•A hydrazone derivative ligand has been used to construct functional MOFs.•Two MOFs are candidates for potential photoactive materials.•Three MOFs are excellent candidates as photocatalysts in decomposing MB.Three novel complexes, namely {[Zn3(L)2(SO4)2(H2O)4]·2H2O}n (1), {[Cd(L)(OAc)]}n (2) and [Hg2(L)(I)3]2 (3) (HL = N′ - isonicotinoylpyrimidine -2- carbohydrazonamide), have been synthesized and characterized by elemental analyses, infrared spectra and single-crystal X-ray diffraction analyze. The 1D complex 1 and complex 2, and the binuclear complex 3 are expanded to 3D networkers by the strong hydrogen bonds and π-π stacking interactions. The photocatalytic degradation of methylene blue (MB) results indicate that complexes 1–3 are excellent candidates as photocatalysts in decomposing MB with the presence of H2O2. In addition, the luminescent properties of these three complexes have been studied in the solid state.

•Bioluminescent calcium fluorapatite nanocrystals (TCaFAp:Eu) with controlled morphology were fabricated.•The resulted TCaFAp:Eu-FA nanoprobe displayed excellent water dispersibility and biocompatibility.•The functional modifications of grafting folic acid made this nanoprobe excellent targeting cell imaging properties.Bioluminescent calcium fluorapatite nanocrystals (TCaFAp:Eu) with controlled morphology were fabricated through an easy one-step method and found to have excellent water dispersibility and biocompatibility. Further modification of conjugation with both optical imaging and cell targeting capabilities provided useful nanoprobes for highly sensitive biorecognition applications, which was realized by grafting folic acid onto the surface of TCaFAp:Eu. The uptake of designed TCaFAp:Eu-FA by HepG2 cancer cells was verified by confocal laser scanning microscopy after 30 min, whereas the uptake of TCaFAp:Eu-FA by MCF-7 cells did not work, indicating that the prepared nanoprobe effectively targeted the imaging of cancer cells with over-expression of folate receptor.Download high-res image (203KB)Download full-size image

The rise in environmental issues due to the catalytic degradation of pollutants in water has received much attention. In this report, a facile method was developed for the generation of a novel thermosensitive Ag-decorated catalyst, SiO2@PNIPAM@Ag (the average particle size is around 540 nm), through atom transfer radical polymerization (ATRP) and mild reducing reactions. First, poly(N-isopropylacrylamide) (PNIPAM) was used to create a shell around mercapto-silica spheres that allowed for enhanced catalyst support dispersion into water. Second, through a mild reducing reaction, these Ag nanoparticles (NPs) were then anchored to the surface of SiO2@PNIPAM spheres. The resulting catalyst revealed catalytic activity to degrade various nitrobenzenes and organic dyes in an aqueous solution with sodium borohydride (NaBH4) at ambient temperature. The catalytic activity can be adjusted in different temperatures through the aggregation or dispersion of Ag catalyst on the polymer supporters, which is due to the thermosensitive PNIPAM shell. The ease of preparation and efficient catalytic activity of the catalyst can make it a promising candidate for the use in degrading organic pollutants for environmental remediation.

•Three nickel(II) complexes based on amino acid reduced Schiff ligands have been obtained.•The thee complexes show significant biological activities.•The complex 1 can induce human hepatic cancer cell to cell apoptosis by activating caspase 3.Three nickel(II) complexes, [Ni2(L1)2(tren)2(H2O)](ClO4)3 (1), [NiL2(tren)2](ClO4)·2.5H2O (2), [NiL2(tren)2]I·1.5H2O·CH3OH (3) based on amino acid reduced Schiff ligands are synthesized and characterized by physico-chemical and spectroscopic methods. The results show that in all complexes, the amino acid ligand is deprotonated and acts as an anionic ligand. In the dinuclear complex 1, each Ni(II) atom has a distorted octahedron geometry while with different coordination environment. However, the complexes 2 and 3 are mononuclear, almost with the same coordination environment. Furthermore, in vitro experiments are carried out, including MTT assay, Annexin V/PI flow cytometry and western blotting, to assess whether the complexes have antitumor effect. And the results show that all the three complexes have moderate anticancer activity towards human hepatic cancer (HepG2), human cervical cancer (HeLa) and human prostate (PC3) cell lines, in a concentration dependent way. The complex 1 exhibit higher cytotoxicity than the other two complexes and can induce human hepatic cancer cell (HepG2) to cell apoptosis by activating caspase 3.Three nickel(II) complexes based on amino acid reduced Schiff ligands have been obtained and the biological activities of them are investigated by MTT assay and crystal violet assay.

