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Boron Dipyrromethene Photocages for Mild and Selective Light-Driven Polymer Chemistry

用于温和选择性光驱动聚合物化学的硼二吡咯亚甲基光笼

基本信息

批准号：
2107877
负责人：
Zachariah Page
金额：
$ 45万
依托单位：
University of Texas at Austin
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：
2021-09-01 至 2024-08-31
项目状态：
已结题

来源：
https://www.nsf.gov/awardsearch/showAward?AWD_ID=2107877&HistoricalAwards=false
关键词：
Boron Dipyrromethene Photocages Mild Selective

项目摘要

With the support of the Macromolecular, Supramolecular and Nanochemistry Program in the Division of Chemistry, Dr. Zachariah A. Page of the University of Texas at Austin is developing light-selective boron containing dyes as catalysts for the synthesis of recyclable polymers. The structure and reactivity of these dyes will first be optimized through systematic studies in order to understand their electronic and chemical properties. Successful candidates will then be used to prepare dynamic poly(urethane) networks using light. Poly(urethanes) are an important class of plastics which is extensively used to make coatings, adhesives and sealants. The light that will connect individual building units into long polymer chains will also be used to disconnect them one at a time by simple changing its wavelength and intensity. Hence, this light-toggling will lead to recyclability. Studies associated with this research have the potential to provide fundamental chemistry knowledge associated with light controlled polymerization and how it can be used to efficiently prepare recyclable polymeric materials. As such, chemistry emphasized in the proposed work also addresses the current and ongoing global issue of plastic waste accumulation. This research will provide new opportunities for undergraduate and graduate student training in polymer chemistry. Diversity seminars will be initiated, as well as development of a new course in undergraduate peer mentoring for organic chemistry. Moreover, the work will also positively support public education and outreach. Dr. Page will create an interdisciplinary polymer teaching module on light as a tool in science to engage middle and high school students from institutions with disproportionate populations of minorities in STEM fields. Outreach activities involving intercollegiate student interactions with North Carolina State University will also be established. This research will focus on development of wavelength-selective boron dipyrromethene (BODIPY) photocages bearing benzyl sulfides as catalysts for controlled anionic photoredox polymerization. The underlying strategy uses mild reaction conditions and visible-to-NIR (near infrared) light to reversibly cleave BODIPY derivatives and generate strong nucleophiles (thiolate anions) that can initiate polymerization. Specifically, the preparation of recyclable dynamic polymer networks bearing (di)thiourethane and imine/hydrazone/oxime functionality will be emphasized as soft materials that remain largely unexamined using light-driven approaches. Strong emphasis will be placed on the optimization of reactivities and kinetics through structural modification of BODIPY-based dyes in order to understand their electronic properties and responses to light with different wavelengths and intensities. Proposed structure-reactivity studies could provide fundamental chemistry knowledge associated with the synthesis of recyclable polymers using photoredox initiated polymerization. The proposed ability to control the polymerization by different light intensities and wavelengths has the potential to permit the precise 2D-patterning and 3D-printing of polymeric materials, with long-term potential scientific impact upon tissue engineering, robotics, optical coatings and image sensing.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，Zachariah A.德克萨斯大学奥斯汀分校的佩奇正在开发光选择性含硼染料，作为合成可回收聚合物的催化剂。这些染料的结构和反应性将首先通过系统的研究进行优化，以了解它们的电子和化学性质。成功的候选者将被用于使用光制备动态聚氨酯网络。聚（乙烯）是一类重要的塑料，广泛用于制造涂料、粘合剂和密封剂。将单个建筑单元连接成长聚合物链的光也将通过简单地改变其波长和强度来一次一个地断开它们。因此，这种轻切换将导致可回收性。与这项研究相关的研究有可能提供与光控聚合相关的基础化学知识，以及如何使用它来有效地制备可回收的聚合物材料。因此，拟议工作中强调的化学也解决了当前和持续的全球塑料废物积累问题。这项研究将为高分子化学的本科生和研究生培养提供新的机会。多样性研讨会将启动，以及开发一个新的课程，在本科生同行指导有机化学。此外，这项工作还将积极支持公众教育和外联。 Page博士将创建一个跨学科的聚合物教学模块，将光作为科学工具，吸引来自STEM领域少数民族人口不成比例的机构的中学生。还将建立涉及与北卡罗来纳州州立大学进行校际学生互动的外联活动。本研究将致力于开发具有波长选择性的二吡咯亚甲基硼（BODIPY）光笼，并将其作为可控阴离子光氧化还原聚合的催化剂。潜在的策略使用温和的反应条件和可见光至NIR（近红外）光来可逆地裂解BODIPY衍生物并产生可以引发聚合的强亲核试剂（硫醇盐阴离子）。具体而言，可回收的动态聚合物网络轴承（二）硫代氨基甲酸酯和亚胺/腙/肟功能的制备将被强调为软材料，在很大程度上保持未检查使用光驱动的方法。重点将放在通过BODIPY染料的结构修饰优化反应性和动力学，以了解其电子特性和对不同波长和强度的光的响应。建议的结构反应性研究可以提供与使用光氧化还原引发的聚合反应的可回收聚合物的合成相关的基本化学知识。所提出的通过不同光强度和波长控制聚合的能力具有允许聚合物材料的精确2D图案化和3D打印的潜力，对组织工程、机器人技术、该奖项反映了NSF的法定使命，并通过使用基金会的智力价值和更广泛的评估被认为值得支持。影响审查标准。