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Engineering cyanine aggregation and self-assembly to access exceptionally red-shifted organic chromophores

设计花青聚集和自组装以获得异常红移的有机发色团

基本信息

批准号：
2204263
负责人：
Ellen Sletten
金额：
$ 60万
依托单位：
University of California-Los Angeles
依托单位国家：
美国
项目类别：
Continuing Grant
财政年份：
2022
资助国家：
美国
起止时间：
2022-08-01 至 2025-07-31
项目状态：
未结题

来源：
https://www.nsf.gov/awardsearch/showAward?AWD_ID=2204263&HistoricalAwards=false
关键词：
Engineering cyanine aggregation self assembly

项目摘要

With the support of the Macromolecular, Supramolecular and Nanochemistry program in the Division of Chemistry, Professors Ellen M. Sletten and Justin R. Caram of the University of California-Los Angeles are developing new fluorescent chemical compounds that emit light in the shortwave infrared region of the electromagnetic spectrum. Shortwave infrared waves are invisible to the human eye but can be detected by special cameras. A major advantage of these waves is that they can pass through tissue and be used for imaging in complex organisms. Additional opportunities are also seen in improving long-haul telecommunications of fiber optical networks. In the first part of this research, small organic molecules will be prepared and structurally modified to achieve desired absorption and emission properties in the infrared region. These photophysical properties will then be amplified several orders of magnitude through self-assembly in solution yielding exceptionally red-shifted aggregates. To aid in experimental design and speed discovery, computational modelling will be used to correlate the structure of these aggregates with their electronic properties. The research activities associated with this award will increase broadening participation and enable training of high school, undergraduate, and graduate students in synthetic organic chemistry and spectroscopy. The creation of a PHOTONbooth and participation in “Illuminating the World of Molecules” events will provide attractive strategies to generate public interest in science and introduce STEM concepts to participants in the greater Los Angeles area. This research will focus on cyanine aggregation and self-assembly to access exceptionally red-shifted organic chromophores for the shortwave infrared region (SWIR) region of the electromagnetic spectrum. In the first objective, modified monomeric cyanine dyes will be synthesized through heteroatom substitution and lengthening of the polymethine chain. This structural modification will promote SWIR J-aggregates above 1300 nm and facilitate investigation of two of the current limitations of such aggregates, namely low quantum yield (objective 2) and their need to be stabilized in a matrix or nanoparticle for use in dilute/complex environments (objective 3). New structures will be investigated using circular and linear dichroism and modelled computationally to access excitonic structures and correlate them with photophysical properties. This work, if successful, will provide fundamental insight on the chromophore-chromophore coupling and long-range order necessary for emissive, band edge J-aggregate formation. The organic SWIR J-aggregates associated with this work have the potential to develop inexpensive, environmentally friendly and scalable nanotechnology in a wavelength regime deemed to be eye safe.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.

在化学系高分子、超分子和纳米化学项目的支持下，加州大学洛杉矶分校的 Ellen M. Sletten 和 Justin R. Caram 教授正在开发新型荧光化合物，这些化合物可在电磁波谱的短波红外区域发光。短波红外波是人眼看不见的，但可以被特殊相机检测到。这些波的一个主要优点是它们可以穿过组织并用于复杂生物体的成像。在改善光纤网络的长途电信方面也存在其他机会。在这项研究的第一部分中，将制备有机小分子并进行结构修饰，以实现红外区域所需的吸收和发射特性。然后，通过在溶液中自组装，这些光物理性质将被放大几个数量级，产生异常红移的聚集体。为了帮助实验设计和加速发现，将使用计算模型将这些聚集体的结构与其电子特性相关联。与该奖项相关的研究活动将扩大参与范围，并为高中生、本科生和研究生提供合成有机化学和光谱学方面的培训。创建 PHOTON 展位并参与“照亮分子世界”活动将为激发公众对科学的兴趣并向大洛杉矶地区的参与者介绍 STEM 概念提供有吸引力的策略。这项研究将重点关注花青聚集和自组装，以获得电磁波谱短波红外区 (SWIR) 区域异常红移的有机发色团。第一个目标是通过杂原子取代和延长聚次甲基链来合成改性单体花青染料。这种结构修饰将促进 SWIR J 聚集体超过 1300 nm，并有助于研究此类聚集体当前的两个局限性，即低量子产率（目标 2）以及它们需要稳定在基质或纳米颗粒中以用于稀释/复杂环境（目标 3）。新结构将使用圆形和线性二色性进行研究，并进行计算建模以获取激子结构并将其与光物理性质相关联。这项工作如果成功，将为发色团-发色团耦合和发射带边缘 J-聚集体形成所需的长程有序提供基本见解。与这项工作相关的有机 SWIR J 聚集体有潜力在被认为对眼睛安全的波长范围内开发廉价、环保和可扩展的纳米技术。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影响审查标准进行评估，被认为值得支持。