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A sensitive detection method combined with an effective on-line concentration may improve the analytical performance of a paper-based analytical device (PAD), and its merits of low cost and portability in POCT are fully demonstrated. Here, a sensitive PAD system with chemiluminescence (CL) detection and electrokinetic preconcentration was introduced, and the performance was demonstrated by the detection of hemin. A commercially available low cost and miniaturized optical detection module was used for the CL detection. Firstly, hemin was stacked on a simple paper fluidic channel based on field amplified stacking (FAS), and then a CL reagent (luminol–H2O2) was loaded on the stacked band to initiate the CL reaction. The photons were directly detected using the detection module. With optimization of the background electrolyte (BGE), voltage and CL reagent, a limit of detection (LOD) of 0.58 nM for hemin was obtained with a linear range of 1–1000 nM (R2 = 0.995). With FAS, the signal intensity was about 13-fold enhanced. This PAD also exhibited satisfactory selectivity over possible interfering components at a 104 times higher concentration. The applicability of the PAD was demonstrated by the detection of hemin from iron supplements and human serum samples. With total manual operation, recovery rates of 84.8–115.6% were obtained with an RSD of less than 14.3%. With the introduction of the optical detection model, and together with FAS, both the LOD and dynamic range of this PAD were effectively improved. [ABSTRACT FROM AUTHOR]

A new oxamido-bridged dicopper(II) complex formulated as [Cu2(ndpox)(bpy)(CH3OH)2]- (ClO4), where H3ndpox is N-(2-hydroxy-5-nitrophenyl)-N′-[3-(diethylamino)propyl]oxamide; and bpy represents 2,2′-bipyridine, was synthesized and structurally characterized using X-ray single-crystal diffraction and other methods. In the molecule, the endo- and the exo-copper(II) ions bridged by the cis-ndpox3− ligand are in {N3O2} and {N2O3} square- pyramidal environments, respectively. There is a three-dimensional hydrogen bonding network dominated by O-H···O and C-H···O interactions in the crystal. The reactivity toward DNA/protein bovine serum albumin (BSA) revealed that the complex could interact with herring sperm DNA (HS-DNA) through the intercalation mode, and effectively quench the intrinsic fluorescence of BSA via a static process. Cytotoxicity studies suggest that the complex displays selective cancer cell antiproliferative activity. The present investigation confirmed that the combined effects of both electron-withdrawing and hydrophobic groups on the bridging ligand in the dicopper(II) complex systems can increase DNA/BSA-binding ability and in vitro anticancer activity. [ABSTRACT FROM AUTHOR]

A new trinickel(II) complex bridged by N-[3-(dimethylamino)propyl]- N′-(2-hydroxylphenyl)oxamido (H3pdmapo), namely [Ni3(pdmapo)2(H2O)2]⋅4CH3OH, was synthesized and characterized by X-ray single-crystal diffraction and other methods. In the molecule, two symmetric cis-pdmapo3− mononickel(II) complexes as a 'complex ligand' using the carbonyl oxygen atoms coordinate to the center nickel(II) ion situated on an inversion point. The Ni···Ni distance through the oxamido bridge is 5.2624(4) Å. The center nickel(II) ion and the lateral ones have octahedral and square-planar coordination geometries, respectively. In the crystal, a three-dimensional supramolecular network dominated by hydrogen bonds is observed. The reactivity toward DNA/protein bovine serum albumin (BSA) revealed that the complex could interact with herring sperm DNA ( HS-DNA) through the intercalation mode and quench the intrinsic fluorescence of BSA via a static mechanism. The in vitro anticancer activities suggested that the complex is active against the selected tumor cell lines. [ABSTRACT FROM AUTHOR]

Reaction of 2-C5H4 NCOSPh, generated from 2-C5H4NCO2H and PhSH in the presence of DCC, with Fe3(CO)12affords (μ-κ2C,N-2-C5H4N)(μ-PhS)Fe2(CO)6(1) and (μ-PhS)2Fe2(CO)6(2). Reaction of (NC)2C=C(SMe)2, formed from NCCH2CN, CS2, and MeI in the presence of NaOH, with Fe3(CO)12provides (μ-κ2C,S-(NC)2C=CSMe)(μ-MeS)Fe2(CO)6(3) and (μ-MeS)2Fe2(CO)6(4). All complexes have been fully characterized by EA, IR,1H NMR, and13C NMR spectroscopy and structurally determined by X-ray crystallography. In1and3, the group attached to the bridging S is at the equatorial position. In2, two phenyl groups are at equatorial positions. Two isomers of4, ae-4 and ee-4, can be separated by thin-layer chromatography. DFT calculations reveal that the Gibbs energy difference between ae-4and ee-4is −2.17 kcal mol−1in THF and −2.29 kcal mol−1in benzene, and the isomerization barrier between ae-4and ee-4is 14.92 kcal mol−1in THF and 16.84 kcal mol−1in benzene. All these results suggest that ae-4is more stable than ee-4in either THF or benzene, and the two isomers do not interconvert. Electrochemical studies of1and3demonstrate that using HOAc as a proton source1and3can catalyze H2production. [ABSTRACT FROM AUTHOR]

A new ternary monocopper(II) complex with co-ligands of 2,2′-diamino-4,4′-bithiazole (dabt) and picrate (pic), namely [Cu(dabt)(pic)2], has been synthesized and characterized using elemental analyses, molar conductance measurements, infrared and electronic spectral studies and single-crystal X-ray diffraction. The crystal structure analyses revealed that the copper(II) ion has a {CuN2O4} distorted octahedral coordination environment. The hydrogen bonding interactions contribute to a three-dimensional supramolecular structure in the crystal. The reactivity towards herring sperm DNA showed that the copper(II) complex can interact with DNA in the mode of intercalation. The molecular docking of the complex with d(ACCGACGTCGGT)2 demonstrated that the copper(II) complex is stabilized by hydrogen bonding interaction. The in vitro anticancer activities suggested that the copper(II) complex is active against selected tumor cell lines. The effects of the two co-ligands in the copper(II) complex on DNA-binding events and in vitro anticancer activity are preliminarily discussed. Copyright © 2016 John Wiley & Sons, Ltd. [ABSTRACT FROM AUTHOR]

The manganese complex of methionine hydroxy analogue was synthesized with methionine hydroxy analogue and manganese chloride as main raw materials. The composition and structure of the complex were characterized by elemental analyses, infrared spectra, and X-ray powder diffraction. The formula of the complex was Mn(C5H9O3S)2. The experimental results indicated that the manganese ion was, respectively, coordinated by the carboxylic and hydroxyl oxygen atoms from the methionine hydroxy analogue ligand. The crystal structure of the complex belonged to monoclinic system with the lattice parameters of a = 1.2775 nm, b = 1.5764 nm, c = 1.5764 nm, and β = 94.06°. The thermal decomposition process of the complex was studied by thermogravimetry and differential thermal analysis. The decomposition of the complex has taken place above 200°C. The residue was mainly manganese sulfide, and the experimental and calculated percentage mass loss was also given. The parameters of thermal decomposition kinetics for the complex, such as activation energy, reaction order, and preexponential factor, were calculated by using Kissinger, Flynn-Wall-Ozawa, and Freeman-Carroll methods, and the kinetic equations of the thermal decomposition were obtained. [ABSTRACT FROM AUTHOR]

ABSTRACT A new one-dimensional (1D) copper(II) coordination polymer {[Cu2(dmaepox)(dabt)](NO3)·0.5 H2O} n, where H3dmaepox and dabt denote N-benzoato- N′-(3-methylaminopropyl)oxamide and 2,2′-diamino-4,4′-bithiazole, respectively, was synthesized and characterized by single-crystal X-ray diffraction and other methods. The crystal structure analysis revealed that the two copper(II) ions are bridged alternately by cis-oxamido and carboxylato groups to form a 1-D coordination polymer with the corresponding Cu···Cu separations of 5.1946(19) and 5.038(2) Å. There is a three-dimensional supramolecular structure constructed by hydrogen bonding and π-π stacking interactions in the crystal. The reactivity towards herring sperm DNA ( HS-DNA) and bovine serum albumin (BSA) indicated that the copper(II) polymer can interact with the DNA in the mode of intercalation, and bind to BSA responsible for quenching of tryptophan fluorescence by the static quenching mechanism. The in vitro cytotoxicity suggested that the copper(II) polymer exhibits cytotoxic effects against the selected tumor cell lines. [ABSTRACT FROM AUTHOR]

