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Sample records for platinumii carbonate complex

  1. Synthesis and characterization of new platinum(II) and platinum(IV) triphyrin complexes.

    Science.gov (United States)

    Xue, Zhaoli; Kuzuhara, Daiki; Ikeda, Shinya; Okujima, Tetsuo; Mori, Shigeki; Uno, Hidemitsu; Yamada, Hiroko

    2013-02-18

    Metalation of 6,13,20,21-tetrakis(4-methylphenyl)-22H-tribenzo[14]triphyrin(2.1.1) with PtCl(2) gave a platinum(II) complex having a square-planar coordination structure with two pyrrolic nitrogen atoms and two chloride ions, with a saddle-shaped macrocycle. This platinum(II) complex was easily oxidized by air to an octahedral platinum(IV) complex coordinated by three pyrrolic nitrogen atoms as a tridentate monoanionic cyclic ligand and three chloride ions. When platinum(II) triphyrin was crystallized in air, an oxygen atom was incorporated between two α-carbon atoms of the pyrroles as an oxygen bridge to intercept the 14π aromatic system.

  2. New Perfluorophtalate Complexes of Platinum(II) With Chemotherapeutic Potential

    OpenAIRE

    de Oliveira, M. B.; J. Miller; Banks, R. E.; Kelland, L R; McAuliffe, C. A.; Mahmood, N; Rowland, I. J.

    1996-01-01

    Two new platinum(II) complexes have been synthesized and their anti-tumour and anti-HIV activities have been evaluated. The new complexes are: (i) cis-tetrafluorophthalate-ammine-morpholine-platinum(II) or MMF3 and (ii) cis-tetrafluorophthalate- ammine-piperidine-platinum(II) or MPF4. They were characterized by elemental analysis, IR spectra and 1H and 13C NMR spectra. They were tested against five human ovarian carcinoma cell lines, viz., CH1, CH1cisR, A2780, A2780cisR and SKOV-3. They were ...

  3. A dual-emissive ionic liquid based on an anionic platinum(II) complex

    OpenAIRE

    Ogawa, Tomohiro; Yoshida, Masaki; Ohara, Hiroki; Kobayashia, Atsushi; Kato, Masako

    2015-01-01

    An ionic liquid fabricated froman anionic cyclometalated platinum(II) complex and an imidazolium cation exhibits dual emission from the monomeric and aggregated forms of the platinum complex anions, leading to temperature-dependent color changes of luminescence.

  4. A dual-emissive ionic liquid based on an anionic platinum(ii) complex.

    Science.gov (United States)

    Ogawa, Tomohiro; Yoshida, Masaki; Ohara, Hiroki; Kobayashi, Atsushi; Kato, Masako

    2015-09-07

    An ionic liquid fabricated from an anionic cyclometalated platinum(ii) complex and an imidazolium cation exhibits dual emission from the monomeric and aggregated forms of the platinum complex anions, leading to temperature-dependent color changes of luminescence.

  5. Platinum(II) complexes as spectroscopic probes for biomolecules

    Energy Technology Data Exchange (ETDEWEB)

    Ratilla, E.

    1990-09-21

    The use of platinum(II) complexes as tags and probes for biomolecules is indeed advantageous for their reactivities can be selective for certain purposes through an interplay of mild reaction conditions and of the ligands bound to the platinum. The use of {sup 195}Pt NMR as a method of detecting platinum and its interactions with biomolecules was carried out with the simplest model of platinum(II) tagging to proteins. Variable-temperature {sup 195}Pt NMR spectroscopy proved useful in studying the stereodynamics of complex thioethers like methionine. The complex, Pt(trpy)Cl{sup +}, with its chromophore has a greater potential for probing proteins. It is a noninvasive and selective tag for histidine and cysteine residues on the surface of cytochrome c at pH 5. The protein derivatives obtained are separable, and the tags are easily quantitated and differentiated through the metal-to-ligand charge transfer bands which are sensitive to the environment of the tag. Increasing the pH to 7.0 led to the modification by Pt(trpy)Cl{sup +}of Arg 91 in cytochrome c. Further studies with guanidine-containing ligands as models for arginine modification by Pt(trpy)Cl{sup +} showed that guanidine can act as a terminal ligand and as a bridging ligand. Owing to the potential utility of Pt(trpy)L{sup n+} as electron dense probes of nucleic acid structure, interactions of this bis-Pt(trpy){sup 2+} complex with nucleic acids was evaluated. Indeed, the complex interacts non-covalently with nucleic acids. Its interactions with DNA are not exactly the same as those of its precedents. Most striking is its ability to form highly immobile bands of DNA upon gel electrophoresis. 232 refs.

  6. New platinum(II complexes with benzothiazole ligands

    Directory of Open Access Journals (Sweden)

    José A. Carmona-Negrón

    2016-03-01

    Full Text Available Four new platinum(II complexes, namely tetraethylammonium tribromido(2-methyl-1,3-benzothiazole-κNplatinate(II, [NEt4][PtBr3(C8H7NS] (1, tetraethylammonium tribromido(6-methoxy-2-methyl-1,3-benzothiazole-κNplatinate(II, [NEt4][PtBr3(C9H9NOS] (2, tetraethylammonium tribromido(2,5,6-trimethyl-1,3-benzothiazole-κNplatinate(II, [NEt4][PtBr3(C10H11NS] (3, and tetraethylammonium tribromido(2-methyl-5-nitro-1,3-benzothiazole-κNplatinate(II, [NEt4][PtBr3(C8H6N2O2S] (4, have been synthesized and structurally characterized by single-crystal X-ray diffraction techniques. These species are precursors of compounds with potential application in cancer chemotherapy. All four platinum(II complexes adopt the expected square-planar coordination geometry, and the benzothiazole ligand is engaged in bonding to the metal atom through the imine N atom (Pt—N. The Pt—N bond lengths are normal: 2.035 (5, 2.025 (4, 2.027 (5 and 2.041 (4 Å for complexes 1, 2, 3 and 4, respectively. The benzothiazole ligands are positioned out of the square plane, with dihedral angles ranging from 76.4 (4 to 88.1 (4°. The NEt4 cation in 3 is disordered with 0.57/0.43 occupancies.

