通过激素-激素相互作用诱导的寡生物的折叠
Yuping Wang1, Marco Frasconi, Wei-Guang Liu
1Department of Chemistry, Northwestern University , 2145 Sheridan Road, Evanston, Illinois 60208, United States.
Journal of the American Chemical Society
|December 11, 2014
概括
带有基离子的Oligoviologens通过由基-基相互作用驱动的折叠自我组装. 这些相互作用影响了分子内部和分子间的结构,创造了具有二级和三级结构的仿生系统.
科学领域:
- 超分子化学 超分子化学
- 材料科学 材料科学 材料科学
- 有机化学 有机化学
背景情况:
- 维奥基因因其氧化还原活性和自我组装特性而闻名.
- 了解自组装机制对于设计功能性材料至关重要.
- 橄生物学提供可调节的结构,用于研究分子相互作用.
研究的目的:
- 用不同的4,4'-双 (BIPY(2+)) 单元合成同类的寡生物.
- 研究它们的基质质子形式的自我组装行为.
- 阐明根基-根基相互作用在折叠和上层结构形成中的作用.
主要方法:
- 用p-xylylene桥梁合成的寡生物原体.
- 紫外线/Vis/NIR光谱仪用于电子表征.
- 密度函数理论 (DFT) 计算用于量子力学见解.
- 固态X射线晶体学用于结构分析.
主要成果:
- 奥利戈维奥基因折叠是由BIPY ((•+) 单元之间的根基-根基相互作用引起的.
- 较短的小分子生物体表现出由分子间相互作用主导的折叠.
- 较长的寡聚生物体表现出由分子内和分子间相互作用影响的折叠,在900nm处的NIR吸收.
- 固态结构显示了由分子间相互作用稳定的二元形成和柱状堆叠.
结论:
- 激素与激素的相互作用是寡聚生物原体自我组装和折叠的关键驱动因素.
- 这项研究介绍了一种模仿核酸和蛋白质结构的人工生物仿真系统.
- 这些发现提供了对具有可调节性质的自我组装分子系统设计的见解.
相关概念视频
Radical Reactivity: Overview
3.0K
Radicals, the highly reactive species, gain stability by undergoing three different reactions. The first reaction involves a radical-radical coupling, in which a radical combines with another radical, forming a spin‐paired molecule. The second reaction is between a radical and a spin‐paired molecule, generating a new radical and a new spin‐paired molecule. The third reaction is radical decomposition in a unimolecular reaction, forming a new radical and a spin‐paired...
3.0K
Radical Formation: Overview
2.8K
A bond can be broken either by heterolytic bond cleavage to form ions or homolytic bond cleavage to yield radicals. A fishhook arrow is used to represent the motion of a single electron in homolytic bond cleavage. There are two main sources from which radicals can be formed:
Radicals from spin-paired molecules:
Radicals can be obtained from spin-paired molecules either by homolysis or electron transfer. While two radicals are formed in the former, an electron is added in the...
Radicals from spin-paired molecules:
Radicals can be obtained from spin-paired molecules either by homolysis or electron transfer. While two radicals are formed in the former, an electron is added in the...
2.8K
Radical Formation: Elimination
2.4K
Another method of radical formation is the elimination process. It is the opposite of the addition route and is driven by the instability of the radical. For example, as depicted in Figure 1, dibenzoyl peroxide yields a pair of unstable radicals upon homolysis. Given its instability, this radical spontaneously undergoes elimination via a C–C bond cleavage to form a relatively more stable phenyl radical. The mechanism involves cleavage of the bond between the α and β positions...
2.4K
Radical Formation: Homolysis
4.7K
A bond is formed between two atoms by sharing two electrons. When this bond is broken by supplying sufficient energy, either two electrons can be taken up by one atom forming ions by the cleavage called heterolysis, or the two electrons are shared by two atoms, with one each creating radicals by the cleavage called homolysis.
4.7K
Radical Formation: Addition
2.4K
Radicals can be formed by adding a radical to a spin-paired molecule. This is typically observed with unsaturated species, where the addition of a radical across the π bond leads to the production of a new radical by dissolving the π bond. For example, the addition of a Br radical to an alkene yields a carbon-centered radical.
Similar to charge conservation in chemical reactions, spin conservation is implicit for radical reactions. Accordingly, the product formed must possess an...
Similar to charge conservation in chemical reactions, spin conservation is implicit for radical reactions. Accordingly, the product formed must possess an...
2.4K
Radical Reactivity: Nucleophilic Radicals
2.8K
Radicals adjacent to electron-donating groups are called nucleophilic radicals. These radicals readily react with electrophilic alkenes. The SOMO–LUMO interactions are the driving force for the reaction, where the high-energy SOMO of the electron-rich, nucleophilic radicals interacts with the low-energy LUMO of the electron-deficient, electrophilic alkenes. Such SOMO–LUMO interactions are the basis of reactive radical traps, affecting the selectivity in radical reactions. For...
2.8K