ABSTRACT Based on the importance of the design and synthesis of transition metal complexes with noncovalent DNA/protein-binding abilities in the field of metallo pharmaceuticals, a new mononuclear ternary copper(II) complex with mixed ligands of diethylenetriamine (dien) and picrate anion (pic), identified as [Cu(dien)(pic)](pic), was synthesized and characterized by elemental analysis, molar conductivity measurement, infrared spectrum, electronic spectral studies, and single-crystal X-ray diffractometry. The structure analysis reveals that the copper(II) complex crystallizes in the monoclinic space group P21/c, and the copper(II) ion has a distorted square pyramidal coordination geometry. A two-dimensional supramolecular structure is formed through hydrogen bonds. The DNA/bovine serum albumin (BSA)-binding properties of the complex are explored, indicating that the complex can interact with herring sperm DNA via intercalation mode and bind to BSA responsible for quenching of tryptophan fluorescence by static quenching mechanism. The in vitro anticancer activity shows that the copper(II) complex is active against the selected tumor cell lines. [ABSTRACT FROM AUTHOR]

A 1-D copper(II) coordination polymer formulated as {[Cu2(bdpox)(dabt)](NO3)·H2O}n, where H3bdpox and dabt denoteN-benzoate-N′-[3-(diethylamino)propyl]oxamide and 2,2′-diamino-4,4′-bithiazole, respectively, was synthesized and characterized by elemental analyses, molar conductance measurement, IR and electronic spectra studies, and single-crystal X-ray diffraction. The crystal structure analysis reveals that copper(II) ions are bridged by bothcis-oxamido and carboxylato groups to form a 1-D coordination polymer with corresponding Cu···Cu separations of 5.2420(10) and 5.1551(8) Å. Theendo- andexo-copper(II) ions of thecis-oxamido-bridge are located in distorted square-planar and square-pyramidal geometries, respectively. There is a 2-D hydrogen bonding network in the crystal. Thein vitroanticancer activities suggest that the copper(II) complex is active against selected tumor cell lines. The reactivities toward herring sperm DNA and bovine serum albumin (BSA) reveal that the copper(II) complex can interact with DNA by intercalation and effectively quench the intrinsic fluorescence of BSA via a static mechanism. The influence of hydrophobicity of the substituents in bridging ligands on DNA and protein binding properties and thein vitroanticancer activities of such copper(II) polymers is discussed. A new 1-D copper(II) coordination polymer was synthesized and structurally characterized.In vitroanticancer activity and reactivity toward DNA and protein of the copper(II) polymer was studied. [ABSTRACT FROM AUTHOR]

ABSTRACT A new μ-oxamido-bridged dicopper(II) complex, [Cu2(papo)(H2O)- (phen)]Cl·CH3OH·H2O, where H3papo and phen represent N-(2-hydroxyphenyl)- N'-(3-aminopropyl)oxamide and 1,10-phenanthroline, respectively, has been synthesized and characterized by elemental analysis, molar conductivity measurement, infrared and electronic spectra studies, and single-crystal X-ray diffraction. The complex crystallizes in the triclinic space group P-1. Each copper(II) ion is located in a slightly distorted square-pyramidal environment. The Cu···Cu distance through the oxamide bridge is 5.1848(7) Å. The three-dimensional supramolecular structure is built-up by hydrogen bonds and π-π stacking interactions. The dicopper(II) complex exhibits cytotoxic activity against the SMMC-7721 and A549 cell lines. The reactivity toward herring sperm DNA and protein bovine serum albumin (BSA) reveals that the dicopper(II) complex can interact with the DNA by the intercalation mode, and effectively quench the intrinsic fluorescence of BSA via a static mechanism. The influence of hydrophobicity of the bridging ligand on DNA-binding properties and in vitro cytotoxic activities of this kind of dicopper(II) complexes was investigated. [ABSTRACT FROM AUTHOR]

A new mononuclear copper(II) complex identified as [Cu(bpy)2(pic)](pic), where bpy represents 2,2ʹ-bipyridine and pic stands for picrate (pic), has been synthesized and characterized by elemental analysis, molar conductivity, IR and electronic spectral studies, and single-crystal X-ray diffraction. The crystal structure analysis reveals that copper(II) has a distorted square-pyramidal coordination geometry. The hydrogen bonding andπ–πstacking interactions contribute to a 3-D supramolecular structure in the crystal. The DNA-binding properties of the copper(II) complex are investigated both theoretically and experimentally, revealing that the copper(II) complex interacts with herring sperm DNA (HS-DNA) by intercalation, and the molecular docking of the copper(II) complex with the self-complementary DNA duplex of sequence d(ACCGACGTCGGT)2facilitates the binding events. Thein vitroanticancer activities suggest that the copper(II) complex is active against selected tumor cell lines. The influence of the complexation of pic in the mononuclear copper(II) complexes on DNA-binding properties andin vitroanticancer activities is discussed. A new monocopper(II) complex was synthesized and structurally characterized. The DNA-binding properties andin vitroanticancer activities of the complex were investigated. [ABSTRACT FROM AUTHOR]

A new tetracopper(II) complex, [Cu(papo)(dabt)](NO)·2HO, where Hpapo and dabt stand for N-(2-hydroxyphenyl)- N′-(3-aminopropyl)oxamide and 2,2′-diamino-4,4′-bithiazole, respectively, has been synthesized and characterized by elemental analyses, molar conductivity, infrared and electronic spectra, and single-crystal X-ray diffraction. The crystal structure reveals that the presence of a circular tetracopper(II) cation [Cu(papo)(dabt)] with an embedded center of inversion is assembled by a pair of cis-oxamido-bridged dicopper(II) units through μ-phenolato bridges, in which the Cu(II) atoms at the inner sites of papo have square-planar environments and those at the outer sites are in square-pyramidal geometries. The separations of the Cu(II) ions bridged by oxamide and phenolate groups are 5.2039(14) and 3.7159(12) Å, respectively. In the crystal, two-dimensional supramolecular structures are formed by hydrogen bonds and π- π stacking interactions. An in vitro cytotoxicity experiment indicates that the tetracopper(II) complex exhibits cytotoxic effects against human hepatocellular carcinoma cell SMMC-7721 and human lung adenocarcinoma cell A549. The reactivity toward HS-DNA and protein BSA suggested that the tetracopper(II) complex can interact with HS-DNA in the mode of intercalation, and the complex binds to BSA responsible for quenching of tryptophan fluorescence by a static quenching mechanism. Graphical abstract: [Figure not available: see fulltext.]The present tetracopper(II) complex constructed from N-(2-hydroxyphenyl)- N′-(3-aminopropyl)oxamide has been synthesized and characterized by X-ray single-crystal diffraction. The cytotoxicities and reactivities toward DNA and protein of the complex have been investigated. [ABSTRACT FROM AUTHOR]

ABSTRACT A new dinuclear copper(II) complex bridged by N-[3-(dimethylamino)propyl]- N′- (2-carbo-xylatophenyl)oxamide (H3dmapob), and endcapped with 2,2′-diamino-4,4′-bithiazole (dabt), namely [Cu2(dmapob)(dabt)(CH3OH)(pic)]·(DMF)0.75·(CH3OH)0.25 has been synthesized and characterized by elemental analysis, molar conductivity measurement, infrared and electronic spectra studies, and single-crystal X-ray diffraction. In the crystal structure, both copper(II) ions have square-pyramidal coordination geometries. The Cu···Cu separation through the oxamido bridge is 5.176(9) Å. A two-dimensional supramolecular framework is formed through hydrogen bonds and π-π stacking interactions. The reactivities toward herring sperm DNA and bovine serum albumin (BSA) show that the complex can interact with the DNA via intercalation mode and bind to the BSA responsible for quenching of tryptophan fluorescence by the static quenching mechanism. The in vitro anticancer activities suggest that the copper(II) complex is active against the selected tumor cell lines. The influence of different bridging ligands in dinuclear complexes on the DNA- and BSA-binding properties as well as anticancer activities is preliminarily discussed. [ABSTRACT FROM AUTHOR]

