Fu-Pei Liang

Synthesis of two potential anticancer copper(II) complex drugs: their crystal structure, human serum albumin/DNA binding and anticancer mechanism

Two hydrazone ligands 8-quinolinecarbaldehyde 3-methoxybenzoylhydrazone (L1) and 8-quinolinecarbaldehyde benzoylhydrazone (L2) and the corresponding mononuclear copper(II) complexes [Cu(L1)(NO3)2] (1) and [Cu(L2)(CH3O)NO3] (2) have been synthesized. The structures of complexes 1 and 2 were characterized by X-ray crystallography, elemental analyses, FT-IR and HRMS (ESI). Efficient binding of the complexes (1 and 2) and ligands (L1 and L2) with protein (human serum albumin, HSA) has been established by UV-vis, fluorescence, synchronous fluorescence spectroscopy, and molecular docking methods. Fluorescence spectra show that both complexes strongly interact with protein. And the Trp residue, the intrinsic fluorophore in HSA, was induced to a less hydrophobic microenvironment with the addition of test complexes. Meanwhile, the fluorescence quenching mechanism was determined to be static quenching. Interaction of the complexes (1 and 2) and ligands (L1 and L2) with calf-thymus DNA (CT-DNA) has been investigated by UV-vis and fluorescence methods which showed that the compounds interacted with CT-DNA through intercalation. Moreover, the molecular docking study indicated that the complex is embedded into site I (subdomain IIA) of HSA. In addition, the complexes exhibited significant cytotoxicity against a human cervical cancer cell line (HeLa), and complexes 1 and 2 showed better activity than cisplatin. The complexes could cause HeLa cell cycle arrest at the G2 phase. And mitochondrial dysfunction was induced by both of the complexes.

Two hydrazone copper(II) complexes: synthesis, crystal structure, cytotoxicity, and action mechanism

Two copper(II) complexes with 8-quinolinecarbaldehyde o-vanilloylhydrazone (H-L1) and 8-quinolinecarbaldehyde salicylhydrazone (H-L2), [Cu(L1)NO3] (1) and [Cu(L2)NO3] (2), were synthesized and structurally characterized, respectively. Complexes 1 and 2 exhibited enhanced cytotoxicity against BEL-7402, Hep-G2, NCI-H460, MGC80-3, HeLa tumor cells compared with free ligands and copper(II) salt and slightly lower than that shown by cisplatin. And MGC80-3 cells are more sensitive to these two complexes relative to the normal liver cells. Cytotoxicity and action mechanism studies suggest 1 and 2 could cause MGC80-3 cell cycle arrest at G1 phase, which is induced by limiting the supply of cyclins D1 and E1 and inhibiting the activity of G1-phase-promoting cyclin–Cdk complexes. And complexes 1 and 2 led to cell apoptosis via the activation of Bcl-2 protein. Moreover, mitochondrial dysfunction was induced by both of complexes.

Synthesis, structure and properties of an octahedral dinuclear-based Cu12 nanocage of trimesoyltri(L-alanine)

The reaction of a three-armed ligand of trimesoyltri(L-alanine) (TMTAH3) with CuCl2 gave [Cu12(TMTA)8(H2O)12]·8CH3CH2OH·40H2O (1) as expected. It features paddlewheel dinuclear secondary building blocks, six of which are connected by eight TMTA3− linkers, forming a Mo6C184+-like dinuclear-based octahedral nanocage. The magnetic studies revealed the presence of antiferromagnetic interactions between the Cu(II) ions in 1. The desolvated sample of 1 presents nice selectivity on the adsorption of H2 and CO2 over CH4.

