在双核铜复合体中,酸盐/二硫化物的联体非无罪性:依赖溶剂的氧化还原异构化和质子合电子转移
Andrew M Thomas1, Bo-Lin Lin, Erik C Wasinger
1Department of Chemistry, Stanford University , Stanford, California 94305, United States.
Journal of the American Chemical Society
|November 28, 2013
概括
合成的铜复合物模仿蛋白质氧化还原过程,在硫酸盐和二硫化物形式之间表现出溶剂依赖的相互转换. 质子添加驱动电子转移,揭示了生物系统中铜离子管理的机制.
科学领域:
- 生物有机化学 生物有机化学
- 协调化学 协调化学
- 生物化学 生物化学
背景情况:
- 铜硫酸盐/二硫化物相互转换在人类Sco1和SOD1.1等蛋白质中至关重要.
- 了解这些氧化还原过程需要明确的合成类似物.
研究的目的:
- 合成和描述模仿蛋白质相互转换的二度铜复合体.
- 为了研究依赖溶剂的氧化还原同质化和质子合电子转移.
主要方法:
- 在X射线中,X射线的衍射效果是不同的.
- 射线吸收光谱学 (XAS) 是一种X射线吸收光谱技术.
- 核磁共振 (NMR) 是一种核磁共振技术.
- 紫外线可见光谱学
主要成果:
- 观察到二次性μ-thiolato Cu (II) Cu (II) 和μ-disulfido Cu (I) Cu (I) 形式之间的溶剂依赖平衡.
- 质子添加 (2 equiv) 通过质子合电子转移诱导了μ-二硫化物Cu (I) Cu (I) 复合物的完全形成.
- 质子去除逆转了反应,证明了可逆的质子化/脱质子化.
结论:
- 这项研究为生物系统中铜离子管理提供了一个新的化学先例.
- 观察到的还原性质子/氧化性去质子机制为金属蛋白的功能提供了洞察力.
更多相关视频
11:04Ion Mobility-Mass Spectrometry Techniques for Determining the Structure and Mechanisms of Metal Ion Recognition and Redox Activity of Metal Binding Oligopeptides
Published on: September 7, 2019
8.3K
14:44Structure and Coordination Determination of Peptide-metal Complexes Using 1D and 2D 1H NMR
Published on: December 16, 2013
9.3K
相关概念视频
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
Preparation and Reactions of Thiols
6.8K
Thiols are prepared using the hydrosulfide anion as a nucleophile in a nucleophilic substitution reaction with alkyl halides. For instance, bromobutane reacts with sodium hydrosulfide to give butanethiol.
6.8K
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
EDTA: Chemistry and Properties
4.2K
Polydentate ligands are most widely used in complexometric titrations because they form more stable complexes with the metal ions than mono- or bidentate ligands due to the chelate effect. Examples of polydentate ligands are ethylenediaminetetraacetic acid (EDTA), crown ethers, and cryptands. The most important feature of optimal polydentate ligands is the ability to form 1:1 complexes in a single-step process. Amino carboxylic acid derivatives are frequently used as complexing agents. EDTA is...
4.2K
Extraction: Advanced Methods
1.3K
Metal ions can be separated from one another by complexation with organic ligands–the chelating agent– to form uncharged chelates. Here, the chelating agent must contain hydrophobic groups and behave as a weak acid, losing a proton to bind with the metal. Since most organic ligands used in this process are insoluble or undergo oxidation in the aqueous phase, the chelating agent is initially added to the organic phase and extracted into the aqueous phase. The metal-ligand complex is...
1.3K
Colors and Magnetism
12.1K
Color in Coordination Complexes
When atoms or molecules absorb light at the proper frequency, their electrons are excited to higher-energy orbitals. For many main group atoms and molecules, the absorbed photons are in the ultraviolet range of the electromagnetic spectrum, which cannot be detected by the human eye. For coordination compounds, the energy difference between the d orbitals often allows photons in the visible range to be absorbed and emitted, which is seen as colors by the human...
When atoms or molecules absorb light at the proper frequency, their electrons are excited to higher-energy orbitals. For many main group atoms and molecules, the absorbed photons are in the ultraviolet range of the electromagnetic spectrum, which cannot be detected by the human eye. For coordination compounds, the energy difference between the d orbitals often allows photons in the visible range to be absorbed and emitted, which is seen as colors by the human...
12.1K