A new tetracopper(II) complex bridged by oxamido and carboxylate, [Cu4(bhyox)2(phen)2(H2O)2](pic)2, where H3bhyox, phen and Hpic denoteN-benzoate-N′-[2-(2-hydroxyethylamino)ethyl]oxamide, 1,10-phenanthroline, and 2,4,6-trinitrophenol, respectively, has been synthesized and characterized by elemental analysis, molar conductivity, IR, electronic spectra, and single-crystal X-ray diffraction. The crystal structure reveals that the cyclic tetracopper(II) cation [Cu4(bhyox)2(phen)2(H2O)2]2+with an embedded center of inversion is assembled by a pair ofcis-oxamido-bridged bicopper(II) units via carboxylate bridges, in which copper(II) ions are distorted square pyramidal. The Cu⋯Cu separations through the oxamido and the carboxylate bridges are 5.1944(6) and 5.3344(7) Å, respectively. In the crystal, the supramolecular structure is composed of classical hydrogen bonding chains assembled by 2D non-classical hydrogen-bonding networks andπ–πstacking interaction.In vitrocytotoxicity experiment shows that the tetracopper(II) complex exhibits cytotoxic activity against the SMMC7721 and A549 cell lines. The reactivity towards herring sperm DNA (HS-DNA) and protein bovine serum albumin (BSA) suggests that the tetracopper(II) complex can interact with the DNA by intercalation, and the complex binds to protein BSA responsible for quenching of tryptophan fluorescence by static quenching mechanism. [ABSTRACT FROM AUTHOR]

ABSTRACT A new oxamido-bridged bicopper(II) complex, [Cu2(pdpox)(bpy)(CH3OH)](ClO4), where H3pdpox and bpy stand for N-(2-hydroxyphenyl)- N′-[3-(diethylamino)propyl]oxamide and 2,2′-bipyridine, respectively, has been synthesized and characterized by elemental analyses, molar conductivity measurements, infrared and electronic spectra studies, and X-ray single crystal diffraction. In the crystal structure, the pdpox3− ligand bridges two copper(II) ions as cisoid conformation. The inner copper(II) ion has a {N3O} square-planar coordination geometry, while the exo- one is in a {N2O3} square-pyramidal environment. There are two sets of interpenetrating two-dimensional hydrogen bonding networks parallel to the planes (2 1 0) and ( [ABSTRACT FROM AUTHOR]

A new dicopper(II) complex bridged byN-benzoato-N′-(hydroxypropyl)oxamide (H3oxbpa) and end-capped with 1,10-phenanthroline (phen), [Cu2(oxbpa)(phen)(H2O)](pic)·2H2O (where pic denotes picrate anion) has been synthesized and characterized by elemental analyses, molar conductance, IR and electronic spectra studies, and single-crystal X-ray diffraction. In the crystal of the dicopper(II) complex, copper(II) ions are bridged by cis-oxamide with a CuCu separation of 5.258(5) Å. The ones at the inner and the exo-sites of the cis-oxbpa3−are square-planar and square-pyramidal coordination, respectively. These complexes are assembled to a one-dimensional chain via classical O–HO hydrogen bonds.In vitrocytotoxicity shows that the dicopper(II) complex exhibits cytotoxic activity against SMMC7721 and A549 cell lines. The reactivity towards (Herring sperm DNA) and protein bovine serum albumin (BSA) revealed that the dicopper(II) complex can interact with DNA by intercalation, and the complex binds to protein BSA responsible for quenching of tryptophan fluorescence by static quenching mechanism. [ABSTRACT FROM AUTHOR]

A 1-D polymeric copper(II) complex alternately bridged by N,N′-bis(N-hydroxyethylaminopropyl)oxamide (heap2−) and terephthalate (tpa2−), [Cu2(heap)(tpa)] n , has been synthesized and characterized by single-crystal X-ray diffraction. The crystal structure reveals that the asymmetric unit of the copper(II) polymer is half a dinuclear copper(II) complex, [Cu2(heap)(tpa)], in which Cu(II) is located in a square-pyramidal coordination environment. Separations of Cu(II) through heap2− and tpa2− bridges are 5.2459(6) and 11.1375(6) Å, respectively. The complex chains, accompanied with glide planes parallel to the a0c plane, can be classified to two groups according to their extending direction. Hydrogen bonds occur between a complex chain and any adjacent ones in the other orientation. Consequently, a 3-D supramolecular network is completed. The polymeric copper(II) complex exhibits potent anticancer activities against human hepatocellular carcinoma cell SMMC-7721 and human lung adenocarcinoma cell A549 tested by sulforhodamine B assays. The interactions of the polymeric copper(II) complex with herring sperm DNA (HS-DNA) are investigated by using electronic absorption titration, fluorescence titration, electrochemical titration, and viscometry measurements. The results suggest that the polymeric copper(II) complex interacts with HS-DNA via intercalation with intrinsic binding constant of 1.8 × 106 (mol L−1)−1. [ABSTRACT FROM PUBLISHER]

Two new dicopper(II) complexes bridged by N-benzoato- N′-(2-amino-2-methylethyl)-oxamidate (oxbm), and end-capped with 2,2′-bipyridine (bpy) and 1,10-phenanthroline (phen), respectively, namely [Cu(oxbm)(bpy)(HO)](pic) ( 1) and [Cu(oxbm)(phen)(HO)(CHOH)](pic) ( 2) (where pic = 2,4,6-trinitrophenol), have been synthesized and characterized by elemental analyses, molar conductivity measurements, IR, electronic spectra, and X-ray single crystal diffraction. In the two complexes, the central copper(II) atoms are bridged by cis-oxbm with Cu···Cu separations of 5.1815 Å ( 1) and 5.1672 Å ( 2), respectively. Atoms Cu1 and Cu2 are both in distorted square-pyramidal coordination geometries. The three-dimensional supramolecular structures in complexes 1 and 2 are built up by classical and non-classical hydrogen bonding chains. The interactions of the two dicopper(II) complexes with herring sperm DNA (HS-DNA) are investigated by using electronic and fluorescence spectra, electrochemical techniques, and viscometry. The results show that the two dicopper(II) complexes interact with HS-DNA in the mode of intercalation and complex 2 possesses stronger intercalating ability. Cytotoxicities experiments reveal that the two dicopper(II) complexes exhibit cytotoxic effects against human hepatocellular carcinoma cell SMMC-7721 and human lung adenocarcinoma cell A549. Cytotoxic activities follow the order 2 > 1, which are thought to be related with their DNA-binding affinities. The influence of the substituent on terminal ligands in the dicopper(II) complexes on DNA-binding properties and anticancer activities is preliminarily discussed. [ABSTRACT FROM AUTHOR]

Two one-dimensional copper(II) coordination polymers with different dissymmetrical N,N′- bis(substituted)oxamide ligands were synthesized, namely {[Cu(dmaepox)(dabt)]pic·HO} (1) and {[Cu(dmapob)(dabt)]NO·0.6HO} (2), where Hdmaepox and Hdmapob stand for N-(2-carboxylatophenyl)- N′-[3-(methylamino)propyl]oxamidate and N-(2-carboxylatophenyl)- N′-[3-(dimethylamino)propyl]oxamidate, respectively, and dabt is 2'2′-diamino-4'4′-bithiazole. Polymer 1 was characterized by elemental analyses, IR and electronic spectra and single-crystal X-ray diffraction. The crystal structure reveals that polymer 1 consists of many binuclear copper(II) units bridged by cis-oxamide and carboxylate groups. The two copper(II) ions are located in square-planar and square-pyramidal coordination environments, respectively. The separations of the Cu(II) atoms bridged by oxamide and carboxylate groups are 5.2035(7) and 5.1196(7) Å, respectively. The crystal structure of polymer 2 has been reported in our previous paper. However, its relative properties were not studied. In order to compare the influence of different bridging ligands on the cytotoxicities and DNA-binding properties, the cytotoxicities and reactivities towards DNA of polymers 1 and 2 were investigated. The results suggest that the two polymers can interact with herring sperm DNA in the mode of intercalation with binding affinities following the order of 1 > 2, and this is consistent with their in vitro cytotoxicities. [ABSTRACT FROM AUTHOR]