Manganese clusters of aromatic oximes: synthesis, structure and magnetic properties

With the aim of tuning the structures by using oxime ligands with different non-coordinating groups, three aromatic oxime ligands were designed by fusing oxime groups ([double bond, length as m-dash]N-OH) onto different non-coordinating groups. Their reactions with the corresponding Mn(ii) salts gave five manganese clusters [Mn(μ3-O)(L1)3(DMF)(H2O)3Cl]·2DMF·CH3OH (1), [Mn(μ3-O)(L2)3(OAc)(CH3OH)2] (2), [Mn(μ3-O)2(L2)6(H2O)(py)7](ClO4)2·py·0.5CH3OH·2H2O (3), [MnO4(L2)8(DMF)4]·DMF·6CH3CN (4), and [MnMnO4(L3)12]·3DMF·6H2O (5), in which H2L1, H2L2 and HL3 represent indane-1,2,3-trione-1,2-dioxime, acenaphthenequinone dioxime, and 9,10-phenanthrenedione-9-oxime, respectively. Their structures were determined and studied in detail. 1 and 2 show planar triangular trinuclear Mn structures. 3 has a hexanuclear Mn skeleton formed from two Mn triangular units through inter-trinuclear mutual coordination. 4 and 5 present octanuclear skeletons constructed from planar triangular Mn3O and tetrahedral Mn4O secondary building units, respectively, with different symmetries and different oxidation states of the manganese ions. Their structural studies reveal a significant contribution of the parent rings for fusing oxime groups, different non-coordinating groups and anions to the formation of different cluster skeletons. Their magnetic properties were investigated and simulated, which revealed the presence of dominant antiferromagnetic interactions between the metal ions in these compounds.

Structure and magnetism of two chair-shaped hexanuclear dysprosium(III) complexes exhibiting slow magnetic relaxation

Two novel hexanuclear DyIII complexes with polyhydroxy Schiff-base ligands, [Dy6(L1)4(μ3-OH)4(MeOH)4]Cl2·2MeOH·2MeCN (1) and [Dy6(HL2)2(μ3-OH)2(μ3-OCH3)2(piv)10(MeOH)2] (2) (H3L1 = N,N′-bis(3-methoxysalicylidene)(propylene-2-ol)-1,3-diamine, H3L2 = 2,3-dihydroxypropylimino)methyl)-6-methoxyphenol, piv = pivalate), have been prepared under solvothermal conditions and structurally characterized by single-crystal X-ray diffraction, elemental analyses, thermal analyses, and IR spectroscopy. Each of the hexanuclear complexes is constructed with Dy3 triangular motifs as building blocks, and the six DyIII ions are arranged in a chair-shaped conformation. Variable-temperature magnetic susceptibility measurements in the temperature range of 2–300 K indicate dominant ferromagnetic exchange interactions between the DyIII ions in the complexes. Both complexes exhibit slow magnetic relaxation behavior.

A family of 3d metal clusters based on N–N single bonds bridged quasi-linear trinuclear cores: the Mn analogue displaying single-molecule magnet behavior

The reactions of the diacylhydrazine ligands N,N′-bisalicyl-2,6-pyridine dicarbohydrazide (H6sphz) and N,N′-bis(3-methoxysalicyl)-2,6-pyridine dicarbohydrazide (H6msphz) with various 3d metal salts, afforded a series of coordination clusters, namely, [MnIII2MnII(sphz)(acac)2(CH3OH)4] (1, acac− = acetylacetone anions), [NiII3(msphz)(Py)4] (2, Py = pyridine), [CuII6(sphz)2(Py)4] (3) and [CuII6(msphz)2(Py)4]·2DMF·2H2O (4). Cluster 1 and 2 are single ligand assembled quasi-linear trinuclear structures. Both 3 and 4 consist a pair of quasi-linear {Cu3} cores, which are linked together by two crossed ligands. The adjacent 3d metal ions in all trinuclear cores of 1–4 are bridged by N–N single bonds of ligands, which convey ferromagnetic (FM) interactions between 3d metal centers of 1, and antiferromagnetic (AFM) interactions between those of 2–4. In particular, the FM interactions and linear arrangement of mixed-valence Mn centers in 1 result in a large spin ground states value (ST) of 13/2, as well as single-molecule magnet (SMM) behavior of slow relaxation and hysteresis of magnetization.

CCDC 1496805: Experimental Crystal Structure Determination

Related Article: Kai Wang, Shen Tang, Zhao-Bo Hu, Hua-Hong Zou, Xiao-Lu Wang, Yan Li, Shu-Hua Zhang, Zi-Lu Chen, Fu-Pei Liang|2018|RSC Advances|8|6218|doi:10.1039/C7RA12844D