可逆调节的较低的临界溶液温度,利用主机-客体复合的支柱[5]arene与三乙烯氧化物替代剂
Tomoki Ogoshi1, Ryohei Shiga, Tada-aki Yamagishi
1Graduate School of Natural Science and Technology, Kanazawa University, Kakuma-machi, Kanazawa 920-1192, Japan. ogoshi@t.kanazawa-u.ac.jp
Journal of the American Chemical Society
|March 1, 2012
概括
一个新型的热反应性宏分子表现出可调节的模糊点. 它的温度依赖行为可以通过添加特定的客体和主体化合物来可逆调整,为智能材料应用提供了潜力.
科学领域:
- 超分子化学 超分子化学
- 聚合物科学 聚合物科学
背景情况:
- 热敏聚合物具有温度依赖的可溶性.
- 支柱[5]arene宏循环以其宿主-客化学能力而闻名.
研究的目的:
- 为了合成和描述一种新型的热反应性宏分子.
- 通过使用客体和宿主化合物来研究巨分子可调的模糊点行为.
主要方法:
- 准备一个巨分子与一个支柱[5]arene核心和三乙烯氧化物臂.
- 测量较低的临界溶液温度 (LCST) 行为.
- 在添加dedecylviologen盐和cucurbit[7]uril.uril.uril.uril.uril.uril.uril.uril.uril.uril.uril.uril.uril.uril.uril.uril.uril.uril.uril.uril.uril.
主要成果:
- 合成的宏分子表现出较低的临界溶液温度 (LCST) 行为.
- 阴影点被外部刺激可逆调整.
- 添加didecylviologen盐增加了云点,而黄[7]uril则降低了云点.
结论:
- 开发的宏分子表现出可控制的热反应性质.
- 该系统为开发具有可调节相变的智能材料提供了一个平台.
相关概念视频
[3,3] Sigmatropic Rearrangement of 1,5-Dienes: Cope Rearrangement
The Cope rearrangement is classified as a [3,3] sigmatropic shift in 1,5-dienes, leading to a more stable, isomeric 1,5-diene. The reaction involves a concerted movement of six electrons, four from two π bonds and two from a σ bond, via an energetically favorable chair-like transition state.
Thermal Electrocyclic Reactions: Stereochemistry
The stereochemistry of electrocyclic reactions is strongly influenced by the orbital symmetry of the polyene HOMO. Under thermal conditions, the reaction proceeds via the ground-state HOMO.
Selection Rules: Thermal Activation
Conjugated systems containing an even number of π-electron pairs undergo a conrotatory ring closure. For example, thermal electrocyclization of (2E,4E)-2,4-hexadiene, a conjugated diene containing two π-electron pairs, gives trans-3,4-dimethylcyclobutene.
Selection Rules: Thermal Activation
Conjugated systems containing an even number of π-electron pairs undergo a conrotatory ring closure. For example, thermal electrocyclization of (2E,4E)-2,4-hexadiene, a conjugated diene containing two π-electron pairs, gives trans-3,4-dimethylcyclobutene.
Thermal Sigmatropic Reactions: Overview
Sigmatropic rearrangements are a class of pericyclic reactions in which a σ bond migrates from one part of a π system to another. These are intramolecular rearrangements where the total number of σ and π bonds remain unchanged.
Sigmatropic shifts are classified based on an order term [i, j ], where i and j indicate the number of atoms across which each end of the σ bond migrates. Below are examples of a [3,3] sigmatropic shift in 1,5-hexadiene, referred to as...
Sigmatropic shifts are classified based on an order term [i, j ], where i and j indicate the number of atoms across which each end of the σ bond migrates. Below are examples of a [3,3] sigmatropic shift in 1,5-hexadiene, referred to as...
Cycloaddition Reactions: MO Requirements for Thermal Activation
Thermal cycloadditions are reactions where the source of activation energy needed to initiate the reaction is provided in the form of heat. A typical example of a thermally-allowed cycloaddition is the Diels–Alder reaction, which is a [4 + 2] cycloaddition. In contrast, a [2 + 2] cycloaddition is thermally forbidden.
Stability of Conjugated Dienes
Introduction
A comparison of the enthalpies of hydrogenation of dienes reveals that conjugated dienes release less heat on hydrogenation, rendering them more stable than their nonconjugated analogs.
A comparison of the enthalpies of hydrogenation of dienes reveals that conjugated dienes release less heat on hydrogenation, rendering them more stable than their nonconjugated analogs.
Diels–Alder Reaction Forming Bridged Bicyclic Products: Stereochemistry
Diels–Alder reactions between cyclic dienes locked in an s-cis configuration and dienophiles yield bridged bicyclic products.


