CAREER: Pnictogen Bonding in Solution: Developing Tools for the Self-assembly of Inverted Bilayer Membranes, Heteromolecular Dyads and Supramolecular Catalysts.

职业：溶液中的磷元素键合：开发倒置双层膜、异分子二元组和超分子催化剂自组装工具。

• 批准号: 1847878
• 负责人: Anthony Cozzolino
• 金额: $ 65.57万
• 依托单位: Texas Tech University
• 依托单位国家: 美国
• 项目类别: Continuing Grant
• 财政年份: 2019
• 资助国家: 美国
• 起止时间: 2019-05-15 至 2025-04-30
• 项目状态: 未结题
• 来源: https://www.nsf.gov/awardsearch/showAward?AWD_ID=1847878&HistoricalAwards=false
• 关键词: CAREER; Pnictogen; Bonding; Solution; Developing

Nature builds complexity through a clever combination of strong and weak chemical bonds/interactions. Weak interactions are used to assemble larger molecules, frameworks and scaffolds. For example, DNA strands are held together by hydrogen bonds to form a double-stranded structure (double helix). These hydrogen bonds can be broken relatively easily to allow separation of the strands when single-stranded DNA is needed for cell replication and protein synthesis. Hydrogen bonds are well studied and widely used not only in nature but also for controlling the assembly and properties of man-made materials. With the support of the Macromolecular, Supramolecular and Nanochemistry Program of the NSF Division of Chemistry, the research group of Professor Cozzolino at Texas Tech University studies weak interactions that lead to larger assemblies of molecules and explores their potential applications. Possible applications range from molecular sensing to crystal engineering, self-assembly of large polymers and gels to solar cells and liquid crystals - all of which are beneficial to society and the economy. This research project also engages high school and undergraduate students (including members of underrepresented groups) in the development of a code for the computational studies of weak interactions, providing an inquiry-based opportunity for involvement in STEM fields.This project seeks to gain a better fundamental understanding of pnictogen bonding and to develop this type of bonding into a useful and predictable supramolecular interaction. There are three main objectives in this project. The first objective is to prepare and study antimony(III) and bismuth(III) compounds that self-assemble through multiple, homo-complementary secondary bonding interactions. The research plan takes advantage of the unique ability of these pnictogens to support up to three interactions at three well-defined sigma-holes. By examining the influence of the pnictogen element, the polarity of the primary bond, the symmetry of the supporting ligand, bond angles, and steric factors on the secondary interactions, this project develops/refines a set of rules for designing supramolecular systems (e.g., inverted bilayer membranes and vesicles) that exploit pnictogen bonding. The second objective of the resesarch is to design and study pnictogen compounds that self-assemble through heteromolecular recognition events that are analogous to the self-assembly of Watson-Crick base pairs. The third objective is to design systems that bind anions through antimony(III) or bismuth(III) secondary bonding interactions. The experimental studies are complemented by the parameterization of a molecular mechanics force field to account for pnictogen secondary bonding interactions.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.

大自然通过强化学键和弱化学键/相互作用的巧妙组合来构建复杂性。弱相互作用用于组装较大的分子、框架和支架。例如，DNA链由氢键连接在一起形成双链结构（双螺旋）。当细胞复制和蛋白质合成需要单链DNA时，这些氢键可以相对容易地断开，从而使链分离。氢键不仅在自然界得到了广泛的研究和应用，而且在控制人造材料的组装和性能方面也得到了广泛的应用。在美国国家科学基金会化学部的大分子、超分子和纳米化学项目的支持下，德克萨斯理工大学Cozzolino教授的研究小组研究了导致更大分子组装的弱相互作用，并探索了它们的潜在应用。可能的应用范围从分子传感到晶体工程，从大型聚合物和凝胶的自组装到太阳能电池和液晶，所有这些都对社会和经济有益。该研究项目还让高中生和本科生（包括代表性不足群体的成员）参与弱相互作用计算研究代码的开发，为参与STEM领域提供了一个基于探究的机会。本项目旨在更好地了解氧原键合的基本原理，并将这种键合发展成一种有用的、可预测的超分子相互作用。这个项目有三个主要目标。第一个目标是制备和研究锑（III）和铋（III）化合物，它们通过多个同源互补的二级键相互作用自组装。该研究计划利用这些致病菌的独特能力，在三个明确定义的西格玛孔中支持多达三种相互作用。通过研究烟原元素、一级键的极性、支持配体的对称性、键角和立体因素对二级相互作用的影响，本项目开发/完善了一套用于设计利用烟原键的超分子系统（例如，倒置双层膜和囊泡）的规则。研究的第二个目标是设计和研究通过异分子识别事件自组装的烟原化合物，类似于沃森-克里克碱基对的自组装。第三个目标是设计通过锑（III）或铋（III）二级键相互作用结合阴离子的系统。实验研究补充了分子力学力场的参数化，以解释烟原的二级键相互作用。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。

项目成果

Triple-Pnictogen Bonding as a Tool for Supramolecular Assembly

三磷键合作为超分子组装的工具

• DOI: 10.1021/acs.inorgchem.9b02761
• 发表时间: 2019
• 期刊: Inorganic Chemistry
• 影响因子: 4.6
• 作者: Moaven, Shiva;Andrews, Miranda C.;Polaske, Thomas J.;Karl, Brian M.;Unruh, Daniel K.;Bosch, Eric;Bowling, Nathan P.;Cozzolino, Anthony F.
• 通讯作者: Cozzolino, Anthony F.

Pnictogen bonding with alkoxide cages: which pnictogen is best?

氮元素与醇盐笼键合：哪种氮元素最好？

• DOI: 10.1039/c9nj03648b
• 发表时间: 2019
• 期刊: New Journal of Chemistry
• 影响因子: 3.3
• 作者: Trubenstein, Henry J.;Moaven, Shiva;Vega, Maythe;Unruh, Daniel K.;Cozzolino, Anthony F.
• 通讯作者: Cozzolino, Anthony F.

Self-Assembly of Complementary Components Using a Tripodal Bismuth Compound: Pnictogen Bonding or Coordination Chemistry?

使用三足铋化合物自组装互补组分：磷元素键合或配位化学？

• DOI: 10.1021/acs.inorgchem.1c01232
• 发表时间: 2021
• 期刊: Inorganic Chemistry
• 影响因子: 4.6
• 作者: Moaven, Shiva;Watson, Brandon T.;Polaske, Thomas J.;Karl, Brian M.;Unruh, Daniel K.;Bowling, Nathan P.;Cozzolino, Anthony F.
• 通讯作者: Cozzolino, Anthony F.

The complicating role of pnictogen bond formation in the solution-phase and solid-state structures of the heavier pnictogen atranes

氮元素键形成在较重的氮元素阿特拉烷的溶液相和固态结构中的复杂作用

• DOI: 10.1039/d2dt01377k
• 发表时间: 2022
• 期刊: Dalton Transactions
• 影响因子: 4
• 作者: Moaven, Shiva;Villanueva, Olivia H.;Unruh, Daniel K.;Cozzolino, Anthony F.
• 通讯作者: Cozzolino, Anthony F.