结合在一起，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在制造现代电子产品的微处理器和存储器中一样司空见惯。理想情况下，最终的纳米结构在结构上将是任意的，并且在未来将像光刻生产的设备一样有用。进行这一跨学科研究的学生将获得广泛而深入的纳米材料科学和聚合物化学知识。所有参与的学生将通过K-12活动向大学预科学生传播这些知识，利用这些研究开发有趣的主题，促进他们对科学技术的兴趣。

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.