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

大自然通过巧妙地结合强化学键和弱化学键/相互作用来构建复杂性。 弱相互作用用于组装较大的分子、框架和支架。 例如，DNA链通过氢键结合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裂以允许链分离。 氢键不仅在自然界中得到了很好的研究和广泛的应用，而且还用于控制人造材料的组装和性能。 在NSF化学部的大分子，超分子和纳米化学计划的支持下，德克萨斯理工大学Cozzolino教授的研究小组研究了导致较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。 该研究项目还邀请高中生和本科生（包括代表性不足的群体成员）参与弱相互作用计算研究的代码开发，为参与STEM领域提供基于调查的机会。该项目旨在更好地了解氮族元素键合的基本原理，并将这种键合发展为有用的和可预测的超分子相互作用。 该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）的化合物，自组装通过多个，同质互补的二级键的相互作用。 该研究计划利用这些氮素的独特能力，在三个明确定义的σ孔中支持多达三种相互作用。 通过研究氮族元素、初级键的极性、支持配体的对称性、键角和空间因素对次级相互作用的影响，该项目开发/完善了一套设计超分子体系的规则（例如，倒置的双层膜和囊泡），其利用氮族元素键合。 研究的第二个目标是设计和研究通过类似于Watson-Crick碱基对的自组装的异分子识别事件自组装的氮族化合物。 第三个目标是设计通过锑（III）或铋（III）次级键合相互作用结合阴离子的系统。 实验研究的补充是分子力学力场的参数化，以解释氮族元素的二级键合相互作用。该奖项反映了NSF的法定使命，并已被认为是值得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的支持。

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.