ヘリカル型デンドロニズドポリフェニラセチレンのシスシソイドからシストランソイドへの熱可逆性イソメリゼーション
Virgil Percec1, Jonathan G Rudick, Mihai Peterca
1Roy & Diana Vagelos Laboratories, Department of Chemistry, University of Pennsylvania, Philadelphia, Pennsylvania 19104-6323, USA. percec@sas.upenn.edu
Journal of the American Chemical Society
|October 27, 2005
まとめ
デンドロニズドポリフェニラセチレン (PPA) ポリマーは螺旋状の多孔性柱を形成し,加熱すると多孔性でない構造に変化します. この制御された構造の変化は,純粋なPPAに見られる劣化を防止し,その安定性を強調します.
科学分野:
- ポリマー化学のポリマー化学について
- 材料科学 材料科学とは
- 超分子化学 超分子化学
背景:
- ポリフェニルアセチレン (PPA) ポリマーは,様々な用途での可能性で知られていますが,分解に弱い可能性があります.
- デンドロニゼーションは,自己組織化と安定性を含むポリマーの性質を修正する経路を提供します.
- ポリマーの形状と自己組み立てを制御することは,高度な材料の設計に不可欠です.
研究 の 目的:
- 高シス含有量ポリフェニルアセチレン (PPA) のポリマーを合成するために,アンフィフィリック自己組み立てデンドロンで覆われています.
- これらの新しいデンドロニズドPPAの自己組織化,相変化,および構造的特性を調査する.
- 熱的ストレス下での原始のcis-PPAと比較して,デンドロニズされたcis-PPAの構造的安定性を評価する.
主な方法:
- マクロモノマーのRh触媒ポリメリゼーションによるデンドロニズされたPPAの合成.
- 微分スキャニングカロメトリー (DSC) を使用した相変化の分析.
- 粉末と指向した繊維の微角と広角X線 difraktion (SAXS/WAXS) を用いた構造的特徴化.
主要な成果:
- 合成された高シス含有量 (81-99%) の円筒形PPAは,六角形柱状の格子 (Phi(h) ((io),Phi(h)) に自己組織化します.
- 特定のデンドロンの長さを持つポリマーは,可逆的な相移行を持つ六角形の柱状結晶相 (Phi,h,k) を表した.
- デンドロニゼーションされたPPAは,Phi (h,k) 段階とPhi (h,io) 段階で螺旋状の多孔柱を形成し,Phi (h,h) 段階では脊椎形状の変化 (cis-cisoidalからcis-transoidal) により,非螺旋形,直径が小さい柱に変形した.
- デンドロニゼーションされたcis-PPAは優れた熱安定性を示し,原始のcis-PPAで観察された分解経路を防止しました.
結論:
- cis-PPAのデンドロニゼーションにより,調節可能な多孔性を持つ秩序ある柱状構造に制御された自己組み立てが可能になります.
- リバーシブルな相変遷は,独特の骨格構造の変化によって引き起こされ,構造的再編成につながります.
- デンドロニゼーションされたcis-PPAは,熱分解に対する安定性を高め,頑丈な機能材料の可能性を開きます.
関連する概念動画
Conformations of Cyclohexane
Cyclohexane does not exist in a planar form due to the high angle and torsional strain it would experience in the planar structure. Instead, it adopts non-planar chair and boat conformations.
The chair form is the most stable and derives its name from its resemblance to the “easy chair.” In the chair conformation, two carbon atoms are arranged out-of-plane — one above and one below, minimizing the torsional strain. In the chair form, the bond angle is very close to the ideal tetrahedral value,...
The chair form is the most stable and derives its name from its resemblance to the “easy chair.” In the chair conformation, two carbon atoms are arranged out-of-plane — one above and one below, minimizing the torsional strain. In the chair form, the bond angle is very close to the ideal tetrahedral value,...
Chair Conformation of Cyclohexane
The chair conformation is the most stable form of cyclohexane due to the absence of angle and torsional strain. The absence of angle strain is a result of cyclohexane’s bond angle being very close to the ideal tetrahedral bond angle of 109.5° in its chair conformer. Similarly, the torsional strain is also absent owing to the perfectly staggered arrangement of bonds.
The hydrogen atoms linked to carbons are arranged in two different axial and equatorial orientations to achieve this staggered...
The hydrogen atoms linked to carbons are arranged in two different axial and equatorial orientations to achieve this staggered...
Disubstituted Cyclohexanes: cis-trans Isomerism
Depending upon the different spatial orientation of the substituents, the disubstituted cycloalkanes exhibit two types of stereoisomers. The cis isomers have the substituents on the same side of the ring, whereas the trans isomers have the substituents on the opposite sides. These stereoisomers exhibit different physical properties and cannot be interconverted without breaking the carbon-carbon bonds.
In cyclohexane, the substituents can occupy different positions generating distinct isomers.
In cyclohexane, the substituents can occupy different positions generating distinct isomers.
Stereoisomerism of Cyclic Compounds
In this lesson, we delve into the role of ring conformation and its stability, which determines the spatial arrangement and, consequently, the molecular symmetry and stereoisomerism of cyclic compounds. 1,2-Dimethylcyclohexane is used as a case study to evaluate the possible number of stereoisomers. Here, given the multiple (n = 2) chiral centers, there are 2n = 4 possible configurations that lack a plane of symmetry, as the ring skeleton exists in a non-planar chair conformation. In addition,...
Isomerism in Alkenes
Alkenes like 1-butene and 2-butene exhibit constitutional isomerism, as they differ in the position of the double bond. Further, 2-butene exhibits stereoisomerism and exists as two distinct compounds differing in spatial arrangement.
An isomer is called cis-2-butene when the methyl groups are on the same side of the double bond, and the other stereoisomer, in which methyl groups are on the opposite side of the double bond, is called trans-2-butene. The cis and trans stereoisomers are not...
An isomer is called cis-2-butene when the methyl groups are on the same side of the double bond, and the other stereoisomer, in which methyl groups are on the opposite side of the double bond, is called trans-2-butene. The cis and trans stereoisomers are not...
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.


