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Like many continental flood basalt (CFB) provinces in the world, the source mantle compositions (peridotites or pyroxenites) of the Emeishan CFB province in SW China are still debated. We have used the combination of olivine O isotopes determined in situ using SIMS and trace element abundances measured in situ using LA-ICP-MS to address this fundamental problem. The newly discovered picrites in the Emeishan CFB province at Yumen are used in this study. In addition, we have also analyzed primitive olivine phenocrysts with known O isotope ratios from four other picrite occurrences (Maoniuping, Tanglanghe, Wuguijing and Wulongba) in the Emeishan CFB province for trace element abundances. Based on whole rock compositions the picrite samples from Wulongba belong to the low-Ti group (Ti/Y < 500) and those from the other locations belong to the high-Ti group (Ti/Y > 500). Mineral chemical data reveal that the two different groups of picrites can be distinguished by using Ti/Al of olivine phenocrysts and Cr-spinel inclusions enclosed in olivine. Specifically, the high-Ti picrite group is characterized by 10Ti/Al (molar) >0.9 and >0.5 for olivine phenocrysts and Cr-spinel inclusions, respectively. In the mantle source discrimination diagrams based on olivine 100Mn/Fe versus 100Ni/Mg or 100Ca/Fe, both groups of picrites plot between the suggested fields of peridotite and pyroxenite mantle sources. In the same type of diagrams based on olivine Mn/Zn and 10000Zn/Fe, both groups of picrites plot exclusively in the fields for a peridotite mantle source. The mean δ18O value of olivine phenocrysts from the Yumen high-Ti picrites is 5.19 ± 0.25‰ (1σ, n = 35), which is significantly lower than that for the Wulongba low-Ti picrites (5.6 ± 0.15‰) but is similar to values (5.1 ± 0.15 to 5.3 ± 0.15‰) for the high-Ti picrites from elsewhere (Maoniuping, Talanghe and Wuguijing) in the Emeishan CFB province. The mean δ18O values of olivine phenocrysts from the Emeishan high-Ti picrites at different locations are all within the range of typical mantle olivine values (5.1 ± 0.3‰). Based on these results, we conclude that the high-Ti picrites in the Emeishan CFB province were primarily derived from a modally enriched peridotite mantle source. Our new olivine Zn-Mn-Fe data are consistent with the view that the Wulongba low-Ti picrites were derived from a lithospheric peridotite mantle source. Unlabelled Image • High-Ti and low-Ti picrites can be distinguished by 10Ti/Al in Cr-spinel and olivine. • Olivine Mn/Zn and Zn/Fe indicate a peridotite mantle source for Emeishan picrites. • Primitive olivine phenocrysts of Emeishan high-Ti picrites all have mantle-like δ18O. • No evidence from olivine to support a pyroxenite mantle source for Emeishan picrites. [ABSTRACT FROM AUTHOR]

A new Ru(ii) polypyridyl complex [Ru(phen)2(addppn)](ClO4)2 (Ru1) has been synthesized and characterized. The DNA-binding constant of the complex with DNA was determined to be 1.93 (±0.12) × 106 M−1. The complex interacts with DNA by an intercalative mode. Cytotoxicity in vitro, apoptosis, cell cycle distribution, apoptotic pathway, reactive oxygen species and mitochondrial membrane potential assays were performed. The IC50 values of Ru1 toward BEL-7402, HeLa, MG-63 and SKBR-3 cell lines are 3.9 ± 0.4, 9.0 ± 0.8, 6.6 ± 0.6 and 5.1 ± 0.6 μM, respectively. Interestingly, Ru1 shows a higher cytotoxicity than cisplatin on BEL-7402 cells under identical conditions. Ru1 can effectively induce apoptosis in BEL-7402 and induces cell cycle arrest at the G0/G1 phase in BEL-7402 cells and at the G2/M phase in SKBR-3 cells. In addition, Ru1 can enhance the level of reactive oxygen species and induce the decrease of the mitochondrial membrane potential. Western blot analysis shows that Ru1 activates caspase-3 and -7, down-regulates the expression of the anti-apoptotic proteins of Bcl-x and Bag-1, and upregulates the levels of the proapoptotic proteins of Bad, Bak, Bax and Bim in BEL-7402 cells. These results show that Ru1 induces apoptosis in BEL-7402 cells through an ROS-mediated mitochondrial dysfunction pathway. [ABSTRACT FROM AUTHOR]

Since morbidity and mortality rates of anaphylaxis diseases have been increasing year by year, how to prevent and manage these diseases effectively has become an important issue. Mast cells play a central regulatory role in allergic diseases. Angiopoietin1 (Ang-1) exhibits anti-inflammatory properties by inhibiting vascular permeability, leukocyte migration and cytokine production. However, Ang-1's function in mast cell activation and anaphylaxis diseases is unknown. The results of our study suggest that Ang-1 decreased lipopolysaccharide (LPS)-induced pro-inflammatory cytokines production of mast cells by suppressing IκB phosphorylation and NF-κB nuclear translocation. Ang-1 also strongly inhibited compound 48/80 induced and FcεRI-mediated mast cells degranulation by decreasing intracellular calcium levels in vitro. In vivo lentivirus-mediated delivery of Ang-1 in mice exhibited alleviated leakage in IgE-dependent passive cutaneous anaphylaxis (PCA). Furthermore, exogenous Ang-1 intervention treatment prevented mice from compound 48/80-induced mesentery mast cell degranulation, attenuated increases in pro-inflammatory cytokines, relieved lung injury, and improved survival in anaphylaxis shock. The results of our study reveal, for the first time, the important role of Ang-1 in the activation of mast cells, and identify a therapeutic effect of Ang-1 on anaphylaxis diseases. [ABSTRACT FROM AUTHOR]

