CAREER: CAS: Radical Cascade-Driven Polymerization and Depolymerization

职业：CAS：自由基级联驱动的聚合和解聚

• 批准号: 1944512
• 负责人: Jia Niu
• 金额: $ 67.5万
• 依托单位: Boston College
• 依托单位国家: 美国
• 项目类别: Continuing Grant
• 财政年份: 2020
• 资助国家: 美国
• 起止时间: 2020-05-01 至 2025-04-30
• 项目状态: 未结题
• 来源: https://www.nsf.gov/awardsearch/showAward?AWD_ID=1944512&HistoricalAwards=false
• 关键词: CAREER; CAS; Radical; Cascade; Driven

With this CAREER Award from the Macromolecular, Supramolecular and Nanochemistry Program in the Chemistry Division, Professor Jia Niu at Boston College is designs and develops new techniques for the synthesis and degradation of plastics. The method uses highly reactive molecules and catalysts based on copper, ruthenium, and iridium. Professor Niu's research is also using computational methods to better understand how these reactions work and how to improve them. Ring-opening and ring-closing polymerization reactions provide unique benefits in sustainability because of their ability use environmentally-friendly building blocks and degrade under mild conditions. This research has the potential to develop next-generation materials that are used in temperature-stable soft matter, stimuli-responsive materials, and targeted drug delivery. The project contributes to the training of a diverse group of students in a highly interdisciplinary research environment. The undergraduate course “Design Your Own Pet-RAFT” trains undergraduate students in a laboratory setting. Professor Niu also implements outreach activities centered on the minicourse “Polymers and You." This course is designed for 6th-9th grade urban homeless children in the greater Boston area.This research is focused on developing a new strategy for polymer synthesis that employs radical cascade reactions that provide the key driving force for the controlled synthesis of polymers and stimuli-triggered degradation of precision main-chain polymers. There are three main objectives associated with the project. The first objective focuses on structure-function relationships in radical ring opening polymerizations and couples experimental and computational techniques aimed at optimization of several important reaction parameters. In the second objective, polymers featuring gamma-lactams in the main backbone are prepared using ring-closing cascade polymerization. The last aim concentrates on the synthesis of self-immolative polymers via step-growth and ring-opening metathesis polymerizations techniques. Research associated with this award enables the synthesis of macromolecules that contain functional groups in the main backbone, rather than side chains which is the traditional approach associated with other polymerization techniques. The research is highly transformative and it could lead to a new exciting platform for industrially-relevant controlled radical polymerizations.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.

获得化学学部大分子、超分子和纳米化学项目颁发的CAREER奖后，波士顿学院的牛佳教授设计并开发了塑料合成和降解的新技术。该方法使用基于铜、钌和铱的高活性分子和催化剂。牛教授的研究也在使用计算方法来更好地理解这些反应是如何起作用的，以及如何改进它们。开环和闭环聚合反应在可持续性方面具有独特的优势，因为它们能够使用环境友好的构建块并在温和条件下降解。这项研究有潜力开发下一代材料，用于温度稳定的软物质、刺激反应材料和靶向药物输送。该项目有助于在高度跨学科的研究环境中培养多样化的学生群体。本科课程“设计你自己的宠物筏”在实验室环境中训练本科生。牛教授还开展了以“聚合物与你”为中心的推广活动。本课程是为大波士顿地区6 -9年级的城市无家可归儿童设计的。本研究的重点是开发一种新的聚合物合成策略，该策略采用自由基级联反应，为聚合物的受控合成和精密主链聚合物的刺激触发降解提供关键驱动力。与该项目相关的主要目标有三个。第一个目标是关注自由基开环聚合的结构-功能关系和偶对，旨在优化几个重要反应参数的实验和计算技术。在第二个目标中，使用闭合环级联聚合制备了具有-内酰胺在主骨架中的聚合物。最后一个目标集中在通过台阶生长和开环复分解聚合技术合成自焚聚合物。与该奖项相关的研究使合成在主骨架中含有官能团的大分子，而不是与其他聚合技术相关的传统方法侧链。这项研究具有高度的变革性，它可能会为工业相关的可控自由基聚合提供一个令人兴奋的新平台。该奖项反映了美国国家科学基金会的法定使命，并通过使用基金会的知识价值和更广泛的影响审查标准进行评估，被认为值得支持。

项目成果

Quantitative, Regiospecific, and Stereoselective Radical Ring-Opening Polymerization of Monosaccharide Cyclic Ketene Acetals

• DOI: 10.1021/jacs.3c14244
• 发表时间: 2024-02-12
• 期刊: JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
• 影响因子: 15
• 作者: Jiang，Na-Chuan;Zhou，Zefeng;Niu，Jia
• 通讯作者: Niu，Jia

Cascade Reactions in Chain-Growth Polymerization

• DOI: 10.1021/acs.macromol.0c00417
• 发表时间: 2020-06
• 期刊: Macromolecules
• 影响因子: 5.5
• 作者: Jingsong Yuan;Wenqi Wang;Zefeng Zhou;Jia Niu

Degradable Vinyl Random Copolymers via Photocontrolled Radical Ring‐Opening Cascade Copolymerization**

通过光控自由基环的可降解乙烯基无规共聚物——开级联聚合**

• DOI: 10.1002/anie.202113302
• 发表时间: 2022
• 期刊: Angewandte Chemie International Edition
• 作者: Wang, Wenqi;Zhou, Zefeng;Sathe, Devavrat;Tang, Xuanting;Moran, Stephanie;Jin, Jing;Haeffner, Fredrik;Wang, Junpeng;Niu, Jia
• 通讯作者: Niu, Jia

Metathesis Cascade‐Triggered Depolymerization of Enyne Self‐Immolative Polymers**

复分解级联 — 引发烯炔自体解聚 — 自分解聚合物**

• DOI: 10.1002/anie.202108239
• 发表时间: 2021
• 期刊: Angewandte Chemie International Edition
• 作者: Yuan, Jingsong;Giardino, Gavin J.;Niu, Jia
• 通讯作者: Niu, Jia

Macrocyclic Allylic Sulfone as a Universal Comonomer in Organocatalyzed Photocontrolled Radical Copolymerization with Vinyl Monomers

• DOI: 10.1021/acs.macromol.2c02025
• 发表时间: 2023-01
• 期刊: Macromolecules
• 影响因子: 5.5
• 作者: Wenqi Wang;B. Rondon;Zeyu Wang;Junpeng Wang;Jia Niu