合作性和复杂性在离子和离子与四级离子对宿主结合时
Ethan N W Howe1, Mohan Bhadbhade, Pall Thordarson
1School of Chemistry, The University of New South Wales , Sydney, NSW 2052, Australia.
Journal of the American Chemical Society
|May 15, 2014
概括
这项研究揭示了四级离子对宿主 (1) 对于离子结合的负合作性. 酸全激活化物结合,为设计合作的超分子系统提供了洞察力.
科学领域:
- 超分子化学 超分子化学
- 主机和客人的化学反应
- 分子识别分子识别
背景情况:
- 在自然和合成的超分子系统中,合作相互作用至关重要.
- 了解这些相互作用是设计高级功能材料的关键.
- 四级离子对宿主为复杂的分子识别事件提供了一个平台.
研究的目的:
- 研究一种新型四型离子对宿主 (1) 的合作结合特性.
- 在主机-客户系统中量化复杂的合作相互作用.
- 探索通过阴离子对结合事件的全调制.
主要方法:
- 对宿主及其复合物的单晶X射线分析.
- 二维核磁共振 (2D NMR) 光谱学.
- 计算研究和绑定模型分析.
主要成果:
- 主体1对化物和酸盐离子表现出强烈的负合作性 (α = 0.010.05).
- 阴离子结合的结果是可变的,但的添加全osterically 激活,否则缺席的结合.
- 详细的结构和计算数据阐明了结合机制.
结论:
- 型离子对宿主 (1) 表现出复杂的合作性结合行为.
- 酸结合可以调节离子识别,使"开关"切换成为可能.
- 这些发现为设计复杂的合作性超分子系统用于催化和信息传输提供了宝贵的见解.
相关概念视频
Cooperative Allosteric Transitions
7.4K
Cooperative allosteric transitions can occur in multimeric proteins, where each subunit of the protein has its own ligand-binding site. When a ligand binds to any of these subunits, it triggers a conformational change that affects the binding sites in the other subunits; this can change the affinity of the other sites for their respective ligands. The ability of the protein to change the shape of its binding site is attributed to the presence of a mix of flexible and stable segments in the...
7.4K
Complexation Equilibria: Overview
1.6K
Complexation reactions take place when dative or coordinate covalent bonds form between metal ions and ligands. The compounds formed in these reactions are called coordination compounds. The number of bonds formed between the metal ion and the ligands is called its coordination number. Generally, most metal ions in an aqueous solution are solvated by water molecules and thus exist as aqua complexes.
The equilibrium constant of the complexation reaction is represented as the formation constant...
The equilibrium constant of the complexation reaction is represented as the formation constant...
1.6K
Complexation Equilibria: Factors Influencing Stability of Complexes
995
In complexation reactions, metal cations are the electron pair acceptors, and the ligands are the electron pair donors. The stability of the metal complexes depends primarily on the complexing ability of the central metal ion and the nature of the ligands. Generally, the complexing ability of the metal ion depends on the size and charge of the ion. As the metal ion size increases, the stability of the metal complexes decreases, provided that the valency of the metal ion and the ligands remain...
995
Complexation Equilibria: The Chelate Effect
1.7K
In complexation reactions, metal atoms or cations interact with ligands to form donor-acceptor adducts called metal complexes. Ligands that bind through one donor site are monodentate, ligands with two donor sites are bidentate, and those with more than two donor sites are polydentate ligands. For example, ethylene diamine is a bidentate ligand that binds through two nitrogen donor atoms, forming a five-membered ring. EDTA is a polydentate ligand that binds through four oxygen and two nitrogen...
1.7K
Metal-Ligand Bonds
19.3K
The hemoglobin in the blood, the chlorophyll in green plants, vitamin B-12, and the catalyst used in the manufacture of polyethylene all contain coordination compounds. Ions of the metals, especially the transition metals, are likely to form complexes.
In these complexes, transition metals form coordinate covalent bonds, a kind of Lewis acid-base interaction in which both of the electrons in the bond are contributed by a donor (Lewis base) to an electron acceptor (Lewis acid). The Lewis acid in...
In these complexes, transition metals form coordinate covalent bonds, a kind of Lewis acid-base interaction in which both of the electrons in the bond are contributed by a donor (Lewis base) to an electron acceptor (Lewis acid). The Lewis acid in...
19.3K
Crystal Field Theory - Octahedral Complexes
28.4K
Crystal Field Theory
To explain the observed behavior of transition metal complexes (such as colors), a model involving electrostatic interactions between the electrons from the ligands and the electrons in the unhybridized d orbitals of the central metal atom has been developed. This electrostatic model is crystal field theory (CFT). It helps to understand, interpret, and predict the colors, magnetic behavior, and some structures of coordination compounds of transition metals.
CFT focuses on...
To explain the observed behavior of transition metal complexes (such as colors), a model involving electrostatic interactions between the electrons from the ligands and the electrons in the unhybridized d orbitals of the central metal atom has been developed. This electrostatic model is crystal field theory (CFT). It helps to understand, interpret, and predict the colors, magnetic behavior, and some structures of coordination compounds of transition metals.
CFT focuses on...
28.4K


