New advances in cyclopentadiene based materials

环戊二烯基材料新进展

• 批准号: 2204077
• 负责人: Javier Read de Alaniz
• 金额: $ 49.5万
• 依托单位: University of California-Santa Barbara
• 依托单位国家: 美国
• 项目类别: Standard Grant
• 财政年份: 2022
• 资助国家: 美国
• 起止时间: 2022-10-01 至 2025-09-30
• 项目状态: 未结题
• 来源: https://www.nsf.gov/awardsearch/showAward?AWD_ID=2204077&HistoricalAwards=false
• 关键词: New; advances; cyclopentadiene; based; materials

With the support of the Macromolecular, Supramolecular and Nanochemistry Program in the Division of Chemistry, Professor Read de Alaniz of University of California at Santa Barbara will construct polymers capable of self-healing and de-polymerizing using “click” chemistry that leverages non-toxic, metal-free, and inexpensive building blocks. To translate this chemistry for biological utility an aqueous soluble photo-click platform will be developed. The successful realization of this goal will provide the high-resolution spatial control over chemical functionalization required to pattern biomaterials for applications in 3D printing and tissue engineering. Simultaneously this project aims to provide outstanding educational opportunities for students at multiple levels, with a particular focus on those from underrepresented groups. A key broader impact aspect of the proposed research will be the highly interdisciplinary nature of this project that will train and educate the next-generation scientists with broad multidisciplinary skills in organic and polymer synthesis and characterization. Outreach activities leveraging virtual/hybrid educational science talks and lessons for 1st and 2nd grade students will also be developed. The structure will allow young students to meet scientists and provide graduate students an opportunity to communicate their work to a broader audience. While the value of Diels–Alder “click” chemistry in material synthesis is well-established, exploration of the strategy for constructing homopolymers using a single-component monomer system is almost completely unknown. Through the proposed studies, access to telechelic cyclopentadiene monomers that are otherwise impossible to prepare will become accessible. Furthermore, the development of the proposed reactions will broadly increase our fundamental understanding of this new approach that have important applications in many fields of chemistry. By developing a light-triggered approach to access cyclopentadiene, the new strategy will also provide the high-resolution spatial control over chemical functionalization required to pattern biomaterials and move beyond current state of the art. Altogether, the one- and two-component cyclopentadiene based materials will address a long-standing challenge of preparing homopolymers with a single component telechelic monomer, and serve as a valuable new addition to the arsenal of available Diels–Alder “click” reactions for preparing functional biomaterials with spatial and temporal control. To accomplish this work, the following specific aims will be pursued: (1) utilize on-demand, metal-free deprotection of norbornadiene with tetrazine to access and isolate cyclopentadiene based monomers for single-component Diels–Alder-based polymerization and (2) develop a photo-click platform based on photolabile norbornadiene–cyclopentadienone adducts for spatiotemporal introduction of cyclopentadiene in materials.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.

在化学系大分子、超分子和纳米化学项目的支持下，加州大学圣巴巴拉分校的Read de Alaniz教授将利用无毒、无金属和廉价的构建单元，利用“点击”化学构建能够自我修复和解聚的聚合物。为了将这种化学转化为生物学效用，将开发水溶性光点击平台。这一目标的成功实现将为3D打印和组织工程中的生物材料图案化所需的化学功能化提供高分辨率的空间控制。同时，该项目旨在为学生提供多层次的良好教育机会，特别关注代表性不足的群体。 拟议研究的一个关键的更广泛的影响方面将是该项目的高度跨学科性质，该项目将培训和教育下一代科学家，他们在有机和聚合物合成和表征方面具有广泛的多学科技能。还将为一年级和二年级学生开展利用虚拟/混合教育科学讲座和课程的外联活动。这一结构将使年轻学生能够与科学家见面，并为研究生提供一个向更广泛的受众宣传其工作的机会。虽然狄尔斯-阿尔德“点击”化学在材料合成中的价值是公认的，但使用单组分单体系统构建均聚物的策略的探索几乎是完全未知的。通过拟议的研究，将可以获得以其他方式无法制备的遥爪环戊二烯单体。此外，所提出的反应的发展将广泛增加我们对这种在许多化学领域具有重要应用的新方法的基本理解。通过开发一种光触发的方法来获取环戊二烯，新的策略还将提供对生物材料图案化所需的化学功能化的高分辨率空间控制，并超越当前的技术水平。总之，基于单组分和双组分环戊二烯的材料将解决用单组分遥爪单体制备均聚物的长期挑战，并作为一个有价值的新的除了可用的狄尔斯-阿尔德“点击”反应，用于制备功能性生物材料的空间和时间控制的武器库。为完成这项工作，将努力实现以下具体目标：（1）按需利用，用四嗪对降冰片二烯进行无金属脱保护以获得和分离用于单组分Diels-Alder基聚合的环戊二烯基单体，和（2）开发基于光不稳定降冰片二烯的光点击平台。用于在材料中时空引入环戊二烯的环戊二烯烯酮加合物。该奖项反映了NSF的法定使命，并被认为值得支持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。

项目成果

Diels‐Alder Photoclick Patterning of Extracellular Matrix for Spatially Controlled Cell Behaviors

Diels-Alder 细胞外基质光点击图案化，用于空间控制细胞行为

• DOI: 10.1002/adma.202303453
• 发表时间: 2023
• 期刊: Advanced Materials
• 影响因子: 29.4
• 作者: Bailey, Sophia J.;Hopkins, Erik;Baxter, Naomi;Whitehead, Isobel;Read de Alaniz, Javier;Wilson, Maxwell Z.
• 通讯作者: Wilson, Maxwell Z.

Controlled Synthesis of a Homopolymer Network Using a Well-Defined Single-Component Diels–Alder Cyclopentadiene Monomer

使用明确的单组分 Diels-Alder 环戊二烯单体控制合成均聚物网络

• DOI: 10.1021/jacs.2c11416
• 发表时间: 2023
• 期刊: Journal of the American Chemical Society
• 影响因子: 15
• 作者: Tran, Thi M.;de Alaniz, Javier Read
• 通讯作者: de Alaniz, Javier Read