A new one-dimensional copper(II) polymer with formula of [Cu(heae)(tpa)]·nHO, where heae and tpa stand for the dianions of N, N′- bis( N-hydroxyethylaminoethyl)oxamide and terephthalic acid, respectively, has been synthesized and characterized by elemental analysis, conductivity measurement, IR and electronic spectral studies, and single-crystal X-ray diffraction. The crystal structure consists of a one-dimensional copper(II) coordination polymeric chain constructed by the [Cu(heae)] cations as the inorganic second building units (SBUs) and the tpa anions as linkers. The Cu···Cu separations through the bridges of heae and tpa are 5.2472(6) and 10.9677(8) Å, respectively. Both the copper(II) ions have square pyramidal coordination geometries. A three-dimensional hydrogen bonding network is observed in the crystal. The measured molar conductivity suggests that the polymer may stay intact in solution as the 1D polymer in the crystal. The cytotoxicities of the polymeric copper(II) complex were tested by Sulforhodamine B (SRB) assays against human hepatocellular carcinoma cell SMMC-7721 and human lung adenocarcinoma cell A549. The polymer exhibits potent cytotoxic effects against the two cell lines. The binding properties of the copper(II) polymer with herring sperm DNA ( HS-DNA) have been investigated by using UV absorption and fluorescence spectra and electrochemical techniques and viscosity. The results show that the copper(II) polymer interacts with HS-DNA in the mode of intercalation with the intrinsic binding constant of 1.07 × 10 M. [ABSTRACT FROM AUTHOR]

Two 1-D coordination polymers have been synthesized and identified as [Zn(ox)(en)] n (H2O)2 n (1) and [Cu2(dmeo)(N3)2] n (2), where en represents diaminoethane, ox and dmeo stand for dianions of oxalic acid and N,N′-bis[2-(dimethylamino)ethyl]oxamide, respectively. Polymer 1 was characterized by elemental analysis, molar conductance measurement, IR and electronic spectra, and single-crystal X-ray diffraction. Polymer 1 consists of 1-D chains bridged by oxalate. The ZnII can be described as a distorted octahedral environment and the ZnII···ZnII separation through the μ-oxalato-bridge is 5.5420(9) Å. Hydrogen bonds assemble the coordination polymers to a 3-D supermolecular structure. The crystal structure of 2 has been reported previously. However, the bioactivities were not studied. The DNA-binding properties and cytotoxic activities of the two coordination polymers are investigated. The results suggest that the two polymers interact with HS-DNA in groove binding with binding affinity following the order of 1 > 2, which is consistent with their anticancer activities. [ABSTRACT FROM AUTHOR]

A new µ-oxamido-bridged dicopper(II) complex, [Cu2(pdmaeox)(bpy)(H2O)](pic) · H2O [H3pdmaeox = N-phenolato-N'-[2-(dimethylamino)ethyl]oxamide, Hpic = 2,4,6-trinitrophenol, bpy = 2,2'-bipyridine], has been synthesized and characterized by elemental analyses, molar conductivity measurement, infrared, and electronic spectra studies, and X-ray single-crystal diffraction. The complex crystallizes in the triclinic system, P 1 space group, with crystallographic data: a = 10.7815(2) Å, b = 11.3598(2) Å, c = 14.1389(3) Å, and z = 2. In [Cu2(pdmaeox)(bpy)(H2O)]+, one copper(II) resides in the inner site with a square-planar coordination geometry and the other is chelated by the two exo-oxygen atoms of the cis-pdmaeox3- ligand in a square-pyramidal environment. The Cu···Cu separation through cis-pdmaeox3- bridge is 5.1834(4) Å. The crystal structure is stabilized by hydrogen bonds and π-π stacking interactions. The interaction of the dicopper(II) complex with herring sperm-DNA (HS-DNA) has been investigated by electronic absorption titration, fluorescence titration, electrochemical titration, and viscosity measurements. The results reveal that the interaction of the dicopper(II) complex with HS-DNA might be electrostatic binding. The effects of bridging ligand on the interaction of the dinuclear complex with HS-DNA were preliminarily investigated. [ABSTRACT FROM AUTHOR]

In this study, a new μ-oxamido-bridged binuclear copper(II) complex [Cu2(heap)(H2O)2](pic)2 ⋅ 2H2O, where heap and pic stand for the anion of N,N'-bis(N-hydroxyethylaminopropyl)oxamide and 2,4,6-trinitrophenol, respectively, has been synthesized and characterized by elemental analyses, IR, UV, molar conductance, and single-crystal X-ray diffraction. The complex has an embedded inversion center at the middle of the C-C bond of the oxamido group. Each copper(II) is in a square-pyramidal coordination geometry. The bridging ligand (heap) adopts a bis-tetradentate trans conformation and the oxamido group is in an imidic acid configuration. Hydrogen bonds contribute to a 3-D supramolecular structure in the crystal. The interaction of the binuclear complex with herring sperm deoxyribonucleic acid (HS-DNA) has been investigated by using absorption and emission spectra, electrochemical techniques, and viscometry. The results suggest that the binuclear copper(II) complex interacts with HS-DNA by electrostatic interaction with intrinsic binding constant of 2.67 × 104 (mol L-1)-1. The influence of anions on the structure and the interaction of the binuclear complex with HS-DNA were preliminarily discussed. [ABSTRACT FROM AUTHOR]

novel one-dimensional copper(II) complex formulated as [Cu(dmaeoxd)(ox)]· nHO (dmaeoxd = N, N′-bis[2-(dimethylamino)ethyl]oxamide, ox = oxalate), which represents the first coordination polymer alternately bridged by oxalate and oxamidate ligands, has been synthesized and characterized by elemental analysis, conductivity measurement and IR spectra. The single-crystal X-ray analysis reveals that the [Cu(dmaeoxd)] building blocks are bridged by oxalate groups to form a neutral 1-D coordination polymer, which involves hydrogen bonds with lattice water molecules and results in a three dimensional supermolecular structure. The voltammetric studies of the copper(II) polymer with DNA interaction are preliminarily investigated. [ABSTRACT FROM AUTHOR]

A new oxamido-bridged tetracopper(II) complex, [Cu4(oxbe)2(bpy)2](ClO4)2 · 2H2O, where H3oxbe and bpy stand for N-benzoato-N'-(2-aminoethyl)oxamide and 2,2'-bipyridine, has been synthesized and characterized by elemental analyses, molar conductivity, infrared and electronic spectra, and single-crystal X-ray diffraction. It crystallizes in triclinic system, space group P-1, with crystallographic data: a = 7.829(5) Å, b = 12.680(5) Å, c = 13.420(5) Å, α = 104.665(5)°, β = 95.275(5)°, γ = 106.931(5)°, and Z = 1. The circular tetranuclear copper(II) cation [Cu4(oxbe)2(bpy)2]2+ with an embedded center of inversion is assembled by a pair of cis-oxbe-bridged dinuclear copper(II) units through coordination between carboxyl and copper(II). One copper(II) is located in a slightly distorted square-planar environment, while the other is in a distorted square-pyramidal geometry. In the crystal structure, abundant hydrogen bonds and aromatic stackings link the tetranuclear copper(II) units into an overall 3-D framework. Interactions of the tetranuclear copper(II) complex with herring sperm DNA (HS-DNA) are investigated by using UV absorption and fluorescence spectra, electrochemical techniques, and viscometry. The results suggest that the tetranuclear copper(II) complex interacts with DNA by intercalation with an intrinsic binding constant of 1.47 × 105 mol-1 L. [ABSTRACT FROM AUTHOR]

A new μ-oxamido-bridged dicopper(II) complex, Cu2(heap)(NO3)2 (1), where heap is the dianion of N,N'-bis(N-hydroxyethylaminopropyl)oxamide, has been synthesized and characterized by elemental analysis, molar conductivity, IR and electronic spectral studies, and X-ray single-crystal diffraction. The complex consists of a neutral centro-symmetric binuclear copper(II) unit with an inversion center at the midpoint of the Cl-Cli bond. The copper(II) has square-pyramidal coordination geometry and the bridging heap adopts a bis-tetradentate conformation. The binuclear units are linked into a 3-D framework by N-H ··· O, O-H ··· O, and C-H ··· O hydrogen bonds. Due to weak coordination between copper(II) and nitrate, the neutral dicopper(II) units are present as binuclear cations and nitrate anions in solution. Antibacterial assays indicate that the complex shows better activity than the ligand. Interactions of the complex with herring sperm DNA (HS-DNA) have been investigated by using cyclic voltammetry, UV absorption titrations, ethidium bromide fluorescence displacement experiments, and viscometry measurements. The results suggest that the binuclear copper(II) complex interacts with HS-DNA by electrostatic interaction with intrinsic binding constant of 3.33 × 104 M-1. [ABSTRACT FROM AUTHOR]

