Functional Nanotubes from Self-Assembled Bis-Urea Macrocycles

自组装双脲大环化合物的功能纳米管

• 批准号: 1904386
• 负责人: Linda Shimizu
• 金额: $ 46万
• 依托单位: University of South Carolina at Columbia
• 依托单位国家: 美国
• 项目类别: Standard Grant
• 财政年份: 2019
• 资助国家: 美国
• 起止时间: 2019-08-01 至 2023-01-31
• 项目状态: 已结题
• 来源: https://www.nsf.gov/awardsearch/showAward?AWD_ID=1904386&HistoricalAwards=false
• 关键词: Functional; Nanotubes; Self; Assembled; Bis

Nature employs self-assembly approaches to control the size and shape of biological structures for performing specific functions. Examples include protein channels and enzymes. A protein channel is formed by a protein that folds into a hollow tubular structure and spans across a membrane to allow passage of small molecules or ions from one side of a membrane to the other side through the channel. An enzyme is a protein that folds into a 3-dimensional structure to create a pocket of specific size and shape for binding and converting target molecules into desired chemical products. Inspired by Nature, Professor Linda Shimizu of the University of South Carolina makes small donut-shaped molecules that assemble in high fidelity into straw like structures called nanotubes. These nanotubes have tiny 1-dimensional channels of less than a nanometer (about 1/1000 times of the width of a strand of hair) in diameter. The Shimizu group conducts research to understand how gases and small molecules are organized and move through these tiny channels. Her research group also uses these nanotubes to restrict how molecules in these channels are oriented with respect to one another, which alters how these trapped guests can react. Fundamental knowledge to be gained from this research could have important implications in separation technologies, flow reactors and the development of new synthetic methods. The broad research approach provides a challenging and interdisciplinary environment to train a diverse group of graduate students as well as provides first research experiences for undergraduates and high school students. In addition, this award supports a chemistry outreach program that broadly promotes public interest in science by bringing chemists into South Carolina K-12 classrooms of high minority enrollment middle schools and high schools. These school visits are intended to showcase the scientific method, highlight cutting edge research, and foster interest in chemistry and in the natural sciences.Work in Professor Linda Shimizu's laboratory, supported by the Macromolecular, Supramolecular and Nanochemistry Program at the National Science Foundation, utilizes the controlled assembly of bis-urea macrocycles to afford functional tubular assemblies to probe fundamental questions. This research investigates structure-property relationship of macrocycles and linear analogues that contain triphenylamines, benzophenones, and other organic triplet sensitizers. After UV-irradiation, these assemblies form radicals within the walls of the nanotubes. The quantity, persistence and properties of these radicals are related to their structure and organization. In this project, the Shimizu group 1) studies the assemblies to understand the origin of the radical stability; 2) probes diffusion within the nanochannels; 3) evaluates how radicals in the channel walls interact with guests encapsulated within the channels; 4) evaluates the assemblies of triplet sensitizers in oxygenated solutions to determine their efficiency at forming reactive oxygen species; and 5) studies the ability of the nanoreactors to facilitate photooxidations, photocycloadditions and photopolymerization reactions in solution. The knowledge acquired should lead to new predictive tools to determine when persistent radicals will form as well as afford a better understanding of the effects of confinement on reactivity. These results should lead to an increase in structural diversity of organic radicals, which are of interest as molecular magnets, as probes in biological systems, for polarizing agents and as radical initiators for polymerization.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.