Olivine compositions are often used to infer the source lithology of basaltic rocks, but the effect of source melting conditions on olivine chemistry remains poorly studied. Here we present mineral chemistry, whole-rock major and trace elements, Sr Nd isotopes, and platinum-group element (PGE) concentrations for high-Ti picritic-basaltic rocks from Yumen area. These data provide new constraints on the source lithology and petrogenesis of these high-Ti rocks in the Emeishan large igneous province (ELIP). The picrites have primitive compositional features (e.g., high Mg# values, depleted Sr Nd isotopic compositions, no PGE depletions and/or fractionations). Some basaltic rocks have negative Nb Ta anomalies, enriched Sr Nd isotopic compositions, and depleted and/or fractionated PGE contents, indicative of fractional crystallisation, variable degrees of crustal contamination, and magmatic sulfide segregation. Combined with published data for the ELIP, the compositions of the primitive magmas and 10000Zn/Fe and FC3MS (FeO/CaO − 3 × MgO/SiO 2 , all in wt%) values of the ELIP high-Ti picrites are similar to those of garnet peridotite-derived experimental melts. Based on the primitive magma compositions, the ELIP high-Ti melts could have been produced by mantle melting at 4.0–5.4 GPa and 1620–1660 °C, and started to crystallise olivine at 1410–1550 °C, based on the Al-in-olivine thermometer, which are higher temperatures than for mid-ocean ridge basalts and ELIP low-Ti magmas. The high-Ni and low-Mn olivine phenocrysts in the ELIP high-Ti samples crystallised from peridotite-derived, MgO-rich melts at high temperatures. Variations in the physicochemical source melting conditions was enough to explain the differences in olivine Ni and Mn contents in the ELIP high- and low-Ti picrites-basalts. Additionally, the almost constant Pd, Pt, and Rh contents with decreasing Mg# values indicate intermediate partition behaviors in the ELIP magmas. No correlations exist between whole-rock 10,000 × Pd/Yb and Mg#, (Th/Nb) N , and ε Nd (t) values, implying that selective assimilation of crustal sulfur resulted in magmatic sulfide saturation. We propose that the ELIP high-Ti magmas were derived from a deep-sourced garnet peridotite, and experienced various igneous processes during ascent through the continental lithosphere to form different types of ELIP high-Ti basaltic rocks. [Display omitted] • ELIP high-Ti magmas were derived from a depleted mantle peridotite. • Polybaric melting process can explain olivine compositions variation in ELIP. • PPGE had intermediate partition behaviors in the ELIP basaltic magma. • Addition of crustal sulfur resulted in the magmatic sulfide saturation in ELIP. [ABSTRACT FROM AUTHOR]

Four new naphthoxazole compounds 1–4 have been synthesized and characterized. The DNA-binding was studied by absorption spectroscopy, viscosity measurements and luminescence spectra. The DNA binding constants were determined to be 5.06×103 for 1, 5.29×104 for 2, 3.58×103 for 3 and 7.75×103 M−1 for 4, respectively. The results show that these compounds can intercalate into the DNA base pairs. The stoichiometries of compound/DNA are 1:1 for 1, 2, 4, and 1.5:1 for 3. Interaction of compounds 1–4 with plasmid pBR322 DNA studied by gel electrophoresis experiments reveals that compounds can cleave pBR322 DNA upon irradiation or hydrolytic conditions. The antioxidant activities of these compounds against hydroxyl radical were also explored. [ABSTRACT FROM AUTHOR]

Abstract: The thermal stability of phthalic anhydride-modified horseradish peroxidase (HRP) in organic solvents was investigated. The modification increased the tolerance of some organic solvents. In order to investigate the molecular mechanism of the stabilization, the changes between native and modified enzyme were also studied using kinetics and spectroscopic methodology. The modified HRP showed greater affinity and catalytic efficiency in some organic solvents for different substrates than native HRP. The substrate affinity and the catalytic efficiency of native and modified HRP increased with the increases of electron-donating efficiency of substituents at 4-position. The improvements of catalytic properties are related to the changes of the conformation of HRP. The modification changed the environment of both heme and tryptophan, increased α-helix content of HRP and decreased the tertiary structure around the aromatic acid residues in HRP. [Copyright &y& Elsevier]

A novel acyclic copper complex of Cu(L)(H2O) (H2L=N,N′-1,2-ethanediyl-bis[N-(4-methoxyphenyl)methylglycine]) has been synthesized and structurally characterized by means of X-ray single crystal diffraction. Interestingly, this Cu(II) complex has been found to cleave supercoiled DNA (pBR 322) to nicked and linear forms in aerobic condition. [Copyright &y& Elsevier]

In this article, the in vitro cytotoxicity of platycodin D was evaluated in human PC-12, SGC-7901, BEL-7402, HeLa and A549 cancer cell lines. PC-12 cells were sensitive to platycodin D treatment, with an IC 50 value of 13.5 ± 1.2 μM. Morphological and comet assays showed that platycodin D effectively induced apoptosis in PC-12 cells. Platycodin D increased the levels of reactive oxygen species (ROS) and induced a decrease in mitochondrial membrane potential. Platycodin D induced cell cycle arrest at the G0/G1 phase in the PC-12 cell line. Platycodin D can induce autophagy. In addition, platycodin D can down-regulate the expression of Bcl-2 and Bcl-x, and up-regulate the levels of Bid protein in the PC-12 cells. The results demonstrated that platycodin D induced PC-12 cell apoptosis through a ROS-mediated mitochondrial dysfunction pathway. [ABSTRACT FROM AUTHOR]

Four new ruthenium(II) polypyridyl complexes [Ru(N–N) 2 (dhbn)](ClO 4 ) 2 (N–N = dmb: 4,4′-dimethyl-2,2′-bipyridine 1 ; bpy = 2,2′-bipyridine 2 ; phen = 1,10-phenanthroline 3 ; dmp = 2,9-dimethyl-1,10-phenanthroline 4 ) were synthesized and characterized. The cytotoxicity in vitro of the ligand and complexes toward HepG-2, HeLa, MG-63 and A549 were assayed by MTT method. The IC 50 values of the complexes against the above cells range from 17.7 ± 1.1 to 45.1 ± 2.8 μM. The cytotoxic activity of the complexes against HepG-2 cells follows the order of 4 > 2 > 3 > 1 . Ligand shows no cytotoxic activity against the selected cell lines. Cellular uptake, apoptosis, comet assay, reactive oxygen species, mitochondrial membrane potential, cell cycle arrest, and the expression of proteins involved in apoptosis pathway induced by the complexes were investigated. The results indicate that complexes 1–4 induce apoptosis in HepG-2 cells through an intrinsic ROS-mediated mitochondrial dysfunction pathway. [ABSTRACT FROM AUTHOR]