A new binuclear zinc(II) complex bridged by μ-oxalate, and end-capped with 2,2'-bipyridine (bpy), [Zn2(ox)(bpy)4](ClO4)2 · H2O, has been synthesized and characterized by elemental analyses, molar conductance, IR, and electronic spectra and single-crystal X-ray diffraction. The single-crystal X-ray analysis reveals that the [Zn2(ox)(bpy)4]2+ cation has two zinc(II) centers bridged by a planar bis(bidentate) oxalate group with Zn···Zn distance of 5.482(3) Å; each zinc(II) is in a distorted octahedral environment. The crystal structure is stabilized by non-classical C-H···O hydrogen bonds and π-π stacking interactions to form a 3-D supramolecular structure. The interaction of the complex with calf-thymus DNA (CT-DNA) was explored by using electronic and fluorescence spectra and viscosity measurements. The results reveal that the complex intercalates with CT-DNA with intrinsic binding constant of 4.1 × 104 M-1. [ABSTRACT FROM AUTHOR]

A new two-dimensional polymeric copper(II) complex, [Cu2(heae)(N3)2]n, where heae stands for the dianion of N,N'-bis(N-hydroxyethylaminoethyl)oxamide, has been synthesized and characterized by elemental analysis, molar conductivity measurement, IR, electronic spectral studies and single-crystal X-ray diffraction. The compound crystallizes in the monoclinic system, P21/c space group with crystallographic data: a = 9.1588(18) Å, b = 6.6238(13) Å, c = 14.602(3) Å and Z = 2. The X-ray analysis reveals a two-dimensional copper(II) polymeric coordination network constructed by bis-tridentate chelated [Cu(trans-heae)Cu]2+ building blocks and end-on azido ligands. The environment around the copper(II) atom can be described as a square-based pyramid. The azido bridge is very asymmetric with one Cu-N bond distance short and the other long. The Cu ··· Cu separations through μ-trans-oxamidate and μ-azido bridges are 5.2996(13) Å and 4.2464(7) Å, respectively. The copper(II) complex is a polymer in the solid state, whereas in solution it exists as discrete neutral binuclear copper(II) species. Coordination mode of the azide in solution is proved by electronic spectra. The DNA-binding properties of the binuclear copper(II) species were investigated by emission spectral and electrochemical techniques, indicating the binuclear copper(II) complex binds to HS-DNA via a groove mode. [ABSTRACT FROM AUTHOR]

new one-dimensional polymeric copper(II) complex, [Cu(heae)(SCN)] · nHO [Hheae is N, N′-bis( N-hydroxyethylaminoethyl)oxamide], has been synthesized and characterized by elemental analysis, molar conductivity measurement, IR and electronic spectra studies, and single-crystal X-ray diffraction. The structure of the complex exhibits a neutral one-dimensional polymeric copper(II) zigzag chain [Cu(heae)(SCN)] constructed by μ- trans-heae and double μ-1,3-thiocyanate ligands. The environment about copper can be described as a square-pyramid. The neighboring second building units (SBUs), [Cu( trans-heae)Cu], are unequal with Cu···Cu separations of 5.287 and 5.273 Å for Cu1···Cu1 and Cu2···Cu2, respectively. The double thiocyanate ligands function as μ(1,3)-bridges to link these unequal SBUs thereby forming zigzag chains with a Cu1···Cu2 separation of 5.454 Å. The hydrogen bonds in the crystal structure self-assemble the one-dimensional chains into a three-dimensional supramolecular structure. The interaction of the polymeric copper(II) complex with herring sperm DNA ( HS-DNA) has been investigated by using absorption and emission spectra, electrochemical techniques and viscometry. The results reveal that the polymeric copper(II) complex interacts with HS-DNA via a groove binding mode with the intrinsic binding constant of 1.38 × 10 M. To the best of our knowledge, this is the first example about the structure and DNA-bonding studies of a one-dimensional polymeric copper(II) complex that is bridged alternately by trans-oxamidate and double-thiocyanate ligands. [ABSTRACT FROM AUTHOR]

new cyano-bridged copper (I) complex {[Cu(phen)CN][Cu(phen)][Cu(CN)]} (1) (phen = 1,10-phenanthroline) was synthesized under the solvothermal conditions, and characterized by elemental analysis, FI-IR spectra and single-crystal X-ray diffraction. The structure analysis reveals that complex 1 contains two [Cu(phen)CN][Cu(phen)][Cu(CN)] subunits, being, respectively, constructed into two chains with different cyano backbones. The resulting chains offer a double curvy chain by Cu···Cu weak interactions and π-π stacking interactions. It is exciting that the double curvy chains adopt anti-parallel array and result in a novel 3D architecture through π-π stacking interactions. According to the supramolecular self-assembly of complex 1, four types of stacking mode of phenanthroline moieties are given and discussed. Absorption and fluorescence titration studies of complex 1 with calf thymus DNA are suggestive of the intercalation binding mode with a intrinsic binding constant of 7.52 × 10 M and a linear Stern-Volmer quenching constant of 1.02 × 10 M. [ABSTRACT FROM AUTHOR]

A new μ-oxamido-bridged dicopper(II) complex, [Cu2(heap)](ClO4)2 · 2H2O [H2heap = N,N'-bis(N- hydroxyethylaminopropyl)oxamido], has been synthesized and structurally characterized by elemental analyses, molar conductance, IR and single-crystal X-ray diffraction. The single crystal X-ray analysis reveals that the asymmetric unit of the complex is composed of half a binuclear cation [Cu2(heap)]2+, one perchlorate anion, and one lattice water molecule. Each copper(II) atom is tetracoordinate in a distorted square-planar geometry and the bridging ligand (H2heap) adopts the trans conformation with an inversion centre at the middle of the C2-C2i bond. The structure cohesion is ensured by hydrogen bonding interactions, which form a two-dimensional supramolecular framework. The antibacterial assay indicates that the complex showed better activity than the ligand. [ABSTRACT FROM AUTHOR]

The title compound, [HgI 2 (CH 4 N 2 S) 2 ]·2C 11 H 6 N 2 O, is comprised of the Hg(II)-thiourea complex and free 4,5-diazafluoren-9-one (DAFONE). The complex assumes a distorted tetrahedral geometry at mercury formed by two thiourea molecules and two I - ions, the S-Hg-S angle [103.7°] being significantly smaller than S-Hg-I angles (115.2 and 114.3°). The complex and DAFONE molecules link to each other via hydrogen bonding to form a supramolecular structure. Significant π-π stacking is observed between neighboring DAFONE molecules. [ABSTRACT FROM AUTHOR]

The lipocalin proteins (lipocalins) are a large family of small proteins characterized by low sequence similarity and highly conserved crystal structures. Lipocalins have been found to play important roles in many human diseases. For this reason, a systemic analysis of the molecular properties of human lipocalins is essential. In this study, human lipocalins were found to contain four structurally conserved regions (SCRs) and could be divided into two subgroups. A human lipocalin protein-protein interaction network (PPIN) was constructed and integrated with their expression data in esophageal carcinoma. Many lipocalins showed obvious co-expression patterns in esophageal carcinoma. Their subcellular distributions also suggested these lipocalins may transfer signals from the extracellular space to the nucleus using the pathway-like paths. These analyses also expanded our knowledge about this human ancient protein family in the background of esophageal carcinoma. [ABSTRACT FROM AUTHOR]

A new potassium europium borate K 3 EuB 6 O 12 has been prepared using a high temperature molten salt method and structurally characterized by single crystal X-ray diffraction (SC-XRD) analyses. Its structure features a three-dimensional (3D) framework composed of isolated [B 5 O 10 ] 5− anions that are bridged by K + and Eu 3+ ions. In this structure, one crystallographic distinct atom site is mixed occupied by K/Eu at a molar ratio of 1:1. The self-activated photoluminescence (PL) of K 3 EuB 6 O 12 was studied. The excitation spectrum covers a wide range from 322 to 466 nm, which suggests that the K 3 EuB 6 O 12 phosphors can be effectively excited by a near-UV light source. The emission spectrum consists of groups of lines in the red spectral region due to the 5 D 0 → 7 F j (j = 1, 2, 3, 4) electronic transitions of Eu 3+ ions, with the most intense line at 611 nm. We may expect that K 3 EuB 6 O 12 has the potential to be a red phosphor pumped by near-UV LED chips. [ABSTRACT FROM AUTHOR]

