New advances in cyclopentadiene based materials

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块，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用途，将开发一种水溶性的照片点击平台。这一目标的成功实现将为3D打印和组织工程应用所需的生物材料提供高分辨率的化学功能化空间控制。同时，该项目旨在为不同层次的学生提供优秀的教育机会，特别关注那些来自弱势群体的学生。拟议研究的一个关键的更广泛的影响方面将是这个项目的高度跨学科性质，它将培养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发利用虚拟/混合教育科学讲座和课程的外展活动。这种结构将允许年轻学生与科学家见面，并为研究生提供向更广泛的受众交流他们的工作的机会。虽然Diels-Alder“点击”化学在材料合成中的价值是公认的，但使用单组分单体体系构建均聚物的策略探索几乎完全未知。通过提出的研究，获得远旋环戊二烯单体，否则不可能制备将成为可能。此外，所提出的反应的发展将广泛地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，单组分和双组分环戊二烯基材料将解决用单组分远旋单体制备均聚物的长期挑战，并作为可用的Diels-Alder“点击”反应库的宝贵新成员，用于制备具有空间和时间控制的功能性生物材料。为了完成这项工作，将追求以下具体目标：(1)利用四嗪对降冰片二烯的按需无金属脱保护，获得并分离环戊二烯单体，用于单组分diels - alder基聚合；(2)开发基于可光性降冰片二烯-环戊二酮加合物的照片点击平台，用于在材料中时空引入环戊二烯。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。

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.