Four new ruthenium(II) polypyridyl complexes [Ru(dmb) 2 (dqtbt)](ClO 4 ) 2 ( 1 ) (dqtbt = 12-(2,3-diphenyl-quinoxalin-6-yl)-4,5,10,13-tetraazabenzo[ b ]triphenylene, dmb = 4,4′-dimethyl-2,2′-bipyridine), [Ru(bpy) 2 (dqtbt)](ClO 4 ) 2 ( 2 ) (bpy = 2,2′-bipyridine), [Ru(phen) 2 (dqtbt)](ClO 4 ) 2 ( 3 ) (phen = 1,10-phenanthroline) and [Ru(dmp) 2 (dqtbt)](ClO 4 ) 2 ( 4 ) (dmp = 2,9-dimethyl-1,10-phenanthroline) were synthesized and characterized. The cytotoxicity in vitro of the complexes was evaluated against human BEL-7402, A549, HeLa, HepG-2 and MG-63 cancer cell lines. These complexes are sensitive to BEL-7402 cells, the IC 50 values are 4.9 ± 0.5, 4.6 ± 0.4, 7.7 ± 1.8 and 1.9 ± 0.3 μM toward BEL-7402 cells. The complexes can increase the levels of reactive oxygen species and induce the decrease of mitochondrial membrane potential. Morphological and comet assay studies show that the complexes can effectively induce apoptosis in BEL-7402 cells. Complexes 1 – 4 inhibit the cell growth at G0/G1 phase in BEL-7402 cell line. The complexes can downregulate the expression of Bcl-2 and Bcl-x proteins and upregulate the levels of Bid protein in BEL-7402 cells. The results show that the complexes induce BEL-7402 cell apoptosis through a ROS-mediated mitochondrial dysfunction pathway. In addition, the complexes show strong protein-binding affinities. [ABSTRACT FROM AUTHOR]

A Ru(II) polypyridyl complex [Ru(bpy) 2 (HMSPIP)](ClO 4 ) 2 ( 1 ) (bpy = 2,2′-bipyridine, HMSPIP = 2-(4-methylsulfonyl)phenyl-1H-imidazo[4,5- f ][1,10] phenanthroline) was synthesized. The IC 50 value of the complex against human hepatocellular cell BEL-7402 is 21.6 ± 2.7 μM. The complex shows no cytotoxic activity toward human lung adenocarcinoma cell A549, human osteosarcoma cell MG-63 and human breast cancer cell SK-BR-3 cells. It is easily for complex 1 to be taken up by BEL-7402 cells. The complex can enhance the reactive oxygen species (ROS) levels and induce the decrease in the mitochondrial membrane potential. The complex inhibits the cell growth in BEL-7402 cells at G2/M phase. Complex 1 can regulate the expression of Bcl-2 family proteins. The results show that the complex induces apoptosis of BEL-7402 cells through a ROS-mediated mitochondrial dysfunction pathway. [ABSTRACT FROM AUTHOR]

A new ruthenium(II) polypyridyl complex [Ru(dmp) 2 (pddppn)](ClO 4 ) 2 Ru1 was synthesized and characterized. The cytotoxic activity in vitro of the complex was evaluated by MTT method. Ru1 shows high effect on the inhibition of the cell growth against BEL-7402, HeLa, MG-63 and A549 cells with low IC 50 values of 1.6 ± 0.4, 9.0 ± 0.8, 1.5 ± 0.2 and 1.5 ± 0.3 μM, respectively. The cellular uptake indicates that Ru1 can enter into the cytoplasm and accumulate in the cell nuclei. Ru1 can induce apoptosis in A549 cells and enhance the levels of reactive oxygen species (ROS) and induce the decrease of mitochondrial membrane potential. In addition, Ru1 can down-regulate the levels of Bcl-2, Bcl-x, Bak, and Bim expression and up-regulate the expression of Bag-1 and Bad. The complex induces apoptosis of A549 cells through an intrinsic ROS-mediated mitochondrial dysfunction pathway, which was accompanied by regulating the expression of caspases and Bcl-2 family proteins. [ABSTRACT FROM AUTHOR]

A new ligand dmdppz and its four ruthenium(II) polypyridyl complexes [Ru(dmb) 2 (dmdppz)](ClO 4 ) 2 ( 1 ), [Ru(bpy) 2 (dmdppz)](ClO 4 ) 2 ( 2 ), [Ru(phen) 2 (dmdppz)](ClO 4 ) 2 ( 3 ) and [Ru(dmp) 2 (dmdppz)](ClO 4 ) 2 ( 4 ) (where dmb, bpy, phen, dmp and dmdppz stand for 4,4′-dimethyl-2,2′-bipyridine, 2,2′-bipyridine, 1,10-phenanthroline, 2,9-dimethyl-1,10-phenanthroline and 5,8-dimethoxylpyrido[3,2- a :2′,3′- c ]phenazine, respectively) have been synthesized and characterized. Their DNA binding behaviors show that the complexes bind to calf thymus DNA by intercalation. The complexes exhibit efficient photocleavage of pBR322 DNA on irradiation. The cytotoxicity of the ligand and the complexes toward HepG-2, HeLa, MG-63, A549 and BEL-7402 were assayed by MTT ((3-(4,5-dimethylthiazo-2-yl)-2,5-diphenyltetrazolium bromide)) method. The IC 50 values of the complexes 1 , 2 , 3 and 4 toward BEL-7402 cells are 14.6, 16.8, 18.0 and 16.7 μM, respectively. Dmdppz shows no cytotoxic activity against selected cell lines. The cellular uptake, apoptosis, comet assay, reactive oxygen species (ROS), mitochondrial membrane potential and western blot analysis were investigated. These results indicate that complexes 1 – 4 exert their toxicity through the intrinsic ROS-mediated mitochondrial pathway, which is accompanied by the regulation of Bcl-2 family proteins. [ABSTRACT FROM AUTHOR]