Abstract: Two new binuclear copper(II) complexes bridged by N-(5-chloro-2-hydroxyphenyl)-N′-[3-(dimethylamino)propyl]oxamide (H3L), and end-capped with 4,4′-dimethyl-2,2′-bipyridine (Me2bpy) or 2,2′-diamino-4,4′-bithiazole (dabt), respectively, namely [Cu2L(H2O)(Me2bpy)][Cu2L(CH3OH)(Me2bpy)](ClO4)2·(CH3OH)0.7 (1) and [Cu2L(CH3OH)0.25(dabt)]ClO4·(H2O)1.5 (2), have been synthesized and characterized by single-crystal X-ray diffraction. In complex 1, the dissymmetric unit of it contains two bicopper(II) cations, the cis-L3− ligands bridge two copper(II) ions with the corresponding separations of 5.1881(11)Å (Cu1···Cu2) and 5.2193(11)Å (Cu3···Cu4), respectively. In complex 2, the L3− ligand is adopting a cis conformation with the Cu···Cu distance of 5.2409 (7)Å. Through π–π stacking and hydrogen bonding interactions, the two bicopper(II) complexes are assembled to 3D supramolecular structures. Cytotoxic activities, and the reactivities towards DNA and protein of the two bicopper(II) complexes are investigated. The results suggest that the two bicopper(II) complexes interact with HS-DNA in the mode of intercalation, and the DNA-binding abilities are consistent with cytotoxic activities following the order of 2 > 1. The protein binding ability has been monitored using bovine serum albumin (BSA) as model protein. [Copyright &y& Elsevier]

Abstract: A new one-dimensional polymeric copper(II) complex, [Cu2(bhpox)(phen)]+ n ·nClO4 −·nH2O, where bhpox3− and phen stand for N-benzoate-N′-[3-(2-hydroxyethylammino)propyl]oxamide and 1,10-phenanthroline, respectively, has been synthesized and characterized by elemental analysis, molar conductivity measurement, IR and electronic spectra studies, and single-crystal X-ray diffraction. The complex crystallizes in monoclinic space group P21/c with crystallographic data: a =13.8500(2)Å, b =13.3321(2)Å, c =15.8532(2)Å, and Z =4. In the crystal structure, the cation [Cu2(bhpox)(phen)] n n + exhibits a one-dimensional zigzag-like structure for copper(II) ions alternately bridged by cis-oxamido and carboxylato groups, with the Cu⋯Cu separations of 5.1928(4) and 5.5240(5)Å, respectively. Each copper(II) ion is located in a slightly distorted square–pyramidal environment. Hydrogen bonds and π–π stacking interactions contribute to a three-dimensional supramolecular structure in the crystal. The interactions between the copper(II) complex and herring sperm DNA (HS-DNA) have been investigated by using electronic absorption titration, fluorescence titration, electrochemical titration and viscometry. All the experiments reveal that the copper(II) complex interacts with HS-DNA in the mode of intercalation with the intrinsic binding constant K b =2.67×104 M−1. The copper(II) complex exhibits potent anticancer activities against human hepatocellular carcinoma cell SMMC-7721 and human lung adenocarcinoma cell A549. [Copyright &y& Elsevier]

Abstract: Two new μ-oxamido-bridged binuclear copper(II) complexes with formulae of [Cu2(heae)(pic)2] (1) and [Cu2(heae)(Me2phen)2](ClO4)2 ·H2O (2), where heae and pic stand for the anion of N,N′-bis(N-hydroxyethylaminoethyl)oxamide and 2,4,6-trinitrophenol, respectively, and Me2phen represents 2,9-dimethyl-1,10-phenanthroline; have been synthesized and characterized by elemental analyses, molar conductivity measurements, IR and electronic spectra studies. The crystal structures of the two binuclear copper(II) complexes have been determined by X-ray single-crystal diffraction. In both the two binuclear complexes the central two copper(II) atoms are bridged by trans-heae. In complex 1 the coordination environment around each copper(II) atom can be described as a distorted octahedral geometry, while in complex 2 each copper(II) atom displays a square-pyramid stereochemistry. Hydrogen bonding and π–π stacking interactions link the binuclear copper(II) complex 1 or 2 into a 3D infinite network. The cytotoxicities of the two binuclear copper(II) complexes were tested by Sulforhodamine B (SRB) assays against human hepatocellular carcinoma cell SMMC-7721 and human lung adenocarcinoma cell A549. Both of the two binuclear copper(II) complexes exhibit potent cytotoxic effects against SMMC-7721 and A549 cell lines. The interactions of the two binuclear complexes with herring sperm DNA (HS-DNA) are investigated by using absorption and emission spectra and electrochemical techniques and viscometry. The results suggest that both the two binuclear copper(II) complexes interact with HS-DNA in the mode of intercalation with the intrinsic binding constants of 1.73×105 M−1 (1) and 1.92×106 M−1 (2). The influence of structural variation of the terminal ligands in the binuclear complexes on DNA-binding properties is preliminarily discussed. [Copyright &y& Elsevier]

Abstract: A two-dimensional copper(II) polymer with formula of [Cu4(H2O)4(dmapox)2(btc)] n ·10nH2O, where dmapox is the dianion of N,N′-bis[3-(dimethylamino)propyl]oxamide and btc is the tetra-anion of 1,2,4,5-benzenetetracarboxylic acid, was synthesized and characterized by elemental analysis, conductivity measurement, IR and electronic spectral studies. The crystal structure of the complex has been determined by X-ray single-crystal diffraction. The structure consists of crystallized water molecules and neutral two-dimensional copper(II) coordination polymeric networks constructed both by the bis-tridentate μ-trans-dmapox and tetra-monodentate μ4-btc bridging ligands. Each btc ligand links four trans-dmapox-bridged binuclear copper(II) building blocks [Cu2(H2O)2(trans-dmapox)]2+ and each binuclear copper(II) building block attaches to two btc ligands forming an infinite 2D layer which consists of 4+4 grids with dimensions of 13.563(5)×15.616(5)Å. The environment around the copper(II) atom can be described as a distorted square-pyramid and the Cu⋯Cu separations through μ-trans-dmapox and μ4-btc bridging ligands are 5.225Å (Cu1–Cu1i), 5.270Å (Cu2–Cu2ii), 6.115Å (Cu1–Cu2), 9.047Å (Cu1–Cu2iii) and 10.968Å (Cu1–Cu1iii), respectively. Abundant hydrogen bonds among the crystallized, the coordinated water molecules, and the uncoordinated carboxyl oxygen atoms cross-link the two-dimensional layers into an overall three-dimensional channel-like framework. The interaction of the copper(II) polymer with calf thymus DNA (CT-DNA) has been investigated by using absorption, emission spectral and electrochemical techniques. The results indicate that the copper(II) polymer interacts with DNA strongly (K b =4.8×105 M−1 and K sv =1.1×104) and the interaction mode between the copper(II) polymer and DNA may be the groove binding. To the best of our knowledge, this is the first report about the crystal structure and DNA-binding studies of a two-dimensional copper(II) polymer bridged both by the trans-oxamidate and btc ligands. [Copyright &y& Elsevier]

Abstract: Two new one-dimensional copper(II) polymers with formulae of [Cu2(H2O)2(dmapox)(ipa)2] n (1) and [Cu2(H2O)2(dmapox)(tpa)2] n (2), where dmapox, ipa and tpa stand for the dianion of N,N′-bis[3-(dimethylamino)propyl]oxamide, isophthalic acid and terephthalic acid respectively, have been synthesized and characterized by elemental analysis, conductivity measurement, IR and electronic spectral studies. The crystal structures of the two complexes have been determined by X-ray single-crystal diffraction. The structures of 1 and 2 consist of one-dimensional copper(II) coordination polymeric chain constructed both by the bis-tridentate trans-dmapox and bis-monodentate phenyldicarboxylate bridging ligands. In the two complexes, the environment around the copper(II) atoms can be described as distorted square–pyramid and the Cu···Cu separations through μ-trans-dmapox and phenyldicarboxylato bridging ligands are 5.245(5) Å and 8.212(3) Å for 1, 5.237(8) Å and 11.171(1) Å for 2, respectively. The binding properties of the two copper(II) polymers with herring sperm DNA (HS-DNA) have been investigated by using absorption and emission spectral and electrochemical techniques and viscometry. The results show that the two copper(II) complexes interact with the HS-DNA in the mode of intercalation with the intrinsic binding constants of 1.22(±0.2)×104 M−1 and 1.45(±0.3)×104 M−1 for 1 and 2, respectively. [Copyright &y& Elsevier]

