Enforced Folding of Oligo(phenylene ethynylenes)

寡核苷酸（亚苯基亚乙炔基）的强制折叠

• 批准号: 0314577
• 负责人: Bing Gong
• 金额: $ 42万
• 依托单位: SUNY at Buffalo
• 依托单位国家: 美国
• 项目类别: Continuing Grant
• 财政年份: 2003
• 资助国家: 美国
• 起止时间: 2003-07-15 至 2007-06-30
• 项目状态: 已结题
• 来源: https://www.nsf.gov/awardsearch/showAward?AWD_ID=0314577&HistoricalAwards=false
• 关键词: Enforced; Folding; Oligo; phenylene; ethynylenes

Unnatural oligomers and polymers consisting of benzene rings linked by ethynyl groups (phenyleneethynylenes) are designed to fold into porous helical structures, enforced by localized intramolecular hydrogen bonds. An oligomer with a sufficiently long backbone folds back on itself, leading to left- and right-handed helices. Such a backbone-based helical programming affords stable helical structures regardless of structural variation of the side groups that determine the outside surface properties. The interior of the resulting helices is lined by aromatic hydrogen atoms, making these tubular cavities rather hydrophobic. The internal diameters of the helices are adjustable (8 angstrom to 40 angstrom and larger), providing access to novel unnatural folding nanotubes with adjustable interior cavities. Furthermore, these unnatural foldamers have backbones that are both helical and unsaturated, features that may endow unusual and useful physical and chemical properties. The design and synthesis of helices with superhydrophobic (fluorinated) or amphiphilic interior cavities, resolution of enantiomers, and induction of helical twist sense by chiral side chains and chiral solvents are also addressed.Nanosized cavities and channels have numerous potential applications in catalysis, separations, nanodevices (sensors, fluidics, etc.), nanoscaffolds for building larger structures, and design of other nanoporous materials. With the support of the Organic and Macromolecular Chemistry Program, Professor Bing Gong, of the Department of Chemistry at the State University of New York - Buffalo and Professor Xiao Cheng Zeng, of the Department of Chemistry at the University of Nebraska - Lincoln, are studying the synthesis and properties of carbon-based molecules designed to fold selectively and efficiently into helical structures. These helical structures contain nanosized channels of adjustable size and functionality, allowing tuning of their properties and their interactions with other molecules. These studies also provide fundamental information about the folding of other large molecules, both natural and unnatural, Students carrying out these interdisciplinary studies gain skills in organic synthesis, bioorganic and supramolecular organic chemistry, and theoretical chemistry.

由乙炔基（亚苯基乙炔基）连接的苯环组成的非天然低聚物和聚合物被设计成折叠成多孔螺旋结构，由局部分子内氢键强化。具有足够长主链的低聚物会自行折叠，形成左旋和右旋螺旋。这种基于主链的螺旋编程提供了稳定的螺旋结构，而不管决定外表面特性的侧基的结构变化如何。由此产生的螺旋内部排列有芳香族氢原子，使这些管状空腔相当疏水。螺旋的内径是可调节的（8埃至40埃或更大），从而提供了具有可调节内腔的新型非自然折叠纳米管。此外，这些非自然折叠体具有螺旋且不饱和的主链，这些特征可能赋予不寻常且有用的物理和化学性质。还讨论了具有超疏水（氟化）或两亲性内部空腔的螺旋的设计和合成、对映体的拆分以及通过手性侧链和手性溶剂诱导螺旋扭转感。纳米尺寸的空腔和通道在催化、分离、纳米器件（传感器、流体等）、用于构建更大结构的纳米支架以及其他纳米多孔材料的设计。在有机与高分子化学项目的支持下，纽约州立大学布法罗分校化学系龚冰教授和内布拉斯加大学林肯分校化学系曾晓成教授正在开展研究旨在选择性且有效地折叠成螺旋结构的碳基分子的合成和特性。这些螺旋结构包含尺寸和功能可调节的纳米级通道，可以调整它们的特性及其与其他分子的相互作用。这些研究还提供了有关其他天然和非天然大分子折叠的基本信息。进行这些跨学科研究的学生获得了有机合成、生物有机和超分子有机化学以及理论化学方面的技能。