•Four new complexes based on 3-ethyl-2-acetylpyrazine semicarbazone were synthesized and characterized.•The effect of the four complexes on human pancreatic cancer, gastric cancer and hepatic cancer cell lines were detected.•The complexes can inhibit cell proliferation and induce cell apoptosis in human cancer cell lines.Four new complexes based on L (where L = 3-ethyl-2-acetylpyrazine semicarbazone), namely [CoL2]Cl2·0.5H2O (1), [CoL2](NO3)2 (2), [CdL(H2O)2(NO3)](NO3)·H2O (3) and [CuL(CH3OH)Cl2]·[CuLCl2] (4) have been synthesized and characterized by X-ray diffraction analyses. The results show that the semicarbazone acts as a tridentate neutral ligand in all complexes. Each of complex 1 and 2 reveals a distorted octahedral geometry around the metal ion provided by two units of the ligand, while the ratio of the ligand and metal is 1:1 in complexes 3 and 4. The effect of complexes 1–4 on cell proliferation, apoptosis of human pancreatic cancer (Patu8988), human gastric cancer (SGC7901) and human hepatic cancer (SMMC7721) cell lines have been detected by MTT assay, Annexin V/PI double staining flow cytometry and TUNEL assay. The results show that complexes 1–4 can inhibit cell proliferation of Patu8988, SGC7901 and SMMC7721 cells, significantly higher than the effect of the ligand. However, the complex 4 reveals higher apoptosis rate, and displays up-regulated expression level of caspase 3, detected by western blotting, which also indicates the complex 4 can induce caspase-dependent cell apoptosis in SMMC7721.

•The biological activity of three dinuclear copper(II) complexes was investigated.•The three complexes can cause DNA damage.•Cell apoptosis was detected by AnnexinV/PI flow cytometry and Western blotting.•All the complexes can effectively induce apoptosis of the human tumor cells.Nowadays, chemotherapy is a common means of oncology. However, it is difficult to find excellent chemotherapy drugs. Here we reported three new ternary copper(II) complexes which have potential chemotherapy characteristics with reduced Schiff base ligand and heterocyclic bases (TBHP), [Cu(phen)(TBHP)]H2O (1), [Cu(dpz)(TBHP)]H2O (2) and [Cu(dppz)(TBHP)]H2O (3) (phen = 1,10-phenanthroline, dpz = dipyrido [3,2:2′,3′-f]quinoxaline, dppz = dipyrido [3,2-a:2′,3′-c]phenazine, H2TBHP = 2-(3,5-di-tert-butyl-2-hydroxybenzylamino)-2-benzyl-acetic acid). The DNA-binding properties of the complexes were investigated by spectrometric titrations, ethidium bromide displacement experiments and viscosity measurements. The results indicated that the three complexes, especially the complex 13, can strongly bind to calf-thymus DNA (CT-DNA). The intrinsic binding constants Kb of the ternary copper(II) complexes with CT-DNA were 1.37 × 105, 1.81 × 105 and 3.21 × 105 for 1, 2 and 3 respectively. Comparative cytotoxic activities of the copper(II) complexes were also determined by 3-(4,5-dimethylthiazol-2yl)-2,5-diphenyltetrazolium bromide (MTT) assay. The results showed that the ternary copper(II) complexes had significant cytotoxic activity against the human lung cancer (A549), human esophageal cancer (Eca109) and human gastric cancer (SGC7901) cell lines. Cell apoptosis were detected by AnnexinV/PI flow cytometry and by Western blotting with the protein expression of p53, Bax and Bcl-2. All the three copper complexes can effectively induce apoptosis of the three human tumor cells.Three new ternary copper(II) complexes which have potential chemotherapy characteristics with reduced Schiff base ligand and heterocyclic bases, and the ternary copper(II) complexes had significant cytotoxic activity against the human cancer cell lines. They also can induce the cancer cell apoptosis.

•Three novel complexes were isolated and characterized by X-ray diffraction analyses.•The three complexes have excellent antitumor activities.•Cell apoptosis was detected by western blotting.Three novel complexes, [Cu4(L)4Cl4]·H2O (1), Zn(L)2 (2) and Cd(L)2 (3), based on HL (where HL = 2-acetylpyridine isonicotinohydrazone) were synthesized and characterized by X-ray diffraction analyses. In the tetranuclear complex 1, each copper(II) ion with a distorted square-planar coordination geometry is five-coordinated by one chloride anion, one ON2 donor set and one 4-pyridine nitrogen atom from another adjacent actylhydrazone ligand. However, the central ions in complexes 2 and 3 possess distorted octahedral coordination geometry, surrounded by two ON2 donor sets. In addition, all the complexes have excellent antitumor activity towards human lung cancer (A549) and human gastric cancer (SGC7901 and BGC823) cell lines. Furthermore, cell apoptosis induced by complex 1 was detected through TUNEL and Annexin V/PI staining with flow cytometric analysis and western blotting analysis.Three novel complexes, [Cu4(L)4Cl4]·H2O (1), Zn(L)2 (2) and Cd(L)2 (3), based on HL (where HL = 2-acetylpyridine isonicotinohydrazone) were synthesized and characterized by X-ray diffraction analyses. The cytotoxic apoptosis and western blotting were investigated.

