Nanostructured Organic-Inorganic Hybrids from AB Diblock and ABC Triblock Copolymers

通过AB二嵌段和ABC三嵌段共聚物的纳米结构有机-无机杂化材料项目，PI提出了在材料科学中最有前途和迅速崛起的研究领域之一的研究。描述了两个研究领域。首先，提出了双连续立方杂化相的研究，它涉及在受限环境中形成磁性结晶部分。这模仿了生物体通过在自组装基质中形成多晶组件来构建骨骼部分的策略。这项工作将阐明关于有机-无机杂化中迷人的双连续立方形态稳定性的基本问题。如果成功，这一部分有可能导致新型介孔材料的有效分离蛋白质。目标材料将具有大的、容易接近的孔和嵌入在壁上的超顺磁性纳米颗粒，结合尺寸排除和磁相互作用进行分离。其次，PI想要探索如何利用AB二嵌段和ABC三嵌段共聚物的聚合物化学来对有机-无机杂化的分子以及介观长度尺度施加前所未有的结构控制。如果成功，拟议项目的这一部分可能导致对模仿自然系统(例如，中性酸碱度和环境温度)的纳米结构二氧化硅类型材料的更良性的化学作用。它还有可能极大地改善形态控制，这是目前自上而下的方法无法获得的。例如，如果可以实现与线性ABC三嵌段共聚物中观察到的相似的形态，则有望获得独特的整体机械性能。此外，可以实现将形状、大小和组成可控的纳米对象的“工具箱”向环形或螺旋方向扩展。两者都对纳米技术领域产生了潜在的影响。拟议的计划建立在过去两年半国际和平研究所实验室取得的进展的基础上。这一提议的一个特别优势来自于与康奈尔大学和国外(德国美因茨Max-Planck聚合物研究所)几个在各自领域享有杰出声誉的个人的持续卓有成效的互动。拟议的研究计划是高度跨学科的。它位于两个传统材料研究领域的交界处，即聚合物科学和陶瓷科学。因此，它将在聚合物科学和固态化学领域提供学生培训和学习，同时促进在新兴的纳米结构有机-无机杂化材料领域的发现和理解。此外，这项工作在合成、表征和性质研究之间进行了平衡，以便学生获得广泛的技术知识，包括阴离子聚合、溶胶-凝胶处理、小角X射线散射(SAXS)、透射电子显微镜(TEM)和固态核磁共振。该项目允许有效利用康奈尔大学提供的基础设施，包括在康奈尔大学用于高分辨率X射线研究的新型能量过滤电子显微镜(EFTEM)和用于高分辨率X射线研究的高能同步加速器(CHESS)的工作。在研究计划的同时，PI建议与康奈尔大学材料研究中心(CCMR)的教育计划办公室合作，扩大他的团队在过去两年半的时间里建立的多方面的外展计划。康奈尔大学位于美国最贫穷和最不发达的地区之一，这让康奈尔大学的教职员工负有特别的责任，帮助康奈尔大学和其他地区的公众了解与材料科学和工程有关的问题。该方案将包括人力资源培训和开发的组成部分，包括代表人数不足的群体的参与(博士后研究人员和学生的培训、本科生的培训、教师方案、K-12方案)、通过设施和仪器加强研究和教育基础设施的努力以及产业拓展。

With a program on nanostructured organic-inorganic hybrid material from AB diblock and ABC triblock copolymers, the PI proposes research in one of the most promising and rapidly emerging research areas in materials science. Two areas of research are described. First, studies on bicontinous cubic hybrid phases are proposed which involve the formation of magnetic crystalline moieties within confined environments. THis mimics a strategy of living organisms to build skeletal parts through formation of polycrystalline assemblies inside self-assembled matrices. The work will elucidate fundamental questions about the stability of fascinating bicontinous cubic morphologies in organic-inorganic hybrids. If successful, this part has the potential to lead to novel mesoporous materials for the efficient separation of proteins. The targeted materials would have large, easily accessible pores and supoerparamagnetic nanoparticles embedded in the walls combining size exclusion and magnetic interactions for separation. Second, the PI wants to explore how the polymer chemistry of AB diblock and ABC triblock copolymers can be exploited to exert unprecedented structure control on the molecular as well as the mesoscopic length scale of organic-inorganic hybrids. If successful, this part of the proposed project could lead to more benign chemistries towards nanostructured silica-type materials that mimic natural systems (e.g., neutral pH and ambient temperatures). It also has the potential to lead to dramatically improved morphology control that currently can not be obtained in top-down approaches. For example, if similar morphologies as observed in linear ABC triblock copolymers could be realized, unique bulk mechanical properties are expected. Furthermore, an expansion of the "tool-box" of nano-objects with controlled shap, size, and composition towards rings or helices could be achieved. Both have potential impact on the field of nanotechnology. The proposed program builds on the progress made over the last two and a half years in the PI's laboratory. A particular strength of this proposal derives from the continuation of very fruitful interactions with several individuals at Cornell and abroad (Max-Planck-Institute for Polymer Research Mainz, Germany) that have outstanding reputation in their field. The proposed research program is highly interdisciplinary. It is positioned at the interface of two traditional areas of materials research, namely, polymer science and ceramics science. It will thus provide student training and learning both in the fields of polymers science and solid state chemistry while simultaneously advancing discovery and understanding in the emerging field of nano-structured organic-inorganic hybrid materials. Furthermore, the work is balanced between synthesis, characterization, and property studies so that the students will gain knowledge in a broad spectrum of techniques including anionic polymerization, sol-gel processing, small angle x-ray scattering (SAXS), transmission electron microscopy (TEM), and solid-state NMR. The project allows effective use of the infrastructure provided at Cornell, including work on a novel energy filtering electron microscope (EFTEM) enabling elemental mapping and at Cornell's High Energy synchrotron Source (CHESS) for high resolution x-ray studies. In parallel to the research program the PI proposes in collaboration with the Educational Program Office of Cornell's Center for Materials Research (CCMR) to expand the multifaceted outreach program that has been constructed over the past two and a half yeats in his group. Cornell is situated in one of the poorest and least developed regions of the US posing a particular responsibility to Cornell faculty to help educate the public in Cornell' region and beyond in issues related to the science and engineering of materials. The program will include components of training and development of human resources including the participation of underrepresented groups (training of postdoctoral researchers and students, in volvement of undergraduates, teacher programs, K-12 programs), efforts to enhance the infrastructure for research and education through facilities and instrumentation, and industrial outreach.