Abstract: Two new binuclear copper complexes, [Cu2(oxpn)(bpy)(pic)(H2O)](pic) (1) and [Cu2(oxpn)(Me2bpy)(pic)](pic) (2) [H2oxpn= N,N′-bis(3-aminopropyl)oxamide; Hpic=2,4,6-trinitrophenol; bpy=2,2′-bipyridine; Me2bpy=4,4′-dimethyl-2,2′-bipyridine], have been synthesized and characterized by elemental analyses, conductivity measurements, IR, UV–visible spectroscopy and single crystal X-ray analyses. Both complexes have similar molecular structures. In complex 1, the central two Cu(II) atoms are bridged by cis-oxpn2− with the Cu1–Cu2 separation of 5.221Å and the polyhedron of each copper atom is a square-pyramid. Similarly, complex 2 is a cis-oxpn2−-bridged binuclear complex with the Cu1–Cu2 separation of 5.196Å. Cu1(II) central atom situated in a tetrahedral geometry is four-coordinated and Cu(II) atom situated in a square-pyramidal geometry is five-coordinated. Hydrogen bonding interactions and π–π stacking interactions link the binuclear copper complex 1 or 2 into a 2D infinite network. The antibacterial assays indicate that the two complexes showed better activities than their ligands. The interactions of the two binuclear complexes with herring sperm DNA (HS-DNA) have been studied by UV absorption titration, fluorescence titration and viscosity measurements. The results suggest that the two binuclear complexes bind to HS-DNA via an intercalative mode. [Copyright &y& Elsevier]

Abstract: A two-dimensional copper(II) polymer with formula of [Cu2(dmapox)(pic)2] n · nCH3OH, where dmapox is the dianion of N,N′-bis[3-(dimethylamino)propyl]oxamide and pic is picrate, was synthesized and characterized by elemental analysis, conductivity measurement, IR and electronic spectra studies. The crystal structure of the complex has been determined by single-crystal X-ray diffraction. It crystallizes in monoclinic, space group P2 1/c with crystallographic data: a =14.076(7)Å, b =13.896(7)Å, c =9.278(5) Å, β =106.909(6)° and Z =2. The structure consists of uncoordinated methanol molecules and two-dimensional copper(II) polymeric coordination network constructed by the bis-tridentate trans-dmapox and tridentate picrate ligands. The environment around the copper(II) atom can be described as a distorted octahedron and the Cu⋯Cu separations through μ-trans-oxamidate and μ2-picrate bridges are 5.227Å and 8.359Å, respectively. The copper(II) complex presents as a polymer in solid state, whereas in solution it presents as discrete neutral binuclear copper(II) species [Cu2(dmapox)(pic)2] due to the weak interactions between the copper(II) atoms and the para-nitro oxygens of the adjacent picrate ligands. The fluorescence titration and the ethidium bromide (EB) fluorescence displacement experiments reveal that the binding mode between the binuclear copper(II) complex [Cu2(dmapox)(pic)2] and Herring Sperm DNA might be intercalation. [Copyright &y& Elsevier]

Graphical abstract Two new bicopper(II) complexes have been synthesized and characterized by X-ray single-crystal diffraction. The cytotoxicities and reactivities towards DNA/BSA of the two complexes have been investigated. Highlights • Two new bicopper(II) complexes were synthesized. • The two complexes were characterized by X-ray single-crystal diffraction. • The DNA-binding abilities are consistent with cytotoxicities in the order of 2 > 1. • BSA-binding studies reveal that the complexes can be easily stored in protein. • The structural variation of the bridging ligand has some effect on the bioactivities. Abstract Two new μ -oxamide or μ -oxamate bridged bicopper(II) complexes, [Cu 2 (mapox)(bpy) 2 ](ClO 4) 2 (1) and Cu 2 (mapoa)(CH 3 OH)(bpy) 2 (pic) 2 ·0.5H 2 O (2) (H 2 mapox = N,N′ -bis[3-(methylamino)propyl]-oxamide, H 2 mapoa = N -[3-(methylamino)propyl]oxamate, bpy = 2,2′-bipyridine, pic = picrate anions), have been synthesized and characterized by elemental analyses, molar conductance measurement, spectroscopic studies and single-crystal X-ray diffraction. In complex 1 , both the copper(II) atoms acquire a square-pyramidal coordination geometry. The distance between Cu1 and Cu2 atoms is 5.2541(8) Å. The structure of complex 2 contains two bicopper(II) cations [Cu 2 (mapoa)(CH 3 OH)(bpy) 2 ]2+, in which the Cu atoms acquire distorted square-pyramid coordination geometry (Cu1, Cu2, Cu4) or distorted trigonal bipyramid coordination geometry (Cu3). The Cu⋯Cu separations are 5.2316(8) Å (Cu1, Cu2) and 5.2187(7) Å (Cu3, Cu4), respectively. The interaction between complexes 1 and 2 and herring Sperm DNA (HS -DNA) were studied by using UV absorption and fluorescence spectra, electrochemical techniques and viscometry. The results indicated that both of the two complexes could bind to HS -DNA by intercalation with the order 1 > 2. Protein binding properties investigations reveal that the two complexes could bind to bovine serum albumin (BSA) by the static quenching mechanism. The in vitro cytotoxicities experiments reveal that complex 1 exhibit better growth-inhibitory effects than complex 2 on human hepatocellular carcinoma cell SMMC-7721 and human lung adenocarcinoma cell A549. [ABSTRACT FROM AUTHOR]

Graphical abstract Two tetranuclear Ln 4 compounds were successfully synthesized based on Tb(III) and Dy(III) ions. Structural analysis reveal that they were isomorphic and both composed of butterfly-shaped [Ln 4 O 2 ] clusters in the center. Thereinto, 1 exhibits four characteristic peaks of Tb(III). For 2 , it is magnetically characterized and alternating-current (ac) magnetic susceptibility suggests slow magnetic relaxation behavior was occurred in 2 with the energy barrier Δ E / k B = 81.76 K. Abstract Two novel tetranuclear lanthanide complexes, [Ln 4 (μ 3 -OH) 2 L 6 (tmhd) 4 ] (Ln = Tb (1) and Dy (2)), were successfully synthesized by using 5-(2-hydroxylbenzylidene)-8-hydroxylquinoline (HL) and 2,2,6,6-tetramethyl-3,5-heptanedione (Htmbd). The investigation of single-crystal X-ray diffraction showed that the structures of 1 and 2 are both composed of butterfly-shaped [Ln 4 O 2 ] clusters in the center, and of which four Ln(III) ions are all eight-coordinated. Moreover, the luminescence test reveal that 1 exhibits four characteristic peaks of Tb(III); while for 2 , it is magnetically characterized and alternating-current (ac) magnetic susceptibility suggests slow magnetic relaxation behavior was occurred in 2 with the energy barrier (Δ E / k B) of 81.76 K. [ABSTRACT FROM AUTHOR]

A anhydrous orthoborate Na 3 Tb(PO 4 ) 2 has been prepared and its crystal structure was determined by X-Ray diffraction of a non-merohedral twinned single crystal. The results show that the compound crystallizes in monoclinic space group C 2/ c and the structure features a 3D framework containing PO 4 , NaO 6 , NaO 7 , NaO 8 and TbO 8 polyhedra. Under near-UV excitation (370 nm), Na 3 Tb(PO 4 ) 2 shows intense characteristic emission bands of Tb 3+ (490 nm, 543 nm, 585 nm and 620 nm) with the CIE coordinate of (0.3062, 0.5901), corresponding to greenish color. The excitation spectrum covers a wide range from 340 nm to 390 nm, which indicates that phosphor Na 3 Tb(PO 4 ) 2 can be efficiently activated by near-UV LED ship. [ABSTRACT FROM AUTHOR]