Two isostructural hydrazide–hydrazone-based complexes, namely [Zn(L)(HL)(ClO4)]·H2O and [Ni(L)(HL)(ClO4)]·H2O (HL = 2-acetylpyridine isonicotinohydrazone), have been obtained and characterized by physicochemical and spectroscopic methods. In each complex, the first ligand is in the neutral keto form, while the second is in the deprotonated monoanionic enolate form. Both complexes have excellent antitumor activity toward A549 human lung cancer, and BGC823 and SGC7901 human gastric cancer cell lines. Furthermore, both complexes are active scavengers for O2−· and OH·, exerting superior activities compared to the free ligand.

•We investigate the biological activity of two new copper(II) complexes.•Drug 2 shows significant inhibitory effect to bacterial strains.•Drug 1 shows significant cytotoxic activities.Two novel Cu(II) complexes, [Cu(L)2(CH3OH)]·CH3OH (1) and [Cu(L)(DMF)Cl] (2) based on HL (where HL = 2-ethoxycarbonyl-5-formyl-3,4-dimethylpyrrole 4-hydroxylbenzoylhydrazone) were synthesized and characterized by X-ray diffraction analyses. The results show that in each complex, the acylhydrazone ligand is deprotonated and coordinated to the copper(II) ion via enolizated oxygen and imine nitrogen atoms. The central metal ion possesses a distorted square pyramidal and a square-planar coordination geometry in complexes 1 and 2, respectively. In addition, complex 2 shows obvious inhibitory effect to bacterial strains Staphylococcus aureus and Salmonella typhimurium, and complex 1 has excellent antitumor activity towards Hepatocellular carcinoma (Hep G2) cells (IC50 = 2.0 μM).Two novel Cu(II) complexes were synthesized and characterized. Complex 2 shows obvious inhibitory effect to bacterial strains, and complex 1 has excellent antitumor activity.

•We investigate the biological activity of three new ternary copper(II) complexes.•Chelated by phenanthroline, the anti-cancer activity of the drugs increases a lot.•Drug 3 shows more significant cytotoxic activities than 1 and 2.•All the complexes can cause DNA damage.Three mononuclear mixed ligand Cu(II) complexes of the type [Cu(L)(DTHA)]H2O⋅CH3OH, where H2DTHA is 2-(3,5-di-tert-butyl-2-hydroxybenzylamino) acetic acid and the co-ligand L is 1,10-phenanthroline (phen, 1), dipyrido[3,2-d:2′,3′-f]quinoxaline (dpq, 2) dipyrido [3,2-a:2′,3′-c]phenazine (dppz, 3) have been isolated and characterized. Absorption and emission spectral studies and viscosity measurements indicated that 3 interacts with DNA more strongly than all of the other complexes through intercalation mode. Furthermore, cytotoxicity studies on the tested four cell line indicated that they can efficiently inhibit the cell proliferation in a time-dependent manner, and the Hoechst 33258 staining assays have also been employed in finding the extent of DNA damage.Three new ternary copper(II) complexes 1–3 are synthesized and characterized. All of them show significant cytotoxic, cell apoptosis and DNA-biding activities.

Three new ternary copper(II) complexes, [Cu2(phen)2(PDIMAla)(H2O)2](ClO4)2·CH3OH (1), [Cu2(dpq)2(PDIMAla)(H2O)2](ClO4)2·CH3OH (2) and [Cu2(dppq)2(PDIMAla)(H2O)2](ClO4)2·CH3OH (3) (phen = 1,10-phenanthroline, dpq = dipyrido[3,2:2′,3′-f]quinoxaline, dppz = dipyrido[3,2-a:2′,3′-c]phenazine, H2PDIMAla = N,N′-(p-xylylene)di-alanine acid) have been synthesized and the complex 1 has been structurally characterized by single-crystal X-ray crystallography, spectrometric titrations, ethidium bromide displacement experiments, CD (circular dichroism) spectral analysis and viscosity measurements. The results indicate that the three compounds, especially the complex 3, can strongly bind to calf-thymus DNA (CT–DNA). The intrinsic binding constants Kb of the ternary copper(II) complexes with CT–DNA are 0.38 × 105, 1.4 × 105 and 7.8 × 105 for 1, 2 and 3, respectively. Comparative cytotoxic activities of the copper(II) complexes are also determined by acid phosphatase assay. The results show that the ternary copper(II) complexes have significant cytotoxic activity against the human hepatic (HepG2), human promyelocytic leukemia (HL60) and human prostate (PC3) cell lines. Investigation of antioxidation property show that all the copper(II) complexes have strong scavenging effects for hydroxyl radicals.Graphical abstractThree novel ternary copper(II) complexes 1–3 are synthesized and characterized. All of them show significant cytotoxic, antioxidation and DNA-biding activities.Highlights► We investigate the biological activity of three new ternary copper(II) complexes. ► Chelated by phenanthroline, the anti-cancer activity of the drugs increase a lot. ► Drug 3 show more significant cytotoxic activities than 1 and 2.