The aim of our study was to investigate DNA-binding and cytotoxic activity of the four new Ru(II) polypyridyl complexes [Ru(dmb) 2 (HMHPIP)](ClO 4 ) 2 ( 1 ), [Ru(bpy) 2 (HMHPIP)](ClO 4 ) 2 ( 2 ), [Ru(phen) 2 (HMHPIP)](ClO 4 ) 2 ( 3 ) and [Ru(dmp) 2 (HMHPIP)](ClO 4 ) 2 ( 4 ). The complexes interact with DNA through intercalative mode and show relatively high cytotoxic activity against A549 cells, no cytotoxicity toward MG-63 cells. Complexes 1 – 4 can enhance the levels of ROS in A549 cells and induce the decrease of the mitochondrial membrane potential. These complexes inhibit the cell growth in A549 cells at G0/G1 or S phase. Complex 3 activated caspase 7, and down-regulated the expression of the anti-apoptotic protein Bcl-2. Complexes 1 – 4 induce apoptosis in A549 cells through ROS-mediated mitochondrial dysfunction pathway. [ABSTRACT FROM AUTHOR]

Two new Ru(II) complexes, [Ru(dmp)2(dadppz)](ClO4)2(1) and [Ru(dip)2(dadppz)](ClO4)2(2), were synthesized and characterized by elemental analysis, ES-MS, and1H NMR. DNA-binding behaviors were investigated by absorption titration and luminescence spectra. The DNA-binding constants were 3.1 (± 0.2) × 104and 3.0 (± 0.2) × 105 M−1for1and2. The antioxidant activity of these complexes against hydroxyl radical () was explored. The cytotoxicitiesin vitrotowards A549, BEL-7402, MG-63, and SKBR-3 cells were studied by 3-(4,5dimethylthiazol-2-yl)-2,5-diphenyltetrazolium bromide method. Complex1shows high cytotoxicity, but2is not cytotoxic towards the selected cell lines. Apoptosis and cell cycle distribution were studied by flow cytometry. The cellular uptake showed that complexes can enter into the cytoplasm. JC-1 was used as a fluorescence probe in detecting the mitochondrial membrane potential and results indicate that the mitochondrial membrane potential decreases. [ABSTRACT FROM AUTHOR]

Two novel ruthenium(II) complexes [Ru(dmb)2(addppn)](ClO4)2 (1) and [Ru(bpy)2(addppn)](ClO4)2 (2) were synthesized. The DNA-binding constants of complexes 1 and 2 were determined to be 4.78 (±0.49) × 105 and 7.42 (±0.53) × 105 M−1. The results indicate that complexes 1 and 2 interact with CT DNA through intercalative mode. The cytotoxicity in vitro of the complexes toward BEL-7402, HeLa, MG-63 and SKBR-3 cells was assessed by MTT assay. The apoptosis was carried out with Hoechst 33258 staining method and flow cytometry. The cellular uptake was observed under fluorescence microscope. The cell cycle arrest shows that the antiproliferative mechanism induced by complexes 1 and 2 on BEL-7402 cells is G0/G1 phase arrest. [ABSTRACT FROM AUTHOR]

Two Ru(II) complexes [Ru(dmb)2(dtmi)](ClO4)2 (1) (dmb = 4, 4'-dimethyl-2, 2'-bipyridine, dtmi = 3-(pyrazin-2-yl)-as-triazino[5, 6-f]-5-methoxylisatin) and [Ru(dmb)2(dtni)](ClO4)2 (2) (dtni = 3-(pyrazin-2-yl)-as-triazino[5, 6-f]-5-nitroisatin) have been synthesized and characterized by elemental analysis, ES-MS, and 1H NMR. DNA-binding behaviors of these complexes have been investigated by spectroscopic titration, viscosity measurements, and thermal denaturation. The results indicate that the two complexes interact with calf thymus DNA by intercalation. [ABSTRACT FROM AUTHOR]

Two polypyridine ruthenium(II) complexes, [Ru(dmp)2(MCMIP)]2+ (1) (MCMIP = 2-(6-methyl-3-chromonyl)imidazo[4,5-f][1,10]-phenanthroline, dmp = 2,9-dimethyl-1,10-phenanthroline) and [Ru(dmb)2(MCMIP)]2+ (2) (dmb = 4,4'-dimethyl-2,2'-bipyridine), have been synthesized and characterized by elemental analysis, ES-MS and 1H NMR. The DNA-binding behaviors of these complexes were investigated by electronic absorption titration, fluorescence spectroscopy, viscosity measurements and thermal denaturation. The results show that 1 and 2 effectively bind to CT-DNA; the DNA-binding affinities are closely related to the ancillary ligand. [ABSTRACT FROM AUTHOR]

Abstract: The one-dimensional (1D) meso polymeric structure {[Cd2(HL)(N3)2(H2O)]·(DMF)3} n 2 has been assembled from a propeller-like chiral mononuclear complex {[Cd(H3L)(H2O)][Cd(H3L)(H2O)2]}(ClO4)4 1 (H3L=tris(5-methyl-2-benzimidazolylmethyl)amine). The assembly process was achieved by the aid of NaN3 which causes N-deprotonation of the 5-methyl-benzimidazole groups and bridges the opposite enantiomers to form 1D meso chain. Both the monomer 1 and polymer 2 have been characterized by single-crystal X-ray diffraction, powder X-ray diffraction, elemental analysis and infrared spectroscopy. The ESI-MS of complex 1 has been studied to understand the assembly process. The photoluminescence measurements of the ligand and the complexes show that the ligand-based emission has been significantly enhanced in the monomer while little changed after polymerization. [Copyright &y& Elsevier]