  7. Binary Diffusion Coefficients of Platinum(II) Acetylacetonate in Supercritical Carbon Dioxide.

    Science.gov (United States)

    Kong, Chang Yi; Siratori, Tomoya; Wang, Guosheng; Sako, Takeshi; Funazukuri, Toshitaka

    2013-11-14

    Binary diffusion coefficients (D12) and retention factors (k) of platinum(II) acetylacetonate at infinitesimal concentration in supercritical (sc) carbon dioxide (CO2) were measured by the chromatographic impulse response method with a poly(ethylene glycol) coated capillary column at temperatures from (308.15 to 343.15) K and pressures from (8.5 to 40.0) MPa, and D12 in liquid ethanol at temperatures from (298.15 to 333.15) K and atmospheric pressure by the Taylor dispersion method. As has been seen for our previously reported data on other metal complexes measured in sc CO2 and organic solvents, the D12 data in sc CO2 and liquid ethanol were represented by a function of temperature and solvent viscosity. The D12 values for metal complexes were not related to the solute molecular weights. The k values in sc CO2 were expressed by a function of temperature and CO2 density.

  8. Synthesis and Luminescent Properties of an Acetylide-Bridged Dinuclear Platinum(II) Terpyridyl Complex

    Institute of Scientific and Technical Information of China (English)

    WANG,You-Wei(王幼薇); YANG,Qing-Zheng(杨清正); WU,Li-Zhu(吴骊珠); ZHANG,Li-Ping(张丽萍); TUNG,Chen-Ho(佟振合)

    2004-01-01

    An acetylide-bridged dinuclear platinum(II) terpyridyl complex, [Pt(4'-p-tolyl-terpy)-≡-phenyl-≡-(4'-p-tolyl- terpy)Pt](ClO4)2 (1), has been successfully synthesized and its photophysical properties are reported.

  9. Cyclometalated NCN platinum(II) acetylide complexes - Synthesis, photophysics and OLEDs fabrication

    Science.gov (United States)

    Szafraniec-Gorol, Grazyna; Slodek, Aneta; Schab-Balcerzak, Ewa; Grucela, Marzena; Siwy, Mariola; Filapek, Michal; Matussek, Marek; Zych, Dawid; Mackowski, Sebastian; Buczynska, Dorota; Grzelak, Justyna; Erfurt, Karol; Chrobok, Anna; Krompiec, Stanislaw

    2016-12-01

    The novel cyclometalated NCN platinum(II) acetylide complexes were synthesized. As precursors of acetylide ligands were used 9,9-dibutyl-2-ethynylfluorene, 9-butyl-3-ethynylcarbazole, and 5-ethynyl-2,2‧-bithiophene, whereas 1,3-di(2-pirydyl)benzene derivatives were cyclometalating NCN ligands. Variable character of ligands allowed to prepare a series of novel platinum(II) complexes, which showed light emission in a wide wavelength range from 410 to 625 nm. The optical and electrochemical properties of new complexes were examined and compared with theoretical DFT calculations. Complexes containing fluorenyl and carbazyl motif were used as emitters in an organic light-emitting diodes. The applicability of these Pt(II) complexes for electroluminescence was examined.

  10. Bent Dinuclear Platinum(II Halo-Bridged Carbonyl Complexes

    Directory of Open Access Journals (Sweden)

    Fabio Marchetti

    2011-07-01

    Full Text Available Crystals of trans-Pt2(μ-X2X2(CO2 (X = Br, I have been grown and their molecular and crystalline structures have been solved by X-ray diffraction methods. In both cases the dinuclear molecules are bent, with a bending angle of 164.6° and 156.5° for the bromide and the iodide, respectively. While the structure of the bromo-derivative is reported here for the first time, a modification of trans-Pt2(μ-I2I2(CO2 with planar centrosymmetric molecules is known. This appears to be a rare case of a platinum(II halo-bridged derivative structurally characterized in both bent and planar forms.

  11. Cellular and biomolecular responses of human ovarian cancer cells to cytostatic dinuclear platinum(II) complexes.

    Science.gov (United States)

    Lin, Miaoxin; Wang, Xiaoyong; Zhu, Jianhui; Fan, Damin; Zhang, Yangmiao; Zhang, Junfeng; Guo, Zijian