Two new tetracopper(II) complexes bridged by N -benzoate- N ′-[3-(diethylamino)propyl]oxamide (H 3 bdpox), and ended with 4,4′-dimethyl-2,2′-bipyridine (Me 2 bpy) or 2,2′-bipyridine (bpy), namely [Cu 4 (bdpox) 2 (Me 2 bpy) 2 ](pic) 2 ( 1 ) and [Cu 4 (bdpox) 2 (bpy) 2 ](pic) 2 ·2H 2 O ( 2 ) (where pic denotes the picrate anion) have been synthesized and characterized by X-ray single-crystal diffraction and other methods. In both complexes, four copper(II) ions are bridged alternately by the cis -oxamido and the carboxylato groups of two bdpox 3 − ligands to form a centrosymmetric cyclic tetranuclear cation, in which, the copper(II) ions at the endo - and exo -sites of cis -bdpox 3 − ligand have square-planar and square-pyramidal coordination geometries, respectively. The reactivity towards DNA/BSA suggests that these complexes can interact with HS -DNA through the intercalation mode and the binding affinity varies as 1 > 2 depending on the hydrophobicity, and effectively quench the fluorescence of protein BSA via a static mechanism. In vitro anticancer activities showed that the two complexes are active against the selected tumor cell lines, and the anticancer activities are consistent with their DNA-binding affinity. [ABSTRACT FROM AUTHOR]

Two new μ-oxamido-bridged dicopper(II) complexes formulated as [Cu 2 (hmdoxd)(H 2 O)(Me 2 bpy)]-(ClO 4 )·DMF ( 1 ) and [Cu 2 (hmdoxd)(bpy)](ClO 4 )·CH 3 OH ( 2 ), where H 3 hmdoxd is N -(2-hydroxy-5-methylphenyl)- N′ -[2-(dimethylamino)ethyl]oxamide; Me 2 bpy and bpy stand for 4,4′-dimethyl-2,2′-bipyridine and 2,2′-bipyridine, respectively, were synthesized and structurally characterized. The single-crystal X-ray diffraction analysis reveals that the copper(II) ions in complexes 1 and 2 are bridged by the cis -hmdoxd 3 − with corresponding Cu ⋯ Cu separations of 5.1596(6) and 5.1562(6) Å, respectively, in which the endo - and exo -copper(II) ions are located in square-planar and square-pyramidal geometries, respectively, for 1 , and square-planar environments for 2 . In the crystals of the two complexes, there are abundant hydrogen bonds and π–π stacking interactions contributing to the supramolecular structure. The DNA/protein-binding property of the two complexes are studied both theoretically and experimentally, indicating that complexes 1 and 2 can interact with DNA in the mode of intercalation and partial intercalation, respectively, and effectively bind to protein BSA via the favored binding sites Trp213 for 1 and Trp134 for 2 . In vitro anticancer activities showed that the two complexes are active against the selected tumor cell lines, and the anticancer activities are consistent with their DNA/protein-binding affinities following the order of 1 > 2 . The effect of the hydrophobicity of both the bridging and terminal ligands in the dicopper(II) complexes on DNA/protein-binding events and in vitro anticancer activities is preliminarily discussed. [ABSTRACT FROM AUTHOR]

A new oxamido-bridged dicopper(II) complex with formula of [Cu 2 (deap)(pic) 2 ], where H 2 deap and pic represent N , N ′-bis[3-(diethylamino)propyl]oxamide and picrate, respectively, was synthesized and characterized by elemental analyses, molar conductance measurements, IR and electronic spectral study, and single-crystal X-ray diffraction. The crystal structure analyses revealed that the two copper(II) atoms in the dicopper(II) complex are bridged by the trans -deap 2 − ligand with the distances of 5.2116(17) Å, and the coordination environment around the copper(II) atoms can be described as a square-planar geometry. Hydrogen bonding and π–π stacking interactions link the dicopper(II) complex into a three-dimensional infinite network. The DNA/protein-binding properties of the complex are investigated by molecular docking and experimental assays. The results indicate that the dicopper(II) complex can interact with HS-DNA in the mode of intercalation and effectively quench the intrinsic fluorescence of protein BSA by 1:1 binding with the most possible binding site in the proximity of Trp134. The in vitro anticancer activities suggest that the complex is active against the selected tumor cell lines, and IC 50 values for SMMC-7721 and HepG2 are lower than cisplatin. The effects of the electron density distribution of the terminal ligand and the chelate ring arrangement around copper(II) ions bridged by symmetric N , N ′-bis(substituted)oxamides on DNA/BSA-binding ability and in vitro anticancer activity are preliminarily discussed. [ABSTRACT FROM AUTHOR]

[Display omitted] • Three Ln 2 compounds (Sm, Eu and Tb) have been synthesized and structurally and fluorescence properties characterized. • Compounds 1 – 3 are isostructural and the center Ln(III) ions are linked via two µ 2 -O atoms forming a "parallelogram-shaped" Ln 2 O 2 core. • Compounds 1 – 3 exhibited strong antibacterial activities against Staphylococcus aureus , Bacillus subtilis , Escherichia coli and Candida albicans. In this paper, three new binuclear Ln‐based compounds with the formula [Ln 2 (dbm) 2 (L) 2 (C 2 H 5 OH) 2 ](Ln = Sm (1), Eu (2) and Tb (3); dbm− = 1,3‐dioxo‐1,3‐ diphenylpropan‐2‐ide) have been synthesized via the solvothermal method by using a polyden‐tate Schiff base ligand (H 2 L = (E)‐N'‐(3‐ethoxy‐2‐hydroxybenzylidene)‐ 3‐hydroxypicolinohydrazide) reacting with Ln(dbm) 3 ·2H 2 O. Single-crystal X-ray structures reveal that compounds 1 – 3 are mainly composed of two LnIII ions, two dbm−, two L2−, two C 2 H 5 OH, and the two central LnIII ions are connected by two µ 2 -O atoms forming a "parallelogram-shaped" Ln 2 O 2 core. The investigations on the solid-state fluorescence properties show that the compounds 1 – 3 display the characteristic lanthanide luminescence at room temperature. Furthermore, biological activities research reveals that compounds 1 – 3 have greater antibacterial activity than the ligand H 2 L, and compounds 1 – 3 with DNA interaction are mainly intercalation, and supplemented by electrostatic binding or groove binding. [ABSTRACT FROM AUTHOR]

Two new dicopper(II) complexes bridged by asymmetric N , N ′-bis(substituted)oxamide ligands: N -(5-chloro-2-hydroxyphenyl)- N ′-[2-(dimethylamino)ethyl]oxamide (H 3 chdoxd) and N -hydroxypropyl- N ′-(2-carboxylatophenyl)oxamide (H 3 oxbpa), and end-capped with 2,2′-bipyridine (bpy), namely [Cu 2 (ClO 4 )(chdoxd)(CH 3 OH)(bpy)]·H 2 O ( 1 ) and [Cu 2 (pic)(oxbpa)(CH 3 OH)(bpy)]·0.5CH 3 OH ( 2 ) (pic denotes picrate anion), have been synthesized and characterized by elemental analysis, molar conductivity measurement, IR and electronic spectral studies, and single-crystal X-ray diffraction. The X-ray diffraction analysis revealed that both the copper(II) ions bridged by the cis -oxamido ligands in dicopper(II) complexes 1 and 2 are all in square-pyramidal environments with the corresponding Cu⋯Cu separations of 5.194(3) and 5.1714(8) Å, respectively. In the crystals of the two complexes, there are abundant hydrogen bonds and π–π stacking interactions contributing to the supramolecular structure. The reactivities toward herring sperm DNA (HS-DNA) and bovine serum albumin (BSA) of the two complexes are studied both theoretically and experimentally, indicating that both the two complexes can interact with the DNA in the mode of intercalation, and effectively bind to BSA via the favored binding sites Trp134 for the complex 1 and Trp213 for the complex 2 . Interestingly, the in vitro anticancer activities of the two complexes against the selected tumor cell lines are consistent with their DNA/BSA-binding affinities following the order of 1 > 2 . The effects of coordinated counterions in the two complexes on DNA/BSA-binding ability and in vitro anticancer activity are preliminarily discussed. [ABSTRACT FROM AUTHOR]

Highlights: [•] A new mononuclear ternary copper(II) complex was synthesized and characterized by X-ray analysis. [•] The in vitro anticancer activities suggest that the copper(II) complex is active against the selected tumor cell lines. [•] The interaction of the complex with DNA was investigated both theoretically and experimentally. [•] The influence of binding fashion of the picrate anions on the structure, cytotoxicity and DNA-binding property was studied. [ABSTRACT FROM AUTHOR]