Abstract: Biodegradation of dimethyl terephthalate (DMT) by individual species of bacteria isolated from mangrove sediment was conducted in batch experiments. Four morphologically distinct microorganisms, two of which showed ability to degrade DMT completely, were obtained and identified. Pasteurella multocida Sa displayed the greatest ability in degrading 98mg within 60h. At this initial concentration the rate of DMT degradation by P. multocida Sa was apparently higher than that by Sphingomonas paucimobilis Sy. Based on the data obtained from HPLC/MS/MS analysis degradation of DMT by these bacteria was observed to proceed with formation of monomethyl terephtlate and terephthalate acid (TA) sequentially. However, addition of TA to the culture medium containing DMT as a co-substrate was found to delay aerobic degradation of DMT by P. multocida Sa. From these results, it is evident that environmental bacteria are capable of metabolizing DMT as sole carbon and energy source and may be used in aerobic treatment of wastewater containing DMT. [Copyright &y& Elsevier]

Abstract: By changing the pH value, the macrocyclic complex monomer [CuL(H2O)2]·6H2O, 1 ·6H2O, (L=3,10-bis(2-butyrate)-1,3,5,8,10,12-hexaazacyclo-tetradecane) and its 2D sheet {[CuH2L](ClO4)2} n , 2, can be reversibly converted. [Copyright &y& Elsevier]

Abstract: A novel asymmetric bidentate ligand, 2-(pyrazin-2-yl)naphthoimidazole (PZNI), and its Ru(II) complexes [Ru(bpy)2(PZNI)]2+ (1) and [Ru(phen)2(PZNI)]2+ (2) have been synthesized and characterized by elemental analysis, mass spectra, 1H NMR, and electronic spectroscopy. The electrochemical behaviors of the novel complexes were studied by cyclic voltammetry. The DNA-binding properties of the complexes were investigated by spectroscopic methods and viscosity measurements. The experimental results indicate that the complexes 1 and 2 interact with calf thymus DNA by intercalative mode via the terminal naphthyl ring into the base pairs of DNA. The two Ru(II) complexes have also been found to promote the cleavage of plasmid pBR 322 DNA from the supercoiled form I to the open circular form II upon irradiation. [Copyright &y& Elsevier]

Two new metabolites, the cyclo-( l -Phe- l -Leu 1 - l -Leu 2 - l -Leu 3 - l -Ile) ( 1 ) and (3 S ,4 R )-dihydroxy-(6 S )-undecyl-α-pyranone ( 2 ) have been produced by the endophytic fungus no. 2524 isolated from a seed of mangrove Avicennia marina in Hong Kong. The structures have been elucidated by spectra including two-dimensional NMR, ESI tandem mass spectrometry and CD. These compounds show no activity toward human cancer cell lines Bel-7402, NCI-4460 and the normal human cell lines L-02. [ABSTRACT FROM AUTHOR]

Two novel Ru(II) complexes [Ru(dppt)(dien)](ClO4)2 (1) and [Ru(pta)(dien)](ClO4)2 (2) (dppt, pta and dien stand for 3-(1,10-phenanthrolin-2-yl)-5,6-diphenyl-as-triazine, 3-(1,10-phenanthrolin-2-yl)-5,6-diphenyl-as-triazino[5,6-f]acenaphthylene and diethylenetriamine, respectively) were synthesized and characterized by elemental analysis, ES-MS and 1H NMR spectroscopy. Due to the strong electron donor ability of dien, the oxidation potentials of complexes 1 and 2 are less positive and their MLCT bands significantly shift to lower energies in comparison with those of the homoleptic complexes [Ru(dppt)2](ClO4)2 and [Ru(pta)2](ClO4)2. The solvatochromic behaviors of the two complexes were also investigated. [Copyright &y& Elsevier]

Within the inner zone of the Emeishan large igneous province (ELIP), SW China, there are several small syenitic and A-type granitic intrusions not spatially related to giant Fe–Ti–V-deposit-bearing mafic–ultramafic layered intrusions. The representative Heime syenitic and Huili granitic intrusions as well as their spatially associated mafic dykes were developed at ca. 260 Ma, contemporaneous with the ELIP. The Heime metaluminous syenites are K-rich and have moderate SiO 2 (60.1–61.4 wt%) and high total-alkali (Na 2 O + K 2 O = 9.68–10.7 wt%) contents with high K 2 O/Na 2 O ratios (1.18 to 1.74). The Huili metaluminous granites are K-rich A-type granites with moderate–high SiO 2 (62.7–68.9 wt%), high total-alkali (7.96–8.62 wt%) and Zr (324–853 ppm) contents, and high 10,000 × Ga/Al ratios (2.68–3.22). Both of them are enriched in high-field-strength elements and light rare-earth elements, with significantly negative Nb–Ta–Sr–P–Ti anomalies. They also have highly evolved whole-rock Sr Nd isotopic compositions (Heime syenites, (87Sr/86Sr) i = 0.7092–0.7105, ε Nd (t) = −7.77 to −6.09; Huili granites, (87Sr/86Sr) i = 0.7116–0.7146, ε Nd (t) = −6.34 to −5.32). Zircon δ18O values of the Heime syenites (5.73‰–6.40‰) are slightly higher than those of the mantle zircons, and lower than those of the Huili granites (5.98‰–7.52‰). Zircon Hf 8isotopic compositions of the Huili granites (ε Hf (t) = −3.30 to +0.73) are higher than those of the Heime syenites (ε Hf (t) = −7.08 to −2.97), possibly indicating a more contribution of mantle component. In addition, the spatially associated mafic dykes display considerably higher ε Nd (t) values (Heime mafic dykes, −3.95 to −3.01; Heime mafic dykes, −0.58 to −0.51) than those of the Heime syenites and Huili granites. The parental magmas of both the Heime syenites and the Huili A-type granites show a close affinity to the K-rich, metaluminous syenitic magmas. Based on the Sr–Nd–O–Hf isotopic compositions of the Heime syenites, Huili granites, and spatially associated mafic dykes, we suggest that the K-rich syenitic magmas parental to the Heime syenites were produced mainly by remelting of Paleo–Mesoproterozoic mafic meta-igneous rocks, whereas those parental to the Huili A-type granites were generated by the remelting of Paleo–Mesoproterozoic basement rocks and mixing with small amounts of coeval mantle-derived basaltic melts. [Display omitted] • The A-type Heime syenites and Huili granites were emplaced at ca. 260 Ma. • Their parental magmas were K-rich metaluminous syenitic magmas. • The syenitic magmas were mainly produced by remelting of ancient crust. • Their generation was a response to the Emeishan plume thermal event. [ABSTRACT FROM AUTHOR]