    2011-03-01

    Polynuclear platinum(II) complexes represent a class of potential anticancer agents that have shown promising pharmacological properties in preclinical studies. The nature of cellular responses induced by these complexes, however, is poorly understood. In this research, the cellular responses of human ovarian cancer COC1 cells to dinuclear platinum(II) complexes {[cis-Pt(NH₃)₂Cl]₂L¹}(NO₃)₂ (1) and {[cis-Pt(NH₃)₂Cl]₂L²}(NO₃)₂ (2) (L¹ = α,α'-diamino-p-xylene, L² = 4,4'-methylenedianiline) has been studied using cisplatin as a reference. The effect of platinum complexes on the proliferation, death mode, mitochondrial membrane potential, and cell cycle progression has been examined by MTT assay and flow cytometry. The activation of cell cycle checkpoint kinases (CHK1/2), extracellular signal-regulated kinases (ERK1/2), and p38 mitogen-activated protein kinase (p38 MAPK) of the cells by the complexes has also been analyzed using phospho-specific flow cytometry. Complex 1 is more cytotoxic than complex 2 and cisplatin at most concentrations; complex 2 and cisplatin are comparably cytotoxic. These complexes kill the cells through an apoptotic or apoptosis-like pathway characterized by exposure of phosphatidylserine and dissipation of mitochondrial membrane potential. Complex 1 shows the strongest inductive effect on the morphological changes of the cells, followed by cisplatin and complex 2. Complexes 1 and 2 arrest the cell cycle in G2 or M phase, while cisplatin arrests the cell cycle in S phase. The influence of these complexes on CHK1/2, ERK1/2, and p38 MAPK varies with the dose of the drugs or reaction time. Activation of phospho-ERK1/2 and phospho-p38 MAPK by these complexes is closely related to the cytostatic activity. The results demonstrate that dinuclear platinum(II) complexes can induce some cellular responses different from those caused by cisplatin.

  12. Platinum(II) and platinum(IV) complexes stabilized by abnormal/mesoionic C4-bound dicarbenes.

    Science.gov (United States)

    Khlebnikov, Vsevolod; Heckenroth, Marion; Müller-Bunz, Helge; Albrecht, Martin

    2013-03-28

    Platinum(II) complexes comprising abnormal diimidazolylidene ligands were synthesized from cis-PtMe(2)(DMSO)(2) using microwave-assisted double C-H bond activation. NMR analysis revealed an unusual solvolysis process, induced by coordinating solvents such as DMSO and MeCN, which has not been observed in related normal dicarbene complexes. NMR and IR spectroscopy and crystallographic analysis of the mono-substituted DMSO complex indicate a sulfur-bonding of the DMSO ligand to the platinum(II) center. Analysis of the DMSO exchange kinetics provided for the first time a quantitative measure of the trans effect of abnormal carbene ligands. The kinetic exchange rate in these bidentate abnormal dicarbene complexes is 0.050(±2) s(-1) and thus similar to analogous platinum(II) complexes containing phenylpyridine, yet significantly slower than that induced by pyridylidene pyridine. Reaction of the dicarbene platinum(II) complexes with PhICl(2), Br(2) and I(2) afforded the corresponding platinum(IV) complexes. Linkage isomerism of the Pt(IV)-bound DMSO was observed when the bromination reaction was performed in DMSO solution. Moreover, solvolysis was less pronounced in the platinum(IV) complexes than in the corresponding platinum(II) analogues.

  13. Infinite dilution partial molar volumes of platinum(II) 2,4-pentanedionate in supercritical carbon dioxide.

    Science.gov (United States)

    Kong, Chang Yi; Siratori, Tomoya; Funazukuri, Toshitaka; Wang, Guosheng

    2014-10-03

    The effects of temperature and density on retention of platinum(II) 2,4-pentanedionate in supercritical fluid chromatography were investigated at temperatures of 308.15-343.15K and pressure range from 8 to 40MPa by the chromatographic impulse response method with curve fitting. The retention factors were utilized to derive the infinite dilution partial molar volumes of platinum(II) 2,4-pentanedionate in supercritical carbon dioxide. The determined partial molar volumes were small and positive at high pressures but exhibited very large and negative values in the highly compressible near critical region of carbon dioxide.

  14. Dialkyl bisphosphonate platinum(II) complex as a potential drug for metastatic bone tumor.

    Science.gov (United States)

    Nakatake, Hidetoshi; Ekimoto, Hisao; Aso, Mariko; Ogawa, Atsushi; Yamaguchi, Asami; Suemune, Hiroshi

    2011-01-01

    Bisphosphonates have high affinity for hydroxyapatite (HA), which is abundantly present in bone. Also, platinum complexes are known that have a wide spectrum of antitumor activities. The conjugate of bisphosphonate and a platinum complex might have HA affinity and antitumor activity, and become a drug for metastatic bone tumor. In this study, the authors synthesized platinum complexes that had dialkyl bisphosphonic acid as a ligand, and evaluated the possibility of the synthesized complexes as a drug for metastatic bone tumor. The synthesized dialkyl bisphosphonate platinum(II) complex was characterized, and its stability in an aqueous solution was also confirmed. The synthesized platinum complex showed higher HA affinity than other platinum complexes such as cisplatin and carboplatin in an experiment of adsorption to HA. In vitro, the platinum complex showed tumor growth inhibitory effect stronger than or equal to cisplatin, which is the most commonly used antitumor agent. Moreover, the platinum complex showed a bone absorption inhibitory effect on the osteoclast. These results suggest potential of dialkyl bisphosphonate platinum(II) complexes as a drug for metastatic bone tumor.

  15. Equilibria, Kinetics, and Mechanism for Rapid Substitution Reactions Trans to Triphenylsilyl in Platinum(II) Complexes.

    Science.gov (United States)

    Wendt, Ola F.; Elding, Lars I.

