ホモキラスの柱は,帽子状の分子の超分子螺旋組織でキラスの自己分類によって構成される
Cécile Roche1, Hao-Jan Sun, Margaret E Prendergast
1Roy & Diana Vagelos Laboratories, Department of Chemistry, University of Pennsylvania , Philadelphia, Pennsylvania 19104-6323, United States.
Journal of the American Chemical Society
|April 25, 2014
まとめ
キラル型デンドロン化サイクロトリベラトリレン (CTV) 化合物は,螺旋状の柱に自己組み立てられます. この研究は,結晶状態での前例のないキラル自己分類を明らかにし,複雑なシステム機能に影響を与えています.
科学分野:
- 超分子化学 超分子化学
- マテリアルサイエンス 材料科学
- 有機化学 オーガニック・ケミストリー
背景:
- デンドロニズドサイクロトリベラトリレン (CTV) 冠は,ユニークな構造特性で知られています.
- 分子の自己組み立ては,高度な材料の開発に不可欠です.
研究 の 目的:
- 様々な周辺アルキル鎖を持つデンドロン化CTV冠のライブラリを合成し,特徴づけること.
- これらのCTV誘導体の自己組み立て行動を,溶液恐怖性溶媒および散発状態で調査する.
- 形成された超分子構造を解明し,キラル自己分類のメカニズムを理解する.
主な方法:
- キラル,ラセミック,アキラルアルキル鎖を持つデンドロン化されたCTV冠の合成.
- 円形二重化 (CD) と溶液と薄膜のUVスペクトロスコーピーを用いて特徴づけました.
- 差分スキャニングカロメトリー (DSC) と繊維X線微分法による散布構造の分析.
- コンピュータシミュレーションと分子モデリング.
- 固体核磁共振 (NMR) スペクトロスコーピー. 固体核磁共振 (NMR) スペクトロスコーピー. 固体核磁共振 (NMR) スペクトロスコーピー. 固体核磁共振 (NMR) スペクトロスコーピー.
主要な成果:
- CTVデリバティブは,ソルボホービックな溶媒と散発剤で螺旋状の柱に自己組み立てます.
- エナティオピュアCTVは単手柱を形成し,ラセミックおよびアキラル化合物も螺旋構造に自己組み立てを示します.
- 大量状態では,超分子列は3D六角形結晶相 (Φ(h) ((k)) または2D柱状六角形液晶 (Φ(h)) を形成します.
- 最高級の結晶相は,歪んだ12折のトリプルヘリックスに似ている,エナティオピュール単手柱で構成されています.
- 脱セミゼーションは,結晶状態において,分子構成の変化とコンフォマー間の柱間移転を経由して発生する.
結論:
- デンドロナイズされたCTVは,調節可能なキラリティを持つ螺旋状の柱に顕著な自己組み立てを示しています.
- この研究は,ラセミックおよびアキラル前駆体からさえも,前例のない超分子キラル自己分類を実証しています.
- これらの発見は,複雑な機能的材料とシステムの設計に重大な意味を持っています.
関連する概念動画
Chirality
23.4K
Chirality is a term that describes the lack of mirror symmetry in an object. In other words, chiral objects cannot be superposed on their mirror images. For example, our feet are chiral, as the mirror image of the left foot, the right foot, cannot be superposed on the left foot.
Chiral objects exhibit a sense of handedness when they interact with another chiral object. For example, our left foot can only fit in the left shoe and not in the right shoe. Achiral objects — objects that have...
Chiral objects exhibit a sense of handedness when they interact with another chiral object. For example, our left foot can only fit in the left shoe and not in the right shoe. Achiral objects — objects that have...
23.4K
Prochirality
4.0K
The concept of prochirality leads to the nomenclature of the individual faces of a molecule and plays a crucial role in the enantioselective reaction. It is a concept where two or more achiral molecules react to produce chiral products. A typical process is the reaction of an achiral ketone to generate a chiral alcohol. Here, the achiral reactant reacts with an achiral reducing agent, sodium borohydride, to generate an equimolar mixture of the chiral enantiomers of the product. For example, an...
4.0K
Molecules with Multiple Chiral Centers
11.6K
Molecules that possess multiple chiral centers can afford a large number of stereoisomers. For instance, while some molecules like 2-butanol have one chiral center, defined as a tetrahedral carbon atom with four different substituents attached, several molecules like butane-2,3-diol have multiple chiral centers. A simple formula to predict the number of stereoisomers possible for a molecule with n chiral centers is 2n. However, there can be a lower number where some of the stereoisomers are...
11.6K
Chirality at Nitrogen, Phosphorus, and Sulfur
5.5K
Chirality is most prevalent in carbon-based tetrahedral compounds, but this important facet of molecular symmetry extends to sp3-hybridized nitrogen, phosphorus and sulfur centers, including trivalent molecules with lone pairs. Here, the lone pair behaves as a functional group in addition to the other three substituents to form an analogous tetrahedral center that can be chiral.
A consequence of chirality is the need for enantiomeric resolution. While this is theoretically possible for all...
A consequence of chirality is the need for enantiomeric resolution. While this is theoretically possible for all...
5.5K
High-Performance Liquid Chromatography: Introduction
3.0K
High-performance liquid chromatography(HPLC), formerly referred to as High-pressure liquid chromatography, is a powerful technique used to separate, identify, and quantify components in complex mixtures. The term "high pressure" refers to using high pressure to push the liquid mobile phase through the tightly packed columns.
In HPLC, two phases play a critical role in the separation process:
In HPLC, two phases play a critical role in the separation process:
3.0K
¹H NMR Chemical Shift Equivalence: Enantiotopic and Diastereotopic Protons
3.7K
Replacing each alpha-hydrogen in chloroethane by bromine (or a different functional group) yields a pair of enantiomers. Such protons are called prochiral or enantiotopic and are related by a mirror plane. Enantiotopic protons are chemically equivalent in an achiral environment. Because most proton NMR spectra are recorded using achiral solvents, enantiotopic hydrogens yield a single signal.
In chiral compounds such as 2-butanol, replacing the methylene hydrogens at C3 produces a pair of...
In chiral compounds such as 2-butanol, replacing the methylene hydrogens at C3 produces a pair of...
3.7K