大自然采用自组装方法来控制生物结构的大小和形状，以执行特定功能。 例子包括蛋白质通道和酶。 蛋白质通道是由蛋白质形成的，该蛋白质会折叠成空心的管状结构并跨膜跨膜，以使小分子或离子从膜的一侧通过通道传递到另一侧。 酶是一种蛋白质，可折叠成3维结构，以创建一个特异性和形状的袋，以结合和转化目标分子为所需的化学产物。 受自然启发的启发，南卡罗来纳大学的琳达·辛祖（Linda Shimizu）教授制作了小甜甜圈形的分子，将高保真组装成稻草，如纳米管的结构。这些纳米管的直径小于纳米的小于纳米的小于1/1000倍的1/1000倍。 Shimizu组进行研究，以了解如何组织气体和小分子并在这些微小的通道中移动。她的研究小组还使用这些纳米管来限制这些渠道中的分子如何相对于彼此的定向，从而改变了这些被困的客人如何反应。 从这项研究中获得的基本知识可能对分离技术，流动反应堆和新合成方法的发展具有重要意义。广泛的研究方法提供了一个具有挑战性的跨学科环境，以培训一群多样的研究生，并为大学生和高中生提供首次研究经验。 此外，该奖项支持化学外展计划，该计划通过将化学家带入南卡罗来纳州K-12教室，该课程广泛地促进了公众对科学的兴趣。 These school visits are intended to showcase the scientific method, highlight cutting edge research, and foster interest in chemistry and in the natural sciences.Work in Professor Linda Shimizu's laboratory, supported by the Macromolecular, Supramolecular and Nanochemistry Program at the National Science Foundation, utilizes the controlled assembly of bis-urea macrocycles to afford functional tubular assemblies to probe fundamental 问题。这项研究研究了含有三苯胺，苯苯甲酮和其他有机三重态敏化剂的大环和线性类似物的结构 - 核关系关系。紫外线辐照后，这些组件在纳米管壁内形成自由基。 这些激进分子的数量，持久性和特性与它们的结构和组织有关。 在这个项目中，Shimizu组1）研究组合以了解根本稳定的起源； 2）探针在纳米通道内的扩散； 3）评估通道壁中的自由基如何与封装在通道内的来宾相互作用； 4）评估三重溶液中三重态敏化剂的组件，以确定它们在形成活性氧中的效率； 5）研究纳米反应器促进溶液中光氧化，光细胞载体和光聚合反应的能力。获取的知识应导致新的预测工具，以确定持续的激进分子何时会形成，并可以更好地理解限制对反应性的影响。 这些结果应导致有机自由基的结构多样性增加，这是分子磁铁，作为生物系统中的探针，两极分化剂和聚合的激进启动者。该奖项反映了NSF的法定任务，并被认为是通过基金会的知识优点和广泛的范围来评估的。

项目成果

Anti‐kooperative Selbstorganisation mit aufrechterhaltener Emission reguliert durch konformationelle und sterische Effekte

反合作自组织，通过信息和保密效应对排放进行监管

• DOI: 10.1002/ange.202200390
• 发表时间: 2022
• 期刊: Angewandte Chemie
• 作者: Helmers, Ingo;Hossain, Muhammad Saddam;Bäumer, Nils;Wesarg, Paul;Soberats, Bartolome;Shimizu, Linda S.;Fernández, Gustavo
• 通讯作者: Fernández, Gustavo

Guest Inclusion Modulates Concentration and Persistence of Photogenerated Radicals in Assembled Triphenylamine Macrocycles

• DOI: 10.1021/jacs.9b11518
• 发表时间: 2020-01-08
• 期刊: JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
• 影响因子: 15
• 作者: Sindt, Ammon J.;DeHaven, Baillie A.;Shimizu, Linda S.
• 通讯作者: Shimizu, Linda S.

Multi-dimensional copper(I) and silver (I) coordination polymers assembled with a pyridyl bis-urea macrocyclic ligand

• DOI: 10.1016/j.poly.2021.115170
• 发表时间: 2021-06
• 期刊: Polyhedron
• 影响因子: 2.6
• 作者: Bozumeh Som;Mark D. Smith;Linda S. Shimizu

Structure–property investigations in urea tethered iodinated triphenylamines

尿素束缚的碘化三苯胺的结构和性质研究

• DOI: 10.1039/d2cp01856j
• 发表时间: 2022
• 期刊: Physical Chemistry Chemical Physics
• 影响因子: 3.3
• 作者: Hossain, Muhammad Saddam;Ahmed, Fiaz;Karakalos, Stavros G.;Smith, Mark D.;Pant, Namrata;Garashchuk, Sophya;Greytak, Andrew B.;Docampo, Pablo;Shimizu, Linda S.
• 通讯作者: Shimizu, Linda S.

Selective host–guest chemistry, self-assembly and conformational preferences of m -xylene macrocycles probed by ion-mobility spectrometry mass spectrometry

通过离子淌度质谱法探测间二甲苯大环的选择性主客体化学、自组装和构象偏好

• DOI: 10.1039/c9cp06938k
• 发表时间: 2020
• 期刊: Physical Chemistry Chemical Physics
• 影响因子: 3.3
• 作者: Link, Benjamin A.;Sindt, Ammon J.;Shimizu, Linda S.;Do, Thanh D.
• 通讯作者: Do, Thanh D.