    1997-12-17

    Fast substitution of chloride for bromide and iodide trans to triphenylsilyl in trans-PtCl(SiPh(3))(PMe(2)Ph)(2) has been studied by stopped-flow spectrophotometry in acetonitrile solution. Substitution is reversible with an observable solvent path via the solvento complex trans-[Pt(SiPh(3))(MeCN)(PMe(2)Ph)(2)](+), which has also been synthesized and characterized in solution. Rate constants for the forward and reverse direct substitution pathways are 2900 +/- 100 and 7500 +/- 300 for bromide and 14300 +/- 1100 and 81000 +/- 11000 M(-)(1) s(-)(1) for iodide as nucleophile. The solvento complex reacts ca. 10(3) times faster with iodide than the parent chloride complex, and its reactivity is some 2 orders of magnitude higher than the most reactive solvento species of platinum(II) studied so far. Halide substitution occurs with negative volumes and entropies of activation, but the nucleophilic discrimination is low, and the leaving ligand plays the most important role in the activation process, indicating an I(d) mechanism. Triphenylsilyl has a very high trans effect, comparable to that of ethene and methylisocyanide, due to extensive bond-weakening in the ground state, probably enforced by pi-acception in the transition state. Due to electronic and solvational effects the platinum(II) silyl moiety acts as a hard or borderline metal center in acetonitrile, the thermodynamic stability sequence of its halide complexes being Cl > Br > I, i.e. the reverse of what is usually observed for platinum(II) complexes.

  16. Sulfur containing platinum(II) complexes with N-heterocyclic carbene ligands obtained by reactions of a hydrosulfido complex.

    Science.gov (United States)

    Maeda, Yuri; Hashimoto, Hideki; Nishioka, Takanori

    2012-10-21

    A hydrosulfido platinum(ii) complex with a chelated N-heterocyclic carbene (NHC) ligand was oxidised with O(2) in the presence of excess hydrogen sulfide, to give a linear tetrasulfido complex, and without hydrogen sulfide, to give a thiosulfato-bridged dinuclear complex. The hydrosulfido complex also reacted with an acetato complex containing the chelating NHC platinum unit to afford a trinuclear platinum complex with two triply bridging sulfido ligands showing an equilibrium in solution between two isomers based on the arrangement of the chelating NHC ligands.

  17. Cytotoxic properties of a new organometallic platinum(II) complex and its gold(I) heterobimetallic derivatives.

    Science.gov (United States)

    Serratrice, Maria; Maiore, Laura; Zucca, Antonio; Stoccoro, Sergio; Landini, Ida; Mini, Enrico; Massai, Lara; Ferraro, Giarita; Merlino, Antonello; Messori, Luigi; Cinellu, Maria Agostina

    2016-01-14

    A novel platinum(ii) organometallic complex, [Pt(pbi)(Me)(DMSO)], bearing the 2-(2'-pyridyl)-benzimidazole (pbiH) ligand, was synthesized and fully characterized. Interestingly, the reaction of this organometallic platinum(ii) complex with two distinct gold(i) phosphane compounds afforded the corresponding heterobimetallic derivatives with the pbi ligand bridging the two metal centers. The antiproliferative properties in vitro of [Pt(pbi)(Me)(DMSO)] and its gold(i) derivatives as well as those of the known coordination platinum(ii) and palladium(ii) complexes with the same ligand, of the general formula [MCl2(pbiH)], were comparatively evaluated against A2780 cancer cells, either sensitive or resistant to cisplatin. A superior biological activity of the organometallic compound clearly emerged compared to the corresponding platinum(ii) complex; the antiproliferative effects are further enhanced upon attaching the gold(i) triphenylphosphine moiety to the organometallic Pt compound. Remarkably, these novel metal species are able to overcome nearly complete resistance to cisplatin. Significant mechanistic insight into the study compounds was gained after investigating their reactions with a few representative biomolecules by electrospray mass spectrometry and X-ray crystallography. The obtained results are comprehensively discussed.

  18. Antitumor activity of platinum(II) complexes of 1,2-diamino-cyclohexane isomers.

    Science.gov (United States)

    Kidani, Y; Noji, M; Tashiro, T

    1980-10-01

    Dichloro, dibromo, oxalato, malonato, dinitrato, sulfato and mono and bis-(D-glucuronato) platinum(II) complexes of 1,2-diaminocyclohexane (dach) isomers were prepared and tested on L1210 mouse leukemia employing the NCI protocol for evaluation of Pt analogs. A large number of long-term survivors were observed with certain analogs, though the therapeutic indices (optimal dose/minimum effective dose) were not large. Among the analogs tested, the oxalato, malonato, dinitrato and mono-(D-glucuronato) Pt(II) complexes of trans-1,2-diaminocyclohexane were found to be particularly effective. The glucuronato Pt complexes appear to be promising candidates for clinical trial since they have the highest solubility in water.

  19. Antitumor activity of phenylene bridged binuclear bis(imino-quinolyl)palladium(II) and platinum(II) complexes.

    Science.gov (United States)

    Motswainyana, William M; Onani, Martin O; Madiehe, Abram M; Saibu, Morounke

    2014-04-01

    Antitumor effects of a known bis(imino-quinolyl)palladium(II) complex 1 and its newly synthesized platinum(II) analogue 2 were evaluated against human breast (MCF-7) and human colon (HT-29) cancer cell lines. The complexes gave cytotoxicity profiles that were better than the reference drug cisplatin. The highest cytotoxic activities were pronounced in complex 2 across the two examined cancer cell lines. Both compounds represent potential active drugs based on bimetallic complexes.

