Citation: Yao HUANG, Yingshu WU, Zhichun BAO, Yue HUANG, Shangfeng TANG, Ruixue LIU, Yancheng LIU, Hong LIANG. Copper complexes of anthrahydrazone bearing pyridyl side chain: Synthesis, crystal structure, anticancer activity, and DNA binding[J]. Chinese Journal of Inorganic Chemistry, ;2025, 41(1): 213-224. doi: 10.11862/CJIC.20240359 shu

Copper complexes of anthrahydrazone bearing pyridyl side chain: Synthesis, crystal structure, anticancer activity, and DNA binding

Yao HUANG ^{1, 2, #} ,
Yingshu WU ^{2, #} ,
Zhichun BAO ² ,
Yue HUANG ² ,
Shangfeng TANG ² ,
Ruixue LIU ^2,, ,
Yancheng LIU ² ,
Hong LIANG ^2,,

1.
School of Chemical Engineering, Yunnan Open University, Kunming 650223, China
2.
School of Chemistry & Pharmaceutical Sciences, Guangxi Normal University, Guilin, Guangxi 541004, China

Corresponding author: Ruixue LIU, rxliu@gxnu.edu.cn Hong LIANG, hliang@gxnu.edu.cn
Received Date: 8 October 2024
Revised Date: 25 December 2024

Figures(5)

To expand the study on the structures and biological activities of the anthracyclines anticancer drugs and reduce their toxic side effects, the new anthraquinone derivatives, 9-pyridylanthrahydrazone (9-PAH) and 9, 10-bispyridylanthrahydrazone (9, 10-PAH) were designed and synthesized. Utilizing 9-PAH and 9, 10-PAH as promising anticancer ligands, their respective copper complexes, namely [Cu(L1)Cl₂]Cl (1) and {[Cu₄(μ₂-Cl)₃Cl₄(9, 10-PAH)₂(DMSO)₂]Cl₂}_n (2), were subsequently synthesized, where the new ligand L1 is formed by coupling two 9-PAH ligands in the coordination reaction. The chemical and crystal structures of 1 and 2 were elucidated by IR, MS, elemental analysis, and single-crystal X-ray diffraction. Complex 1 forms a mononuclear structure. L1 coordinates with Cu through its three N atoms, together with two Cl atoms, to form a five-coordinated square pyramidal geometry. Complex 2 constitutes a polymeric structure, wherein each structural unit centrosymmetrically encompasses two five-coordinated binuclear copper complexes (Cu1, Cu2) of 9, 10-PAH, with similar square pyramidal geometry. A chlorine atom (Cl2), located at the symmetry center, bridges Cu1 and Cu1A to connect the two binuclear copper structures. Meanwhile, the two five-coordinated Cu2 atoms symmetrically bridge the adjacent structural units via one coordinated Cl atom, respectively, thus forming a 1D chain-like polymeric structure. In vitro anticancer activity assessments revealed that 1 and 2 showed significant cytotoxicity even higher than cisplatin. Specifically, the IC₅₀ values of 2 against HeLa-229 and SK-OV-3 cancer cell lines were determined to be (5.92±0.32) μmol·L^-1 and (6.48±0.39) μmol·L^-1, respectively. 2 could also block the proliferation of HeLa-229 cells in S phase and significantly induce cell apoptosis. In addition, fluorescence quenching competition experiments suggested that 2 might interact with DNA by an intercalative binding mode, offering insights into its underlying anticancer mechanism.
- anthrahydrazone,
- metal complex,
- crystal structure,
- anticancer activity,
- cell apoptosis
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沈阳化工大学材料科学与工程学院沈阳 110142