In order to constrain its petrogenesis and mineralization, a detailed study of Miocene quartz diorite porphyry from the Ciemas area of West Java, Indonesia, was undertaken, including geochronology and major and trace element analyses. Ciemas quartz diorite porphyry contains medium–coarse-grained quartz and hornblende phenocrysts in a matrix of primarily cryptocrystalline quartz and feldspar. The rocks belong to the calc-alkaline-high K calc-alkaline series. The quartz diorite porphyry and Miocene dacite and andesite wall rocks have similar compositions, both being enriched in large-ion lithophile elements (LILEs) K, Rb, Th, and U, depleted in high-field strength elements (HFSEs) Nb, Ta, Zr, Hf, and P; with light rare earth element (LREE)-enriched patterns and negative Eu anomalies, which are typical for arc magmatic rocks. LA-ICP-MS U-Pb zircon ages of andesite, amphibolic tuff breccia, and quartz diorite porphyry are 17.5 ± 0.3, 16.9 ± 0.3, and 17.1 ± 0.4 Ma, respectively. The quartz diorite porphyry formed by mid-Miocene arc magmatism. This intrusion and surrounding volcanics developed together as the Indian–Australian Plate subducted northward beneath Java, releasing fluids that triggered partial melting of the overlying mantle wedge and felsic melts that evolved further in the crust. Petrogenesis and ages of Ciemas magmatic rocks are important to gaining an understanding of Cenozoic Sunda Arc magmatism, and also provide insights into related epithermal gold deposits. [ABSTRACT FROM AUTHOR]

Compositions of the earliest Jurassic basalts (190–188 Ma) from the the Baimianshi, Changpu, and Dongkeng basins in southern Jiangxi Province provide insight into the nature of their mantle sources as well as evidence for asthenosphere–lithospheric mantle interaction beneath Southeastern China. We report for the first time elemental and Sr Nd isotopic data for the basalts collected from new drill cores. The basalts are mainly tholeiitic and subordinate alkaline basalts. The alkaline basalts have high TiO 2 contents (3.13–4.19 wt%), and high Ti/Y (596–699) and Nb/Y ratios (0.85–0.92) and Nb/La ratios (0.80–0.95). These basalts are characterised by ocean island basalt (OIB)-like trace element characteristics, and have primitive mantle-like ε Nd (t) values (−0.85 to +0.33) and moderately elevated (87Sr/86Sr) i ratios (0.7074–0.7082). The tholeiitic basalts have a large range of TiO 2 contents (1.26–3.26 wt%) and Nb/La ratios (0.40–0.88), plus relatively low Ti/Y (135–534) and Nb/Y ratios (0.32–0.69). Based on Nb/La ratios, the tholeiitic basaltic rocks can further divided into two sub-types: high Nb/La (Nb/La > 0.70) and low Nb/La (Nb/La < 0.70) tholeiitic basalts. The high Nb/La tholeiitic basalts exhibit slight Nb Ta depletions (Nb/La = 0.73–0.88), mostly positive ε Nd (t) values (−0.04 to +2.5) and slightly elevated (87Sr/86Sr) i ratios (0.7061–0.7088), whereas the low Nb/La tholeiitic basalts exhibit moderate to large Nb Ta depletions (Nb/La = 0.40–0.65), much lower ε Nd (t) values (−7.4 to −0.60) and higher (87Sr/86Sr) i ratios (0.7082–0.7115). In particular, the two low Nb/La tholeiitic basalts (termed as "high-Ba tholeiitic basalts" in this study) are characterised by island arc-like trace element features, such as significant enrichments in Ba and Th, and depletions in Nb, Ta, P, and Ti (Nb/La = 0.40). The two high-Ba basalts also exhibit significantly lower ε Nd (t) values (−7.3 to −7.4) and higher (87Sr/86Sr) i ratios (0.7112–0.7115). Based on the results, we propose that the parental magmas of the alkaline basalts were produced by low degrees (& 5%–7%) of partial melting of an asthenospheric mantle source at the depth within the garnet–spinel-bearing mantle with more garnet than spinel, the parental magmas of the high Nb/La tholeiitic basalts were generated by moderate degrees (& 15%–20%) of partial melting of a depleted asthenospheric mantle at a relatively shallow depth within the garnet–spinel stability field, the parental magmas of the high-Ba tholeiitic basalts were derived from lithospheric mantle that had been metasomatised by subducted sediment-derived melts and/or fluids. We envision the formation of tholeiitic to alkaline basaltic magmas in the earliest Jurassic in South China records was the result of interactions between the asthenosphere and metasomatised lithosphere during upwelling of the asthenospheric mantle that was triggered by the foundering and/or delamination of a subducted flat slab beneath this region and steep NW-ward palaeo-Pacific subduction. [Display omitted] • Coeval ~190 Ma tholeiitic and alkaline basalts in southeastern China. • The high Nb/La tholeiitic basalts and alkaline basalts were derived from the depleted asthenospheric mantle. • Geochemical variation provides evidence for interactions between asthenospheric and metasomatized lithospheric mantle. • Asthenosphere upwelling triggered by foundering of a previously subducted oceanic slab. [ABSTRACT FROM AUTHOR]