  20. Reactions of Dinuclear Platinum(II) Complexes with Peptides.

    Science.gov (United States)

    Rajković, Snežana; Živković, Marija D; Djuran, Miloš I

    2016-01-01

    The present review article highlights recent findings in the reactions between different dinuclear Pt(II) complexes with peptides containing cysteine, methionine and histidine residues. The reactions of {trans-[Pt(NH3)2Cl]2(μ-X)}(2+) and {trans-[Pt(NH3)2(H2O)]2(μ-X)}(4+) type complexes with different bridging ligands (X) (X = pyrazine, 4,4'-bipyridyl and 1,2-bis(4-pyridyl)ethane) with the tripeptide glutathione proceeded in two steps. In the first step, one water or chlorido ligand of the dinuclear Pt(II) complex was substituted by the sulfhydryl group of GSH, while in the second step, the remaining water or chlorido ligand from the dinuclear Pt(II)-peptide complex was replaced by the second molecule of glutathione, finally leading to the formation of the {trans-[Pt(NH3)2(GS)]2(μ-X)}(2+) complex. It was shown that the bridging ligand had an important influence on the reactivity of these complexes with glutathione. No hydrolytic cleavage of any amide bond was observed in the reactions between these complexes and glutathione. However, in reactions performed in acidic media (2.0 complexes with the general formulae {[Pt(L)(H2O)]2(μ-diazine)}(4+) (L is different bidentate coordinated diamine ligands and diazine is a pyrazine- or pyridazine-bridging ligand) and Nacetylated peptides containing L-methionine and L-histidine amino acids in the side chains (Ac-L-Met-Gly, Ac-L-His-Gly and Ac-L-Met-Gly-L-His-GlyNH2), regioselective cleavage of these peptides occurred. The mechanism of these hydrolytic reactions was discussed in relation to the structure of the diazine-bridged Pt(II) complex and the investigated peptides. A systematic summary of these results could contribute to the future design of new dinuclear Pt(II) complexes as potential reagents for regioselective cleavage of peptides and proteins.

  1. Preparation and Biological Properties of Platinum(II Complex-Loaded Copolymer PLA-TPGS

    Directory of Open Access Journals (Sweden)

    Ha Phuong Thu

    2013-01-01

    Full Text Available A new nanodrug system containing bis(menthone thiosemicarbazonato Platinum(II complex (Pt-thiomen encapsulated with the block copolymers polylactide-d-α-tocopheryl polyethylene glycol 1000 succinate (PLA-TPGS was prepared by a modified solvent extraction/evaporation technique. The characteristics of the nanoparticles including surface morphology, size distribution, structure, and biological activities such as antimicrobial and cytotoxic activities were in vitro investigated. The spherical nanoparticles were around 50 nm in size with core-shell structure and narrow-size distribution. The encapsulated Pt-thiomen can avoid interaction with proteins in the blood plasma. The inhibitory activity of Pt-thiomen-loaded PLA-TPGS nanoparticles on the growth of some bacteria, fungi, and Hep-G2 cells suggests a possibility of developing PLA-TPGS-Pt-thiomen nanoparticles as one of the potential chemotherapeutic agents.

  2. Modulation of Intersystem Crossing Rate by Minor Ligand Modifications in Cyclometalated Platinum(II) Complexes.

    Science.gov (United States)

    Shafikov, Marsel Z; Kozhevnikov, Dmitry N; Bodensteiner, Michael; Brandl, Fabian; Czerwieniec, Rafał

    2016-08-01

    Photophysical properties of four new platinum(II) complexes comprising extended ppy (Hppy = 2-phenylpyridine) and thpy (Hthpy = 2-(2'-thienyl)pyridine) cyclometalated ligands and acetylacetonate (acac) are reported. Substitution of the benzene ring of Pt-ppy complexes 1 and 2 with a more electron-rich thiophene of Pt-thpy complexes 3 and 4 leads to narrowing of the HOMO-LUMO gap and thus to a red shift of the lowest energy absorption band and phosphorescence band, as expected for low-energy excited states of the intraligand/metal-to-ligand charge transfer character. However, in addition to these conventional spectral shifts, another, at first unexpected, substitution effect occurs. Pt-thpy complexes 3 and 4 are dual emissive showing fluorescence about 6000 cm(-1) (∼0.75 eV) higher in energy relative to the phosphorescence band, while for Pt-ppy complexes 1 and 2 only phosphorescence is observed. For dual-emissive complexes 3 and 4, ISC rates kISC are estimated to be in order of 10(9)-10(10) s(-1), while kISC of Pt-ppy complexes 1 and 2 is much faster amounting to 10(12) s(-1) or more. The relative intensities of the fluorescence and phosphorescence signals of Pt-thpy complexes 3 and 4 depend on the excitation wavelength, showing that hyper-intersystem crossing (HISC) in these complexes is observably significant.

  3. Novel platinum(II) complexes of long chain aliphatic diamine ligands with oxalato as the leaving group: Comparative cytotoxic activity relative to chloride precursors

    Energy Technology Data Exchange (ETDEWEB)

    Silva, Heveline; Barra, Carolina V.; Rocha, Fillipe V.; Fontes, Ana Paula S. [Universidade Federal de Juiz de Fora (UFJF), MG (Brazil). Dept. de Quimica; Lopes, Miriam T.P. [Universidade Federal deMinas Gerais (UFMG), Belo Horizonte, MG (Brazil). Dept. de Farmacologia; Frezard, Frederic, E-mail: frezard@icb.ufmg.b [Universidade Federal de Minas Gerais (UFMG), Belo Horizonte, MG (Brazil). Dept. de Fisiologia e Biofisica

    2010-07-01

    Platinum complexes play an important role in the development of anticancer drugs. Their cytotoxicity can be influenced by the nature of the leaving ligands, due to the hydrolysis reaction that occurs prior to the binding of the platinum complex to DNA. Also, non-leaving groups such as lipophilic diamines may affect cellular uptake. In this work, we describe the synthesis of platinum(II) complexes having oxalato and long chain aliphatic N-alkyl ethylenediamines as ligands. The products were characterized by elemental analyses, infrared spectroscopy and {sup 1}H, {sup 13}C and {sup 195}Pt NMR spectroscopy. Biological activity was assessed against tumor cell lines (A{sub 549}, B16-F1, B16-F10, MDA-MB-231) and non-tumor cell lines (BHK-21 and CHO). The length of the carbon chain affects the cytotoxicity and the oxalato complexes were less cytotoxic than the respective chloride-containing analogues. (author)

  4. Structures of polynuclear complexes of palladium(II) and platinum(II) formed by slow hydrolysis in acidic aqueous solution.

