New Anions to Understand Recognition Chemistry and Drive Hierarchical Assembly with Cyanostars

新阴离子可帮助理解识别化学并利用 Cyanostars 驱动分层组装

• 批准号: 2105848
• 负责人: Amar Flood
• 金额: $ 49万
• 依托单位: Indiana University
• 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=2105848&HistoricalAwards=false
• 关键词: New; Anions; Understand; Recognition; Chemistry

With support of the Macromolecular, Supramolecular, and Nanochemistry Program in the Division of Chemistry, Professor Amar Flood of Indiana University will undertake a project to understand how to design molecular compounds to capture negatively charged ions (anions) and use them to synthesize more complex chemical compounds. The significance of studying anions stems from their many global impact areas spanning from the use of nitrate and phosphate as fertilizer, which impact food production and water quality, through to organic phosphates that are the workhorse anions in lithium ion batteries. The significance of anion-directed synthesis is inspired by Nature's use of bottom-up self-assembly and has the potential to impact the future of nano-manufacturing. The planned activity will benefit society by training graduate, undergraduate and postdoctoral coworkers in research, communication and collaboration both nationally and internationally. Inclusive practices will be developed that foster a culture that embraces diversity and equity in STEM (Science, Technology, Engineering and Mathematics). This project also has the potential to broaden understanding of anion-based chemistry for the public and undergraduate communities with videos and laboratory experiments. Outputs from this research are expected to offer benefits to researchers in other areas of chemistry, and to industries that need to manipulate anions.In this project on anion recognition and anion-driven hierarchical assembly, Professor Amar Flood and his team will synthesize a series of anions to control their modes of self-assembly, study their anion recognition by cyanostar macrocycles, and examine their mechanisms and cooperativities of self-assembly. The project has three Aims. Aim 1 seeks to determine how the sterics, electronics and charge of substituents on anions composed of trifluoroborates control formation of cyanostar complexes by using synthesis, titration data and crystal structures. Aim 2 aims to establish the correlation between the structures of substituted phosphates and their mechanisms of threading inside cyanostar macrocycles and to make threaded polymers with beads-on-a-string structures. Aim 3 seeks to expand the role of anions in hierarchical self-assembly synthesis by understanding how anions and cyanostar structures need to be programmed to produce specific architectures that include network gels, cyclic polymers, and spherical cages.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，印第安纳大学的Amar Flood教授将开展一个项目，了解如何设计分子化合物来捕获带负电的离子（阴离子），并利用它们合成更复杂的化学物质化合物。研究阴离子的重要性源于其许多全球影响领域，从影响粮食生产和水质的硝酸盐和磷酸盐肥料的使用，到锂离子电池中主要阴离子的有机磷酸盐。阴离子定向合成的重要性受到自然使用自下而上自组装的启发，并有可能影响纳米制造的未来。计划中的活动将通过培训研究生、本科生和博士后同事进行国内和国际的研究、交流和合作，造福社会。我们将开发包容性实践，培育一种拥抱 STEM（科学、技术、工程和数学）多样性和公平的文化。该项目还有可能通过视频和实验室实验扩大公众和本科生社区对阴离子化学的理解。这项研究的成果预计将为其他化学领域的研究人员以及需要操纵阴离子的行业带来益处。在这个关于阴离子识别和阴离子驱动的分层组装的项目中，Amar Flood 教授和他的团队将合成一系列阴离子来控制其自组装模式，研究氰星大环对阴离子的识别，并检查其自组装的机制和协同性。该项目有三个目标。目标 1 旨在通过使用合成、滴定数据和晶体结构来确定由三氟硼酸盐组成的阴离子上的空间、电子和取代基的电荷如何控制氰星配合物的形成。目标 2 旨在建立取代磷酸酯的结构与其在氰星大环内的螺纹机制之间的相关性，并制备具有串珠结构的螺纹聚合物。目标 3 旨在通过了解如何对阴离子和氰星结构进行编程以产生包括网络凝胶、环状聚合物和球形笼在内的特定架构，来扩大阴离子在分层自组装合成中的作用。该奖项反映了 NSF 的法定使命，并具有通过使用基金会的智力优点和更广泛的影响审查标准进行评估，被认为值得支持。

项目成果

Quantifying the barrier for the movement of cyclobis(paraquat- p -phenylene) over the dication of monopyrrolotetrathiafulvalene

量化环双（百草枯-对亚苯基）相对于单吡咯四硫富瓦烯的二价移动的障碍

• DOI: 10.1039/d1ob02263f
• 发表时间: 2022
• 期刊: Organic & Biomolecular Chemistry
• 影响因子: 3.2
• 作者: Kristensen, Rikke;Neumann, Mathias S.;Andersen, Sissel S.;Stein, Paul C.;Flood, Amar H.;Jeppesen, Jan O.
• 通讯作者: Jeppesen, Jan O.

Rigidity and Flexibility in Rotaxanes and Their Relatives; On Being Stubborn and Easy-Going

轮烷及其相关化合物的刚性和灵活性；

• DOI: 10.3389/fchem.2002.856173
• 发表时间: 2022
• 期刊: Frontiers in chemistry
• 影响因子: 5.5
• 作者: Fadler, R. E.;Flood, A. H.
• 通讯作者: Flood, A. H.

Receptor Induced Doping of Conjugated Polymer Transistors: A Strategy for Selective and Ultrasensitive Phosphate Detection in Complex Aqueous Environments

• DOI: 10.1002/aelm.202101353
• 发表时间: 2022-03
• 期刊: Advanced Electronic Materials
• 影响因子: 6.2
• 作者: Anthony R. Benasco;J. Tropp;Vikash Kaphle;Yusheng Chen;Wei Zhao;N. Eedugurala;T. Ng;A. Flood;J. Azoulay

High‐fidelity Recognition of Organotrifluoroborate Anions (R−BF 3 − ) as Designer Guest Molecules

高保真度识别有机三氟硼酸根阴离子 (R–BF 3–) 作为设计客体分子

• DOI: 10.1002/chem.202201584
• 发表时间: 2022
• 期刊: Chemistry – A European Journal
• 作者: Sheetz, Edward G.;Zhang, Zhao;Marogil, Alyssa;Che, Minwei;Pink, Maren;Carta, Veronica;Raghavachari, Krishnan;Flood, Amar H.
• 通讯作者: Flood, Amar H.

Steric Control over the Threading of Pyrophosphonates with One or Two Cyanostar Macrocycles during Pseudorotaxane Formation

• DOI: 10.1002/chem.202300899
• 发表时间: 2023-06-09
• 期刊: CHEMISTRY-A EUROPEAN JOURNAL
• 影响因子: 4.3
• 作者: Vogel，Julian;Chen，Yusheng;von Delius，Max
• 通讯作者: von Delius，Max