Abstract: Two new ligands APIP, HAPIP and their relative ruthenium(II) complexes [Ru(bpy)2(APIP)](ClO4)2 1 and [Ru(bpy)2(HAPIP)](ClO4)2 2 have been synthesized and characterized. The DNA binding constants for complexes 1 and 2 have been determined to be 6.08 (±0.29)×104 M−1 and 1.78 (±0.30)×105 M−1. The results suggest that these complexes intercalate between the base pairs of DNA. The cytotoxicity of complexes has been evaluated by MTT assay. The apoptosis assay was carried out with AO/EB staining methods. The cellular uptake was observed under fluorescence microscopy. The studies on the mechanism of photocleavage demonstrate that superoxide anion radical (O2 −) and singlet oxygen (1O2) may play an important role. The antioxidant activity against hydroxyl radical ( OH) was also studied. [Copyright &y& Elsevier]

Two new ruthenium(II) complexes, [Ru(phen)2(DNPIP)](ClO4)2 (1) and [Ru(phen)2(DAPIP)](ClO4)2 (2), were synthesized and characterized. The DNA-binding properties of these complexes were investigated using UV/vis absorption titration, viscosity measurements, thermal denaturation, and photoactivated cleavage. The DNA binding constants for complexes 1 and 2 are 2.63 ± 0.25 × 105 M−1 ( s = 2.45) and 1.51 ± 0.18 × 105 M−1 ( s = 1.34). The results indicated that these complexes interacted with DNA through the intercalative mode. The cytotoxicity in vitro of complexes 1 and 2 were assessed against BEL-7402, HepG-2, and MCF-7 cell lines by the 3-(4,5-dimethylthiazol-2-yl)-2,5-diphenyltetrazolium bromide (MTT) assay. Apoptosis was studied with the acridine orange/ethidium bromide staining method. The antiproliferative mechanism was explored with flow cytometry. Cellular uptake studies showed that complexes 1 and 2 can enter into the cytoplasm and accumulate in the nuclei. Cell cycle arrest and antioxidant activity were also investigated. [ABSTRACT FROM AUTHOR]

Two ruthenium (II) complexes [Ru(dmb)2(APIP)](ClO4)2 (APIP = 2-(2-aminophenyl)imidazo[4,5-f ][1,10]phenanthroline, dmb = 4,4′-dimethyl-2,2′-bipyridine; 1) and [Ru(dmb)2(HAPIP)](ClO4)2 (HAPIP = 2-(2-hydroxyl-4-aminophenyl)imidazo[4,5-f ][1,10]phenanthroline; 2) were synthesized and characterized. DNA binding was investigated by electronic absorption titration, luminescence spectra, thermal denaturation, viscosity measurements, and photocleavage. The DNA binding constants for complexes 1 and 2 were 4.20 (±0.14) × 104 and 5.45 (±0.15) × 104 M−1. The results suggest that these complexes partially intercalate between the base pairs. The cytotoxicity of complexes 1 and 2 was evaluated by MTT assay. Cellular uptake was observed under fluorescence microscopy; complexes 1 and 2 can enter into the cytoplasm and accumulate in the nuclei. Apoptosis and the antioxidant activity against hydroxyl radicals (•OH) were also explored. [ABSTRACT FROM AUTHOR]

Abstract: A new ligand and two ruthenium(II) complexes [Ru(bpy)2(DNPIP)](ClO4)2 1 and [Ru(bpy)2(DAPIP)](ClO4)2 2 were synthesized and characterized. The DNA-binding constants for complexes 1 and 2 were determined to be 2.24 (±0.30) × 105 M−1 (s = 1.29) and 6.34 (±0.32) × 104 M−1 (s = 2.84). The photocleavage of pBR322 DNA by Ru(II) complexes was investigated. The cytotoxicity of complexes 1 and 2 were assessed against three tumor cell lines. The apoptosis and cellular uptake were studied. The retardation assay of pGL 3 plasmid DNA was explored. The cell cycle arrest was analysized by flow cytometry. The antioxidant activities of the ligand and complexes were also investigated. [Copyright &y& Elsevier]

Abstract: Ruthenium(II) polypyridyl complexes [Ru(phen)2(APIP)](ClO4)2 1 and [Ru(phen)2(HAPIP)](ClO4)2 2 have been synthesized and characterized. The DNA-binding behaviors were investigated by electronic absorption titration, luminescence spectra, viscosity measurements, thermal denaturation and photoactivated cleavage. The DNA-binding constants K b for complexes 1 and 2 were determined to be 3.38 (±0.42) × 105 M−1 (s = 1.48) and 3.93 (±0.60) × 105 M−1 (s = 3.14), respectively. The studies on the photocleavage demonstrated that the effects of cleavage are concentration-dependent. The results showed that complexes 1 and 2 interact with CT-DNA by intercalative mode. The cytotoxicity of complexes 1 and 2 has been evaluated by MTT method. The apoptosis assay was carried out with acridine orange/ethidium bromide (AO/EB) staining methods. The cellular uptake showed that complexes can enter into the cytoplasm and accumulate in the nuclei. The antioxidant activity studies suggested that the ligands and complexes may be potential drugs to eliminate the radical. [Copyright &y& Elsevier]

Abstract: Two new ruthenium(II) polypyridyl complexes [Ru(dmb)2(Fpp)](ClO4)2 1 (Fpp=2-(3′,3′-difluoro-3,4-methylenedioxyphenyl)imidazo[4,5-f][1,10]phenanthroline, dmb=4,4′-dimethyl-2,2′-bipyridine) and [Ru(bpy)2(Fpp)](ClO4)2 2 (bpy=2,2′-bipyridine) have been synthesized and characterized by elemental analysis, FAB-MS, ES-MS, IR, 1H NMR and 13C NMR. The DNA-binding behaviors of these complexes were investigated by absorption spectroscopic titration, viscosity measurements, thermal denaturation and photocleavage. The mechanism studies of photocleavage reveal that singlet oxygen (1O2) and superoxide anion radical (O2 −) may play an important role in the photocleavage. The cytotoxicity of complexes 1 and 2 have been evaluated by MTT (3-(4,5-dimethylthiazol-2-yl)-2,5-diphenyltetrazolium bromide) method. [Copyright &y& Elsevier]