    Science.gov (United States)

    Torapava, Natallia; Elding, Lars I; Mändar, Hugo; Roosalu, Kaspar; Persson, Ingmar

    2013-06-07

    The aqua ions of palladium(II) and platinum(II) undergo extremely slow hydrolysis in strongly acidic aqueous solution, resulting in polynuclear complexes. The size and structures of these species have been determined by EXAFS and small angle X-ray scattering, SAXS. For palladium(II), the EXAFS data show that the Pd-O and Pd···Pd distances are identical to those of crystalline palladium(II) oxide, but the intensities of the Pd···Pd distances in the Fourier transform at 3.04 and 3.42 Å are significantly lower compared to those of crystalline PdO. Furthermore, no Pd···Pd distances beyond 4 Å are observed. These observations strongly indicate that the polynuclear palladium(II) complexes are oxido- and hydroxido-bridged species with the same core structure as solid palladium(II) oxide. Based on the number of Pd···Pd distances, as derived from the EXAFS data, their size can be estimated to be approximately two unit cells, or ca. 1.0 nm(3). For platinum(II), EXAFS data of the polynuclear species formed in the slow hydrolysis process show Pt-O and Pt···Pt distances identical to those of amorphous platinum(II) oxide, precipitating from the solution studied. The Pt···Pt distances are somewhat different from those reported for crystalline platinum(II) oxide. The polynuclear platinum(II) complexes have a similar structure to the palladium ones, but they are somewhat larger, with an estimated diameter of 1.5-3.0 nm. It has not been possible to precipitate any of these species by ultracentrifugation. They are detectable by SAXS, indicating diameters between 0.7 and 2 nm, in excellent agreement with the EXAFS observations. The number of oxido- relative to hydroxido bridges will increase with increasing size of the complex. The charge of the complexes will remain about the same, +4, at growth, with approximate formulas [Pd10O4(OH)8(H2O)12](4+) and [Pt14O8(OH)8(H2O)12](4+) for complexes with a size of 2 and 3 unit cells of the corresponding solid metal oxide

  5. Circular dichroism spectroscopy study of crystalline-to-amorphous transformation in chiral platinum(II) complexes.

    Science.gov (United States)

    Zhang, Xiao-Peng; Wu, Tao; Liu, Jian; Zhao, Jin-Cheng; Li, Cheng-Hui; You, Xiao-Zeng

    2013-07-01

    Two couples of enantiomeric platinum(II) complexes: Pt(L1a )Cl (1a), Pt(L1b )Cl (1b) and Pt(L1a )(C ≡ C - Ph) (2a), Pt(L1b )(C ≡ C - Ph) (2b) (L1a  = (+)-1,3-di-(2-(4,5-pinene)pyridyl)benzene, L1b  = (-)-1,3-di-(2-(4,5-pinene)pyridyl)benzene) were synthesized and characterized. Their absolute configurations were determined by single crystal X-ray diffraction and further verified by circular dichroism (CD) spectra (including electronic circular dichroism [ECD] and vibrational circular dichroism [VCD]). These complexes show interesting mechanoluminescence and/or vapoluminescence due to crystalline-to-amorphous transformation. The crystalline solids, grinding-induced amorphous powders, and vapor-induced amorphous powders of complexes 2a and 2b were comparatively investigated by solid-state ECD and VCD spectra. The transformation from crystalline solids to amorphous powders was accompanied by significant variances of the spectral feature in both ECD and VCD spectra. © 2013 Wiley Periodicals, Inc.

  6. Structural properties of platinum(II) biphenyl complexes containing 1,10-phenanthroline derivatives

    Science.gov (United States)

    Rillema, D. Paul; Cruz, Arvin J.; Tasset, Brandon J.; Moore, Curtis; Siam, Khamis; Huang, Wei

    2013-06-01

    Seven platinum(II) complexes formulated as Pt(bph)L, where bph is the 2,2'-biphenyl dianion and L = 4-methyl-1,10-phenanthroline (4-Mephen), 5-methyl-1,10-phenanthroline (5-Mephen), 5-chloro-1,10-phenanthroline (5-Clphen), 5,6-dimethyl-1,10-phenanthroline (5,6-Me2phen), 4,7-dimethyl-1,10-phenanthroline (4,7-Me2phen), 4,7-diphenyl-1,10-phenanthroline (4,7-Ph2phen) and 3,4,7,8-tetramethyl-1,10-phenanthroline (3,4,7,8-Me4phen) are reported. Protons attached to the phen ligand resonate downfield from those attached to the bph ligand and two proton signals are split by interaction with 195Pt. Pt(bph)(3,4,7,8-Me4phen), Pt(bph)(4,7-Me2phen), Pt(bph)(5,6-Me2phen), Pt(bph)(4,7-Ph2phen) and Pt(bph)(5-Mephen) crystallize in the space groups Pna21, P21/n, P21/c, P - 1 and Pca21, respectively. The structures of the complexes deviate from true planarity and divide themselves into two groups where the bph and phen ligands cross in an X configuration or bow out in a butterfly (B) configuration. Circular dichroism revealed two different spectra with respect to the X and B configurations.

