NSF-BSF: Tapered Bottlebrush Block Copolymers: Synthesis, Solution Self-Assembly, and Simulations

NSF-BSF：锥形洗瓶刷嵌段共聚物：合成、溶液自组装和模拟

• 批准号: 2104602
• 负责人: John Matson
• 金额: $ 44.15万
• 依托单位: Virginia Polytechnic Institute and State University
• 依托单位国家: 美国
• 项目类别: Standard Grant
• 财政年份: 2021
• 资助国家: 美国
• 起止时间: 2021-06-01 至 2025-05-31
• 项目状态: 未结题
• 来源: https://www.nsf.gov/awardsearch/showAward?AWD_ID=2104602&HistoricalAwards=false
• 关键词: NSF; BSF; Tapered; Bottlebrush; Block

NON-TECHNICAL SUMMARY:With funding from the Polymers Program of the Division of Materials Research, Professor John B. Matson of Virginia Tech and Prof. Ronit Bitton of Ben-Gurion University in Israel lead a team that is creating new polymers that take on a conical shape. How cone-shaped polymers behave and interact in solution is currently unknown because methods to synthesize these polymers were only recently developed. This work is important because polymers that interact in water to form aggregates on the size range of 1-100 nanometers are used in a variety of applications, but fundamental studies on how cone shape influences aggregate shape and size are lacking. The research team will rely on an approach that connects polymer synthesis, characterization of nanometer-scale aggregates, and computer simulations of aggregates to generate theories describing how these unique polymers behave in water. Collectively, these efforts will advance the field of polymer self-assembly, offering potential benefits in the design of polymers for applications in biomedicine, catalysis, food science, and other areas. Due to the collaborative and cross-cultural aspects of this NSF-BSF proposal, this platform will be used to enhance scientific communication with assistance from the Virginia Tech Center for Communicating Science. Off-campus educational goals of this proposal focus on enhancing the Youth Experiencing Science (YES) program for 4th–8th graders in southwestern Virginia.TECHNICAL SUMMARY:This NSF-BSF project focuses on tapered amphiphilic bottlebrush block copolymers (BCPs), which are graft polymers with high grafting density designed to take on an approximately conical shape. The work incorporates an integrated approach to the synthesis, characterization, and simulations of tapered bottlebrush BCPs. Synthetic efforts will rely on ring-opening metathesis (ROMP) grafting-through methods to make a wide range of tapered bottlebrush BCPs with variable degrees of polymerization for the backbone and side chains. The solution self-assembly of tapered bottlebrush BCPs will be systematically investigated using a range of characterization techniques including electron microscopy and small-angle X-ray and neutron scattering (SAXS, SANS). Modeling studies will include coarse-grained models, in a feedback loop, to explain the observed morphologies and suggest new tapered bottlebrush BCPs that could self-assemble into unique or unexpected solution morphologies. The central hypothesis for this project is that the cone angle of the tapered bottlebrush BCPs will influence self-assembled morphology and size distribution. Expected outcomes from this synthesis–characterization–modeling approach include discovering how cone angle influences polymer self-assembly, ultimately revealing new understanding of how polymer structure influences material properties. .This award reflects NSF's statutory mission and has been deemed worthy of support through evaluation using the Foundation's intellectual merit and broader impacts review criteria.

