Micellar, Lyotropic and Interfacial Assembly of Amphiphilic Block Copolymers Having Bottlebrush Architectures

包含亲水段和不亲水段的分子在各种生物和人工过程中发挥着核心作用，并广泛用作乳化剂、洗涤剂、药物输送载体、纳米材料模板和采油剂。该奖项的研究将开发和探索一类具有高度可调节的刷子状结构的新型巨型表面活性剂分子。这些分子构建块在水中的自发组装将作为一种快速生成具有多种特性的材料的手段。拟议的研究活动将促进目前对分子自组装的理解，并为能源和健康相关应用的潜在利用提供高价值纳米材料。该研究项目的科学目标将与更广泛的推广和教育计划相结合，旨在改善k -12学前教育和本科STEM教育，并培养具有全球竞争力的STEM劳动力。新组织的西纽约STEM论坛将作为教师专业发展的平台，而本科化学课程将通过基于聚合物的实验室模块得到加强。本项目旨在开发新型瓶刷基大分子表面活性剂，并了解其水相行为。该基金支持的研究将集中在(1)制备两亲性瓶刷嵌段共聚物，(2)在稀溶液中形成胶束，(3)溶性组装，以及(4)利用形状持久的瓶刷共聚物作为分子构建块制造纳米结构界面和材料。该聚合物将通过接枝和透枝两种方法合成，为表面活性剂提供精确的结构和功能控制。开环和控制自由基聚合技术将用于合成具有良好定义的共聚物。采用小角x射线散射和低温透射电子显微镜研究了具有不同主链和侧链不对称的瓶刷表面活性剂在稀、浓水溶液中的自组装。区隔化两亲瓶刷共聚物的界面组装将用于制备介孔颗粒和膜。所提出的研究活动的成功结果将导致对巨大瓶刷表面活性剂的形状依赖组装的现象学理解，以及用于各种应用的以前无法实现的纳米结构材料的制造。实验结果将通过协作计算和建模工作得到增强。

NON-TECHNICAL SUMMARYMolecules that contain both water-friendly and water-unfriendly segments play a central role in a variety of biological and artificial processes, and are in widespread use as emulsifiers, detergents, drug delivery vehicles, templates for nanomaterials and oil recovery agents. The research in this award will develop and explore a new class of giant surfactant molecules with a highly adjustable brush-like structure. Spontaneous assembly of these molecular building blocks in water will be pursued as a means of rapidly generating materials with a diverse set of properties. The proposed research activities will advance the current understanding of molecular self-assembly, and provide access to high-value nanomaterials for potential utilization in energy- and health-related applications. The scientific goals of this research project will be integrated with broader outreach and educational initiatives, aimed at improving pre-K-12 and undergraduate STEM education, and developing a globally competitive STEM workforce. A newly organized Western New York STEM Forum will be used as a platform for teacher professional development, while undergraduate chemistry curricula will be enhanced via polymer-based laboratory modules.TECHNICAL SUMMARYThis project aims to develop new bottlebrush-based macromolecular surfactants and understand their aqueous phase behavior. The research supported by this grant will focus on (1) preparation of amphiphilic bottlebrush block copolymers, (2) micelle formation in dilute solutions, (3) lyotropic assembly, and (4) fabrication of nanostructured interfaces and materials by utilizing shape-persistent bottlebrush copolymers as molecular building blocks. The polymers will be synthesized by grafting-from and grafting-through methods to provide surfactants with precise structural and functional control. Ring-opening and controlled radical polymerization techniques will be employed for the synthesis of well-defined copolymers. Self-assembly of bottlebrush surfactants with varying backbone and side chain asymmetries will be investigated in dilute and concentrated aqueous solutions by means of small angle x-ray scattering and cryogenic transmission electron microscopy. Interfacial assembly of the compartmentalized amphiphilic bottlebrush copolymers will be utilized for the preparation of mesoporous particles and membranes. The successful outcome of the proposed research activities will result in phenomenological understanding of the shape-dependent assembly of giant bottlebrush surfactants and the fabrication of previously unattainable nanostructured materials for a variety of applications. The experimental results will be augmented by collaborative computational and modeling efforts.