  7. N6-Benzyladenosine Derivatives as Novel N-Donor Ligands of Platinum(II Dichlorido Complexes

    Directory of Open Access Journals (Sweden)

    Ján Vančo

    2013-06-01

    Full Text Available The platinum(II complexes trans-[PtCl2(Ln2]∙xSolv 1–13 (Solv = H2O or CH3OH, involving N6-benzyladenosine-based N-donor ligands, were synthesized; Ln stands for N6-(2-methoxybenzyladenosine (L1, involved in complex 1, N6-(4-methoxy-benzyladenosine (L2, 2, N6-(2-chlorobenzyladenosine (L3, 3, N6-(4-chlorobenzyl-adenosine (L4, 4, N6-(2-hydroxybenzyladenosine (L5, 5, N6-(3-hydroxybenzyl-adenosine (L6, 6, N6-(2-hydroxy-3-methoxybenzyladenosine (L7, 7, N6-(4-fluoro-benzyladenosine (L8, 8, N6-(4-methylbenzyladenosine (L9, 9, 2-chloro-N6-(3-hydroxy-benzyladenosine (L10, 10, 2-chloro-N6-(4-hydroxybenzyladenosine (L11, 11, 2-chloro-N6-(2-hydroxy-3-methoxybenzyladenosine (L12, 12 and 2-chloro-N6-(2-hydroxy-5-methylbenzyladenosine (L13, 13. The compounds were characterized by elemental analysis, mass spectrometry, IR and multinuclear (1H-, 13C-, 195Pt- and 15N- and two-dimensional NMR spectroscopy, which proved the N7-coordination mode of the appropriate N6-benzyladenosine derivative and trans-geometry of the title complexes. The complexes 1–13 were found to be non-toxic in vitro against two selected human cancer cell lines (HOS and MCF7; with IC50 > 50.0 µM. However, they were found (by ESI-MS study to be able to interact with the physiological levels of the sulfur-containing biogenic biomolecule L-methionine by a relatively simple 1:1 exchange mechanism (one Ln molecule was replaced by one L-methionine molecule, thus forming a mixed-nitrogen/sulfur-ligand dichlorido-platinum(II coordination species.

  8. Novel dinuclear platinum(II) complexes containing mixed nitrogen-sulfur donor ligands.

    Science.gov (United States)

    Hochreuther, Stephanie; Puchta, Ralph; van Eldik, Rudi

    2011-12-19

    A series of novel dinuclear platinum(II) complexes were synthesized containing a mixed nitrogen-sulfur donor bidentate chelate system in which the two platinum centers are connected by an aliphatic chain of variable length. The bidentate chelating ligands were selected to stabilize the complex toward decomposition. The pK(a) values and reactivity of the four synthesized complexes, namely, [Pt(2)(S(1),S(4)-bis(2-pyridylmethyl)-1,4-butanedithioether)(OH(2))(4)](4+) (4NSpy), [Pt(2)(S(1),S(6)-bis(2-pyridylmethyl)-1,6-hexanedithioether)(OH(2))(4)](4+) (6NSpy), [Pt(2)(S(1),S(8)-bis(2-pyridylmethyl)-1,8-octanedithioether)(OH(2))(4)](4+) (8NSpy), and [Pt(2)(S(1),S(10)-bis(2-pyridylmethyl)-1,10-decanedithioether)(OH(2))(4)](4+) (10NSpy), were investigated. This system is of special interest because only little is known about the substitution behavior of dinuclear platinum complexes that contain a bidentate chelate that forms part of the aliphatic bridging ligand. Moreover, the ligands as well as the dinuclear complexes were examined in terms of their cytotoxic activity, and the 10NSpy complex was found to be active. Spectrophotometric acid-base titrations were performed to determine the pK(a) values of all the coordinated water molecules. The substitution of coordinated water by thiourea was studied under pseudo-first-order conditions as a function of nucleophile concentration, temperature, and pressure, using stopped-flow techniques and UV-vis spectroscopy. The results for the dinuclear complexes were compared to those for the corresponding mononuclear reference complex [Pt(methylthiomethylpyridine)(OH(2))(2)](2+) (Pt(mtp)), by which the effect of the increasing aliphatic chain length of the bridged complexes could be investigated. The results indicate that there is a clear interaction between the two platinum centers, which becomes weaker as the chain length between the metal centers increases. Furthermore, differences and similarities of the N,S-system were compared to

  9. Reaction Mechanism for Olefin Exchange at Chloro Ethene Complexes of Platinum(II).

    Science.gov (United States)

    Plutino, Maria Rosaria; Otto, Stefanus; Roodt, Andreas; Elding, Lars I.

