CAREER: Programming Molecules for Helix Formation and Self-Assembly into Helical Bundles

在化学系有机动力学项目的支持下，马萨诸塞大学阿默斯特分校的格雷戈里·N·图教授(Gregory N.Tew)将把这些设计扩展到螺旋结构，并将其自组装成螺旋束。他之前的工作证明了利用双层有序自组装的元膜设计两亲性片状结构的能力。具体地说，他将设计、合成和表征具有图案化两亲性螺旋结构的新型邻苯乙炔(PE)低聚物，这些结构被编程为自定向自组装成更高阶螺旋束。蛋白质使用一组弱的非共价力来构建强大而复杂的结构。这些作用力包括疏水-亲水图案化、氢键、pi-pi堆积、静电和偶极-偶极相互作用等。这些力量的具体和精确的放置标志着天然生物聚合物和合成大分子之间的最大区别之一。我们将研究这些两亲性杂序列通过将疏水结构域掩埋在远离极性环境的地方而自组装成螺旋束。这种将分子从二级结构元件定向自组装成螺旋束的方法将建立这种组装的规则，从而产生新的结构和性质。例如，设想了非生物的、从头设计的、人工金属酶类催化剂，并且在螺旋或二级结构水平上，将确定偶极-偶极相互作用对折叠稳定性的贡献。有机化学和高分子化学计划支持马萨诸塞大学阿默斯特分校的格雷戈里·N·图教授的研究，他的研究将协同结合计算和实验方法，对计算在非生物结构设计中的使用提供独特的见解。该教育计划将开发一个多层次的基础设施，为代表不足的少数族裔和社会经济困难的学生建立正式的指导关系。将通过强大的指导计划、课堂讲座和互动研讨会，开发针对代表性不足的少数族裔以及社会经济弱势本科生和研究生的领导力和科学管理课程。这类活动将使更多的人参与，并加强领导作用。这项工作的跨学科性质将在重要的科学领域培养学生，包括有机和高分子合成、超分子有机化学和生物物理学。

With the support of the Organic Dynamics Program in the Chemistry Division, Professor Gregory N. Tew of the University of Massachusetts- Amherst, whose previous work demonstrated the ability to design amphiphilic sheet-like structures from meta PEs that self-assembled with bilayer order, will now extend these designs to helical structures and their self-assembly into helical bundles. Specifically, he will design, synthesize, and characterize new ortho phenylene ethynylene (PE) oligomers with patterned amphiphilic helical structures programmed for self-directed self-assembly into higher order helical bundles. Proteins use a collection of weak non-covalent forces to build strong and complex structures. These forces include hydrophobic-hydrophilic patterning, hydrogen bonding, pi-pi stacking, electrostatics, and dipole-dipole interactions to name a few. The specific and precise placement of these forces marks one of the biggest differences between native biopolymers and synthetic macromolecules. The self-assembly of these amphiphilic hetero-sequences into helical bundles by burying the hydrophobic domains away from polar environments will be studied. This approach to programming molecules for directed self-assembly beyond secondary structural elements into helical bundles would establish the rules for this assembly leading to novel structures and properties. For example, abiotic, de novo designed, artificial metallo-enzyme-like catalysts are envisaged, and, at the helix, or secondary structure level, the contribution of dipole-dipole interactions toward folding stability will be determined. The Organic and Macromolecular Chemistry Program supports Professor Gregory N. Tew of the University of Massachusetts- Amherst whose research will synergistically combine computational and experimental methods to provide unique insight on the use of computation in abiotic structural design. The educational program will develop a multi-tiered infrastructure to formalize mentoring relationships for underrepresented minority and socio-economically disadvantaged students. Leadership and scientific management programs targeting underrepresented minority as well as socio-economically disadvantaged undergraduate and graduate students will be developed through a strong mentoring program, class lectures, and interactive workshops. Such activities will enable greater participation and strengthen leadership roles. The interdisciplinary nature of the work will train students in important scientific areas including organic and macromolecular synthesis, supramolecular organic chemistry, and biophysics.