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Universal Anticancer Cu(DTC)2 Discriminates between Thiols and Zinc(II) Thiolates Oxidatively
Luyan Xu1,2,3, Jialin Xu1, Jingwei Zhu4
1School of Physical Science and Technology, ShanghaiTech University, 393 Middle Huaxia Road, Pudong new area, Shanghai, 201210, P. R. China.
Angewandte Chemie (International Ed. in English)
|March 7, 2019
Summary
This study reveals that copper(II) complexes with diethyldithiocarbamate (DTC) can selectively oxidize zinc(II) thiolates without affecting cellular thiols. This discovery offers a new strategy for developing anticancer drugs that bypass cellular defenses.
Area of Science:
- Biochemistry
- Inorganic Chemistry
- Chemical Biology
Background:
- Aerobic organisms utilize intracellular thiols to protect proteins, particularly zinc(II) thiolate sites, from oxidative damage.
- Understanding redox interactions between metal complexes and biological thiols is crucial for cellular protection mechanisms.
Purpose of the Study:
- To investigate the selective reactivity of copper(II) complexes towards zinc(II) thiolates in the presence of free thiols.
- To establish a new chemical principle for designing oxidants that can overcome cellular reductive defenses.
Main Methods:
- Model studies involving reactions between well-defined zinc(II) thiolate and copper(II) complexes.
- Systematic evaluation of various copper(II) ligands, focusing on diethyldithiocarbamate (DTC).
Main Results:
- Diethyldithiocarbamate (DTC) ligand uniquely enabled copper(II) to resist reduction by thiols.
- Copper(II)-DTC complexes selectively oxidized zinc(II) thiolates to disulfides.
- Demonstrated the possibility of discriminating between thiols and zinc(II) thiolates using specific oxidants.
Conclusions:
- Developed a novel chemical principle for selective oxidation of zinc(II) thiolates.
- Identified copper(II)-DTC as a potential agent to circumvent intracellular reductive defenses.
- Suggests a new mechanism for anticancer agents like Cu(DTC)2 to target malignant cells by overcoming thiol-based protection.
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