Control Nanoparticle Patterning via Asymmetric Functionalization

美国国家科学基金会-化学与运输系统部门-颗粒与多相过程项目（1415）提案号：0730738首席研究员：Li， Christopher隶属：Drexel大学提案题目：通过不对称功能化控制纳米颗粒的模式。将纳米颗粒（NPs）组装成所需的模式是将这些迷人的材料带入许多实际应用的主要障碍之一。合成定制的非对称功能化NPs （AFNPs）是克服这一障碍的关键。我们最近开发了一种聚合物-单晶模板法来合成AFNPs。利用表面带有官能团的聚合物单晶对NPs进行功能化。这些晶体的固态性质导致了不对称功能化。在本次研究中，我们的目标是进一步探索这种方法来合成各种AFNPs并将其组装成不同的结构以用于不同的应用。具体目标是：1)合成各种具有不同光学和电子性质的可控AFNPs。一些精心挑选的官能团（包括-OH，-COOH， NH2和不同的聚合物）将与这些AFNPs偶联。还将合成含np的三嵌段共聚物。特别的努力将致力于合成单功能化的NP，其中只有一个聚合物链连接到NP上。2)将上述定制的AFNPs组装成各种结构。AFNPs可以看作是人造原子。通过使用具有适当官能团的配体，它们可以选择性地与其他配体结合并形成簇（人工分子）。将合成含有一种或两种NP的NP二聚体、h2o形簇和NP链。含np的三嵌段共聚物的自组装也将被研究。通过精心调整三嵌段共聚物的结构，可以形成ABCCBA片层状和核壳柱状等纳米结构。逼近法是实现多种afnp的通用方法。与AFNP领域的最新技术相比，我们提出的研究的关键优势是使用聚合物单晶作为偶联反应的固体底物。使用这种独特的基材的好处可以总结如下。(1)聚合物单晶为AFNP合成提供了可逆底物；多功能也是可行的；(2)可获得独立的单层或多层NP膜，且NP面密度可控；(3)单功能化的NPs也可以实现；(4)各种NP配合物，如二聚体、h2o形NP和NP链（同质NP和共NP链）都可以很容易地制备。更广泛的影响。这项研究旨在解决纳米技术领域的一个具有挑战性的问题。如果成功，它将有助于将许多迷人的np带入市场。该提案的教育部分包括：(1)通过开发将用于“纳米结构聚合物材料”课程的“纳米混合材料”模块，解决聚合物纳米科学和纳米技术现代发展教育的需求。(2)让高中学生和教师，特别是代表性不足的人群参与拟议的研究活动。这些拟议的教育活动具有广泛的影响。首先，将通过多种辅导项目，让高中学生和教师参与研究活动，缩小教育发展水平之间的差距。其次，由于费城地区未被充分代表的群体人口众多，拟议的外展计划将专门针对鼓励未被充分代表的群体参与。第三，通过科学媒体和公众研讨会宣传拟议的研究。这些信息的传播以及中学教师的实践经验将通过与费城周边地区的学区建立合作努力，使更多的教师有能力教育未来。

National Science Foundation - Division of Chemical &Transport Systems Particulate & Multiphase Processes Program (1415)Proposal Number: 0730738 Principal Investigators: Li, Christopher Affiliation: Drexel University Proposal Title: Control Nanoparticle Patterning via Asymmetric Functionalization Intellectual Merit. Assembling nanoparticles (NPs) into desired patterns is one of the major hurdles to bringing these fascinating materials into many practical applications. Synthesizing tailor-made, asymmetrically functionalized NPs (AFNPs) holds the key to overcoming this hurdle. We recently developed a polymer-single-crystal-templating method to synthesize AFNPs. Polymer single crystals with functional groups on the crystal surface were used to functionalize NPs. The solid state nature of these crystals renders the asymmetric functionalization. In the proposed research, we aim to further explore this method to synthesize a variety of AFNPs and assemble them into various structures for different applications. The specific objectives are: 1) to synthesize a variety of well-controlled AFNPs with different optical and electronic properties. A number of carefully selected functional groups (including -OH,-COOH, NH2 and different polymers) will be coupled with these AFNPs. NP-containing triblock copolymers will also be synthesized. Special efforts will be devoted to synthesizing monofunctionalized NPs where only one polymer chain is attached to the NP. 2) to assemble the above tailor-made AFNPs into various structures. The AFNPs can be regarded as artificial atoms. By using ligands with proper functional groups, they can selectively bond with others and form a cluster (artificial molecule). NP dimers, H2O-shaped clusters and NP chains containing one or two types of NPs will be synthesized. Self-assembly of the NP-containing triblock copolymers will also be investigated. Nanostructures such as ABCCBA lamellar and core-shell cylinder could be formed by carefully tuning the triblock copolymer structures. The approach method is a generic way to achieve a variety of AFNPs. Compared to the state-of-the-art in the AFNP field, the key advantage of our proposed research is using polymer single crystals as the solid substrate for coupling reaction. The benefits of using this unique substrate can be summarized as the follows. (1) The polymer single crystal provides a reversible substrate for AFNP synthesis; multifunctionality is also feasible; (2) Free standing mono- or multi-layer NP films can be obtained with controlled NP areal density; (3) Monofunctionalized NPs can also be achieved; (4) A variety of NP complexes such as dimers, H2O-shaped NPs and NP chains (both homo-NP and co-NP chain) can be readily fabricated.Broader Impact. The research aims to tackle a challenging problem in the nanotechnology field. If successful, it could help to bring many fascinating NPs into the market place. The educational component of the proposal includes: (1) Addressing the need for the education of modern developments in polymer nanoscience and nanotechnology by developing "Nanohybrid Materials" modules which will be used in the "Nanostructured Polymeric Materials" course. (2) Involving high school students and teachers, particularly under-represented populations, in the proposed research activities. These proposed educational activities encompass a broad impact. First, the proposed plan will help bridge the existing gap between levels of educational developments by involving high school students and teachers in research activities through a number of mentoring programs. Second, due to the high population of underrepresented groups in the Philadelphia region, the proposed outreach program will be specifically geared towards encouraging the participation of under-represented populations. Third, the proposed research will be publicized through scientific media and public workshops. The dissemination of this information along with hands on experiences for secondary education teachers will result in more informed teachers capable of educating the future by establishing collaborative efforts with school districts in the surrounding Philadelphia region.