基于单核Cu复合体的4H+/4e电子合质子缓冲器
Tong Wu1, Khashayar Rajabimoghadam2, Ankita Puri1
1Department of Chemistry, Carnegie Mellon University, Pittsburgh, Pennsylvania15213, United States.
Journal of the American Chemical Society
|September 9, 2022
概括
这项研究引入了一种新型的4H+/4e电子合质子缓冲系统 (ECPB),使用铜和氧化还原活性联体. 这种ECPB系统有效催化氧降解和有机基板脱反应.
科学领域:
- 无机化学
- 电化学
- 催化剂
背景情况:
- 开发高效的电子合质子缓冲系统对于催化应用至关重要.
- 有氧化还原活性联体的铜基复合物为多电子转移过程提供了有希望的途径.
研究的目的:
- 设计和描述一种基于铜和氧化还原活性联体的新型4H+/4e-ECPB.
- 研究ECPB系统在氧气减少和有机基板脱中的催化活性.
- 阐明控制ECPB在合和脱反应模式中的机械路径.
主要方法:
- 使用X射线衍射,1H-NMR光谱学合成和表征铜复合物.
- 电化学研究探测ECPB系统的氧化还原行为.
- 密度函数理论 (DFT) 计算以了解电子结构和反应机制.
主要成果:
- 一个基于Cu (I) /Cu (II) 的4H+/4e-ECPB (复合物) 和一个氧化还原活性 bis (urea) 连接物被成功合成和表征.
- 该ECPB系统显示了O2到H2O的4H+/4e-降解的催化活性.
- 该系统还在合和脱模式下催化了有机基质的脱.
- 机理学研究显示了保持ECPB平衡的快速不成比例反应.
结论:
- 开发的基于的ECPB系统为多质子和多电子转移反应提供了一个高效的平台.
- 该系统能够催化降氧和有机脱,突出了其在各种催化应用中的潜力.
- 分离和合的反应途径可以对氧化和还原过程进行调节.
相关概念视频
Electron Transport Chain: Complex III and IV
8.0K
During the electron transport chain, electrons from NADH and FADH2 are first transferred to complexes I and II, respectively. These two complexes then transfer the electrons to ubiquinol, which carries them further to complex III. Complex III passes the electrons across the intermembrane space to Cyt c, which carries them further to complex IV. Complex IV donates electrons to oxygen and reduces it to water. As electrons pass through complexes I, III, and IV, the energy released aids the pumping...
8.0K
Extraction: Advanced Methods
513
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...
513
EDTA: Auxiliary Complexing Reagents
654
EDTA titrations are usually carried out in highly basic conditions, where the fully deprotonated form of EDTA, Y4−, actively complexes with the free metal ions in the solution. Several metal ions precipitate as hydrous oxide (hydroxides, oxides, or oxyhydroxides) under these conditions, lowering the concentration of free metal ions in the solution. For this reason, auxiliary complexing agents or ligands such as ammonia, tartrate, citrate, or triethanolamine are used in EDTA titrations to...
654
Protein Buffers in Blood Plasma and Cells
1.2K
The human body utilizes protein buffer systems to maintain a stable pH. These systems capitalize on the dual role of amino acids, which can act as acids or bases by accepting or releasing hydrogen ions in response to pH changes. Protein buffer systems are particularly significant in the extracellular fluid (ECF) and intracellular fluid (ICF) of active cells, where structural and functional proteins provide substantial buffering capacity.
Certain amino acids can exist in a zwitterion state at a...
Certain amino acids can exist in a zwitterion state at a...
1.2K
Formation of Complex Ions
23.9K
A type of Lewis acid-base chemistry involves the formation of a complex ion (or a coordination complex) comprising a central atom, typically a transition metal cation, surrounded by ions or molecules called ligands. These ligands can be neutral molecules like H2O or NH3, or ions such as CN− or OH−. Often, the ligands act as Lewis bases, donating a pair of electrons to the central atom. These types of Lewis acid-base reactions are examples of a broad subdiscipline called coordination...
23.9K
Buffers: Overview
4.7K
Buffers play a crucial role in stabilizing the pH of a solution by mitigating the effects of small amounts of added acid or base. They consist of a weak acid and its conjugate base or a weak base and its conjugate acid. A solution of acetic acid and sodium acetate is an example of a buffer that consists of a weak acid and its salt: CH3COOH (aq) + CH3COONa (aq). An example of a buffer that consists of a weak base and its salt is a solution of ammonia and ammonium chloride: NH3 (aq) + NH4Cl (aq).
4.7K

![[DPEPhosbcpCu]PF6: A General and Broadly Applicable Copper-Based Photoredox Catalyst](/_next/image?url=https%3A%2F%2Fcloudfront.jove.com%2FCDNSource%2Fteasers%2F59739.jpg&w=3840&q=50)
![Protein Film Infrared Electrochemistry Demonstrated for Study of H2 Oxidation by a [NiFe] Hydrogenase](/_next/image?url=https%3A%2F%2Fcloudfront.jove.com%2FCDNSource%2Fteasers%2F55858.jpg&w=3840&q=50)