Abstract: Four cationic porphyrin–anthraquinone (Por–AQ) hybrids differing in lengths of flexible alkyl linkage, 5-[4-(1-N-anthraquinonon-yl)-l-oxophenyl]-10,15,20-tris(N-methylpyridinium-4-yl)porphyrin triiodide, (l =acetyl, pentanoyl, octanoyl, undecanoyl, designed as [AQATMPyP]I3, [AQPTMPyP]I3, [AQOTMPyP]I3 and [AQUTMPyP]I3, respectively, see Fig. 1), were synthesized and their interactions with DNA were investigated. The results of spectroscopic, denaturation and viscosity measurements suggest that [AQATMPyP]I3 binds to DNA through non-intercalative mode while the other three hybrids with longer links bind via bis-intercalative mode. Ethidium bromide (EB) competition experiment was carried out to determine the binding constants (K b) of these compounds for CT DNA, and [AQPTMPyP]I3 shows the largest K b among these hybrids. The photocleavage mechanism and wavelength-dependent cleaving abilities of these hybrids to pBR322 plasmid DNA were also comparably investigated. [Copyright &y& Elsevier]

Abstract: The 2,3-disubstituted 1,4-benzoquinones were synthesized through the regioselective addition of 4-hydroxycoumarins with 1,4-benzoquinone in aqueous acetone, which were different from 2,5-disubstituted adducts generated by the previously reported reaction of compounds possessing an activated methylene with 1,4-benzoquinone. [Copyright &y& Elsevier]

Early Jurassic igneous rocks are abundant in the Nanling Range, southeastern China. They are closely related with economically significant deposits, but the tectonic-magmatic controls on their formation are still controversial. This paper reports zircon U–Pb–Hf–O isotopes for the rhyolites, and whole-rock major–trace element and Sr Nd isotope compositions for the rhyolites and andesites/dacites in the Changpu and Dongkeng basins located in the southern part of Jiangxi Province. The Changpu and Dongkeng rhyolites have high K 2 O contents (4.1–7.6 wt%) and K 2 O/Na 2 O ratios (> 1). Both groups are enriched in HFSE, LREE and show pronounced Nb–Ta–Eu–Sr–P–Ti negative anomalies. Geochemically, they can be classified as A-type and are similar to A 2 -type granitoids globally. Their highly evolved whole-rock Sr Nd isotopes and elevated zircon δ18O (Changpu rhyolites: (87Sr/86Sr) i = 0.7140 to 0.7156, ε Nd (t) = −7.2 to −8.7, δ18O = 8.76 to 9.93‰; Dongkeng rhyolites: (87Sr/86Sr) i = 0.7149 to 0.7162, ε Nd (t) = −6.4 to −7.9, δ18O = 7.04 to 9.78‰) are consistent with their generation dominated by remelting of exisiting crustal materials in an extensional environment. The slightly more radiogenic zircon Hf isotopes of the Dongkeng rhyolites, ε Hf (t) = −2.1 to −7.1 as compared with −6.1 to −8.3 of Changpu rhyolites, likely signify some mantle contribution. The Changpu high-Mg andesites–dacites are geochemically similar to high-Mg andesites (HMAs) of the Setouchi arc volcanic belt in Japan and the Piip Volcanos in the western Aleutian Arc. They have very low ε Nd (t) from −7.8 to −11.3 and highly radiogenic (87Sr/86Sr) i values from 0.7143 to 0.7154. Similar to HMAs in Setouchi, we suggest that they may be derived from melting of subducted sediments and followed by melt-mantle interaction. SIMS zircon U Pb dating yielded extrusive ages of ~190 Ma for both Changpu and Dongkeng rhyolites. The new dating results constrain the minimum age of extrusion of rhyolites and andesites-dacites from the same volcanic sequence to be the earliest Jurassic period. Igneous rocks of this age have very limited distribution in south China. While those found in the coastal regions show features similar to arc rocks, these in the hinterland are rift related. We propose that formation of the Early Jurassic A-type rhyolites and high-Mg andesites–dacites may provide evidence for foundering/delamination of a previously subducted oceanic plateau beneath southeastern China. Unlabelled Image • The volcanic rocks in the Changpu and Dongkeng basins were erupted at ~190 Ma • The A 2 -type rhyolites were mainly derived from exisiting crustal materials • The andesites are similar to arc high-Mg andesites worldwide in trace elements • The magmas were produced by sediment-derived melt–mantle interaction [ABSTRACT FROM AUTHOR]

• Chemistry of magnetite is primarily reflective of evolution of ore-forming fluids. • High-V hydrothermal magnetite (V = ~10000 ppm) was discovered. • High-V magnetite formed in highly-reduced marine environments. The Dahongshan Fe-Cu ore deposit, hosted in the Paleoproterozoic meta-volcanic and meta-sedimentary sequences, is a giant deposit in the Fe-Cu metallogenic province of southwestern China. Two ore types have been identified: (1) massive and disseminated Fe ores hosted dominantly in meta-volcanic rocks and (2) disseminated and banded Fe-Cu ores in meta-sedimentary rocks. Magnetite presents in all orebodies, and is dominant in the Fe ores. Chemistry of magnetite suggest that the fluids for iron mineralization in the Fe and Fe-Cu orebodies are likely chemically similar and cogenetic. Minor sulfides (e.g., molybdenite) occur at the end of iron mineralization stage, indicating the gradually decrease in oxygen fugacity for the mineralizing fluids with magnetite precipitation. Along with evolution, mineralizing fluids generate magnetite with depletions in Cr, Ni, Ga and V, but enrichments in Mn, Sn and Co, which are primarily reflective of the temperature decrease of fluids. We have discovered some magnetite grains that are extremely rich in V (~10000 ppm), but low in Ti and Cr. Geochemical patterns suggest that they were formed by fluids similar to those of ordinary ores. Available knowledge about the unique high-V magnetite indicates highly-reduced marine environments for its generation. Ore bulk REE patterns showing remarkable positive Eu anomalies and absence of obvious Ce anomalies suggest a BIF-like marine environment, consistent with the morphology of both Fe and Fe-Cu orebodies. Our results provide independent evidence for submarine environment in the formation of the giant Precambrian stratiform Fe(-Cu) ore deposit. [ABSTRACT FROM AUTHOR]