非技术摘要：材料研究部聚合物计划的资助，弗吉尼亚理工大学的约翰·B·马特森教授和以色列本·古里安大学的罗尼特·比顿教授领导的团队正在创建一个新的聚合物，以呈现圆锥形的形状。目前尚不清楚锥形聚合物在溶液中的表现和相互作用，因为合成这些聚合物的方法直到最近才开发。这项工作很重要，因为在水中相互作用以在1-100纳米尺寸范围内形成聚集体的聚合物用于多种应用中，但是关于锥形如何影响骨料形状和大小的基础研究。研究团队将依靠一种方法，该方法将聚合物合成，纳米尺度骨料的表征以及聚集体的计算机模拟来生成描述这些独特聚合物在水中的表现的理论。总的来说，这些努力将推进聚合物自组装领域，从而为生物医学，催化，食品科学和其他领域的应用提供潜在的好处。由于该NSF-BBF提案的合作和跨文化方面，该平台将用于在弗吉尼亚理工大学交流科学中心的帮助下加强科学交流。该提案的校外教育目标着重于增强弗吉尼亚州西南部4至8年级的青年体验科学（是）计划。技术摘要：该NSF-BSF项目的重点是锥形的载荷瓶瓶布块共聚物（BCP），这些瓶瓶块共聚物（BCP）是具有高度涂接涂鸦密度的嫁接聚合物的近似换剂构造的型号。这项工作结合了锥形瓶洗BCP的合成，表征和模拟的综合方法。合成的工作将依靠开环的转学（ROMP）嫁接方法来制作各种锥形瓶洗BCP，用于主链和侧链的聚合度可变。锥形瓶洗BCP的解组装将使用一系列特征技术进行系统研究，包括电子显微镜和小角X射线和中子散射（SAX，SANS）。建模研究将包括在反馈循环中的粗粒模型，以解释观察到的形态，并提出可以自组装成独特或意外的溶液形态的新锥形瓶洗BCP。该项目的中心假设是锥形瓶洗BCP的锥角将影响自组装的形态和尺寸分布。这种合成 - 特征化 - 建模方法中的预期结果包括发现锥角如何影响聚合物自组装，最终揭示了对聚合物结构如何影响材料特性的新理解。该奖项反映了NSF的法定任务，并通过使用基金会的知识分子优点和更广泛的影响审查标准评估被认为是宝贵的支持。

项目成果

Influence of the Norbornene Anchor Group in Ru-Mediated Ring-Opening Metathesis Polymerization: Synthesis of Bottlebrush Polymers

• DOI: 10.1021/acs.macromol.3c00214
• 发表时间: 2023-05
• 期刊: Macromolecules
• 影响因子: 5.5
• 作者: Samantha J. Scannelli;Mohammed Alaboalirat;Diego Troya;John B. Matson

Influence of the Norbornene Anchor Group in Ru-Mediated Ring-Opening Metathesis Polymerization: Synthesis of Linear Polymers

降冰片烯锚定基团对钌介导的开环复分解聚合反应的影响：线性聚合物的合成

• DOI: 10.1021/acs.macromol.3c00172
• 发表时间: 2023
• 期刊: Macromolecules
• 影响因子: 5.5
• 作者: Scannelli, Samantha J.;Paripati, Anshul;Weaver, Jeffrey R.;Vu, Clark;Alaboalirat, Mohammed;Troya, Diego;Matson, John B.
• 通讯作者: Matson, John B.

Radical–radical coupling effects in the direct-growth grafting-through synthesis of bottlebrush polymers using RAFT and ROMP

• DOI: 10.1039/d2py00794k
• 发表时间: 2022
• 期刊: Polymer Chemistry
• 影响因子: 4.6
• 作者: Mohammed Alaboalirat;Clark Vu;John B. Matson

Complex Polymer Architectures Using Ring-Opening Metathesis Polymerization: Synthesis, Applications, and Practical Considerations

• DOI: 10.1021/acs.macromol.2c00338
• 发表时间: 2022-06-14
• 期刊: MACROMOLECULES
• 影响因子: 5.5
• 作者: Blosch, Sarah E.;Scannelli, Samantha J.;Matson, John B.
• 通讯作者: Matson, John B.

Solvent Effects in Grafting-through Ring-Opening Metathesis Polymerization

• DOI: 10.1021/acs.macromol.2c00254
• 发表时间: 2022-04-22
• 期刊: MACROMOLECULES
• 影响因子: 5.5
• 作者: Blosch, Sarah E.;Alaboalirat, Mohammed;Matson, John B.
• 通讯作者: Matson, John B.