通过溶剂诱导的螺旋性反转螺旋式聚乙烯在石墨上进行二维表面性控制
Shin-ichiro Sakurai1, Kento Okoshi, Jiro Kumaki
1Yashima Super-structured Helix Project, Exploratory Research for Advanced Technology (ERATO), Japan Science and Technology Agency (JST), 101 Creation Core Nagoya, Shimoshidami, Moriyama-ku, Nagoya 463-0003, Japan.
Journal of the American Chemical Society
|April 28, 2006
概括
这项研究表明,螺旋性聚合物可以在不同的溶剂中翻转它们的手性. 使用原子力显微镜可视化了这种表面性变化.
科学领域:
- 聚合物化学 聚合物化学
- 超分子化学 超分子化学
- 表面科学是一门学科.
背景情况:
- 螺旋型聚合物表现出独特的手术特征.
- 已知聚合物中的溶剂诱导的形状变化.
- 控制超分子组合对于先进材料至关重要.
研究的目的:
- 在螺旋式聚乙烯中提供宏分子螺旋性逆转的直接证据.
- 研究不同溶剂中的二聚体螺旋结构的自我组装.
- 为了可视化和量化溶剂诱导的表面性变化.
主要方法:
- 原子力显微镜 (AFM) 用于高分辨率的表面成像.
- 用X射线衍射 (XRD) 来分析聚合物薄膜的结构.
- 使用聚甲烯与性氨酸和基链.
主要成果:
- 使用AFM直接可视化宏分子螺旋体逆转.
- 在石墨上形成有序的2D螺旋捆,以受控的音调和手性.
- 证明从极性溶剂到非极性溶剂的螺旋逆转,反之亦然.
- 通过X射线衍射量化结构变化的量化.
结论:
- 宏分子螺旋体逆转是直接可观测的,并通过溶剂操纵可控制.
- 螺旋型聚合物可以形成有序的超分子结构,具有可调节的特性.
- 表面性可以动态改变,为性传感和响应材料提供潜力.
相关概念视频
Polymer Classification: Stereospecificity
Polymerization generates chiral centers along the entire backbone of a polymer chain. Accordingly, the stereochemistry of the substituent group has a significant effect on polymer properties. Polymers formed from monosubstituted alkene monomers feature chiral carbons at every alternate position in the polymer backbone. Relative to the predominant orientation of substituents at the adjacent chiral carbons, the polymer can exist in three different configurations: isotactic, syndiotactic, and...
Anionic Chain-Growth Polymerization: Overview
The polymerization process that involves carbanion as an intermediate is called anionic polymerization. It is also a type of addition or chain-growth polymerization. Anionic polymerization gets initiated by a strong nucleophile such as an organolithium or a Grignard reagent. The most commonly used initiator for anionic polymerization is butyl lithium. Monomers involved in anionic polymerization must possess a vinyl group bonded to one or two electron-withdrawing groups. For instance,...
Anionic Chain-Growth Polymerization: Mechanism
The mechanism for anionic chain-growth polymerization involves initiation, propagation, and termination steps. In the initiation step, a nucleophilic anion, such as butyl lithium, initiates the polymerization process by attacking the π bond of the vinylic monomer. As a result, a carbanion, stabilized by the electron‐withdrawing group, is generated. The resulting carbanion acts as a Michael donor in the propagation step and attacks the second vinylic monomer, which acts as a Michael acceptor.
Cationic Chain-Growth Polymerization: Mechanism
The cationic polymerization mechanism consists of three steps: initiation, propagation, and termination. In the initiation step of the polymerization process, the π bond of a monomer gets protonated by the Lewis acid catalyst, which is formed from boron trifluoride and water. The protonation of the π bond generates a carbocation stabilized by the electron‐donating group. In the propagation step, the π bond of the second monomer acts as a nucleophile and attacks the generated carbocation,...
Step-Growth Polymerization: Overview
Step-growth or condensation polymerization is a stepwise reaction of bi or multifunctional monomers to form long-chain polymers. As all the monomers are reactive, most of the monomers are consumed at the early stages of the reaction to form small chains of reactive oligomers, which then combine to form long polymer chains in the late stages. Hence, the reaction has to proceed for a long time to achieve high molecular weight polymers.
Many natural and synthetic polymers are produced by...
Many natural and synthetic polymers are produced by...
Olefin Metathesis Polymerization: Ring-Opening Metathesis Polymerization (ROMP)
Ring-opening metathesis polymerization or ROMP involves strained cycloalkenes as starting materials. The mechanism of ROMP proceeds by reacting cycloalkene with Grubbs catalyst to give metallacyclobutane intermediate which undergoes a ring-opening reaction to form new carbene. The new carbene reacts with another molecule of cycloalkene. Repetition of these steps leads to the formation of an unsaturated open-chain polymer product. All these steps are reversible, however, relieving the ring...


