Fundamental Studies of the Hydrogen Bond Enhanced Halogen Bond (HBeXB) for Molecular Folding and Anion Transport

蒙大拿大学的Orion Berryman教授得到了大分子、超分子和纳米化学（MSN）以及化学系化学结构、动力学和机制B （CSDM-B）项目的支持，设计了控制链状分子如何形成管状螺旋结构（折叠体）的方法。该项目利用了最近的一项观察，即在链分子中合理地放置氢键可以使分子折叠，模仿蛋白质和核酸的折叠能力。特殊的功能单元被战略性地放置在分子管中，以允许阴离子的运输。该项目有助于确定有效地将氢键结合到分子设计中的要求，从而产生一种用于分子识别和自组装的新工具。该项目预计将影响许多领域，如药物开发、分离科学、环境修复、生物工程、材料开发和传感。在这项研究的过程中，研究生、本科生和高中的学生都接受了先进化学研究方法的培训。此外，Berryman博士和他的团队将在当地的科学博物馆建立一个永久性的模块，以及一个巡回展览，以使K-8学生和公众熟悉化学概念。该项目建立在Berryman教授和他的合作者最近的观察基础上，他们策略性地将氢键和卤素键放在链式分子上，协同诱导折叠成螺旋结构。初步溶液、计算和单晶衍射研究表明，氢键增强卤素键重组了分子结构，加强了结合，并且在溶液中具有足够的鲁棒性。该项目探讨了氢键类型、距离和角度对卤素键强度、结构和方向性的影响。这项建议的具体目标有三个方面。该团队试图量化近端氢键对卤素键强度和方向性的影响。它们将确定分子内氢键如何影响卤素键的选择性。最后，它们会促进折叠和阴离子传输，氢键增强卤素键。一套仪器测量技术和DFT计算将被用来支持研究工作。产生协同作用的机制原则上可以应用于氢键和卤素键以外的非共价相互作用对，为开发一套分子工程工具铺平了道路。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。

Professor Orion Berryman of the University of Montana is supported by the Macromolecular, Supramolecular, and Nanochemistry (MSN) and the Chemical Structure, Dynamics, and Mechanisms B (CSDM-B) Programs of the Division of Chemistry to devise means to control how chain molecules are shaped into tubular helical structures (foldamers). The project exploits a recent observation that a hydrogen bond that is judicially placed in a chain molecule can cause the molecule to fold, mimicking the folding ability of proteins and nucleic acids. Special functional units are strategically placed inside the molecular tube to allow for the transport of anions. The project helps define the requirements to efficiently incorporate the hydrogen bonding into molecular design, producing a new tool for molecular recognition and self-assembly. The project is expected to impact many fields, such as drug development, separation science, environmental remediation, bioengineering, materials development, and sensing. During the course of this research, students at the graduate, undergraduate and high school levels are trained in advanced chemistry research methods. In addition, Dr. Berryman and his team will establish a permanent module at a local science museum as well as a travelling exhibit to familiarize K-8 students and members of the public with chemistry concepts. The project builds on a recent observation by Professor Berryman and his collaborators that strategically placed hydrogen bonds and halogen bonds on chain molecules synergistically induce folding into helical structures. Preliminary solution, computational and single crystal diffraction studies show that hydrogen bond enhanced halogen bonds reorganize molecular structure, strengthen binding, and are robust enough to be measured in solution. The project explores the effect of the hydrogen bond type, distance and angle on the strength, structure and directionality of the halogen bond. The specific aims of this proposal are threefold. The team seeks to quantify the influence of a proximal hydrogen bond on halogen bond strength and directionality. They will determine how halogen bonding selectivity is influenced by an intramolecular hydrogen bond. Finally, they will promote folding and anion transport with the hydrogen bond enhanced halogen bond. A suite of instrumental measurement techniques and DFT calculations will be employed to support the research effort. The mechanism causing the synergistic interaction can, in principle, be applied to pairs of noncovalent interactions other than hydrogen bonding and halogen bonding, which paves the way for the development of a set of tools for molecular engineering.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.