    1999-03-22

    Complex equilibria in methanol/chloroform/dichloromethane solutions containing Zeise's anion, [PtCl(3)(C(2)H(4))](-) (1), the solvento species, trans-[PtCl(2)(C(2)H(4))(MeOH)] (2), and the dinuclear complex, trans-[PtCl(2)(C(2)H(4))](2) (3), have been studied by UV-vis, (1)H, and (195)Pt NMR spectroscopy, giving average values of K(Cl) = (1.6 +/- 0.2)10(3) M(-)(1) and K(S) = (0.16 +/- 0.02) M(-)(1) for the equilibrium constants between 2 and 1 and 3 and 2, respectively. The bridged complex 3 is completely split into monomeric solvento complexes 2 in methanol and in chloroform or dichloromethane solutions with [MeOH] > 0.5 M. Ethene exchange at the mononuclear complexes 1 and 2 was studied by (1)H NMR line-broadening experiments in methanol-d(4). Observed overall exchange rate constants decrease with an increase in free chloride concentration due to the displacement of the rapid equilibrium between 1 and 2 toward the more slowly exchanging parent chloro complex 1. Ethene exchange rate constants at 298 K for complexes 1 and 2 are k(ex1) = (2.1 +/- 0.1)10(3) M(-)(1) s(-)(1)and k(ex2) = (5.0 +/- 0.2)10(5) M(-)(1) s(-)(1), respectively, with corresponding activation parameters DeltaH(1)() = 19.1 +/- 0.3 kJ mol(-)(1), DeltaS(1)() = -117 +/- 1 J K(-)(1) mol(-)(1), DeltaH(2)() = 10.2 +/- 0.4 kJ mol(-)(1), and DeltaS(2)() = -102 +/- 2 J K(-)(1) mol(-)(1). The activation process is largely entropy controlled; the enthalpy contributions only amounting to approximately 30% of the free energy of activation. Ethene exchange takes place via associative attack by the entering olefin at the labile site trans to the coordinated ethene, which is either occupied by a chloride or a methanol molecule in the ground state. The intimate mechanism might involve a two-step process via trans-[PtCl(2)(C(2)H(4))(2)] in steady state or a concerted process via a pentacoordinated transition state with two ethene molecules bound to the platinum(II).

  10. DNA interaction and cytotoxic activities of square planar platinum(II) complexes with N, S-donor ligands

    Science.gov (United States)

    Patel, Mohan N.; Patel, Chintan R.; Joshi, Hardik N.; Thakor, Khyati P.

    2014-06-01

    The platinum(II) complexes with N, S-donor ligands have been synthesized and characterized by physicochemical methods viz. elemental, electronic, FT-IR, 1H NMR and LC-MS spectra. The binding mode and potency of the complexes with HS DNA (Herring Sperm) have been examined by absorption titration and viscosity measurement studies. The results revealed that complexes bind to HS DNA via covalent mode with the intrinsic binding constant (Kb) in the range 1.37-7.76 × 105 M-1. Decrease in the relative viscosity of HS DNA also supports the covalent mode of binding. The DNA cleavage activity of synthesized complexes has been carried out by gel electrophoresis experiment using supercoiled form of pUC19 DNA; showing the unwinding of the negatively charged supercoiled DNA. Brine shrimp (Artemia Cysts) lethality bioassay technique has been applied for the determination of toxic property of synthesized complexes in terms of μM.

  11. Electron transfer and hydrogen generation from a molecular dyad: platinum(II) alkynyl complex anchored to [FeFe] hydrogenase subsite mimic.

    Science.gov (United States)

    Wang, Wen-Guang; Wang, Feng; Wang, Hong-Yan; Tung, Chen-Ho; Wu, Li-Zhu

    2012-02-28

    A PS-Fe(2)S(2) molecular dyad 1a directly anchoring a platinum(II) alkynyl complex to a Fe(2)S(2) active site of a [FeFe] H(2)ase mimic, and an intermolecular system of its reference complexes 1b and 2, have been successfully constructed. Time-dependence of H(2) evolution shows that PS-Fe(2)S(2)1a as well as complex 2 with 1b can produce H(2) in the presence of a proton source and sacrificial donor under visible light irradiation. Spectroscopic and electrochemical studies on the electron transfer event reveal that the reduced Fe(I)Fe(0) species generated by the first electron transfer from the excited platinum(II) complex to the Fe(2)S(2) active site in PS-Fe(2)S(2)1a and complex 2 with 1b is essential for photochemical H(2) evolution, while the second electron transfer from the excited platinum(II) complex to the protonated Fe(I)Fe(0) species is thermodynamically unfeasible, which might be an obstacle for the relatively small amount of H(2) obtained by PS-Fe(2)S(2) molecular dyads reported so far.

  12. Methyl 6-Amino-6-deoxy-d-pyranoside-Conjugated Platinum(II) Complexes for Glucose Transporter (GLUT)-Mediated Tumor Targeting: Synthesis, Cytotoxicity, and Cellular Uptake Mechanism.

    Science.gov (United States)

    Li, Taoli; Gao, Xiangqian; Yang, Liu; Shi, Yunli; Gao, Qingzhi

    2016-05-19

    Methyl 6-aminodeoxy-d-pyranoside-derived platinum(II) glycoconjugates were designed and synthesized based on the clinical drug oxaliplatin for glucose transporter (GLUT)-mediated tumor targeting. In addition to a substantial improvement in water solubility, the conjugates exhibited cytotoxicity similar to or higher than that of oxaliplatin in six different human cancer cell lines. GLUT-mediated transport of the complexes was investigated with a cell-based fluorescence competition assay and GLUT-inhibitor-mediated cytotoxicity analysis in a GLUT-overexpressing human colorectal adenocarcinoma (HT29) cell line. The antitumor effect of the aminodeoxypyranoside-conjugated platinum(II) complexes was found to depend significantly on the GLUT inhibitor, and the cellular uptake of the molecules was regulated by GLUT-mediated transport. The results from this study demonstrate the potential advantages of aminodeoxypyranosides as sugar motifs for glycoconjugation for Warburg-effect-targeted drug design. These fundamental results also support the potential of aminodeoxypyranoside-conjugated platinum(II) complexes as lead compounds for further preclinical evaluation.

  13. New binary and ternary platinum(II) formamidine complexes: Synthesis, characterization, structural studies and in-vitro antitumor activity

    Science.gov (United States)

    Soliman, Ahmed A.; Alajrawy, Othman I.; Attaby, Fawzy A.; Linert, W.

    2016-07-01

    A series of new binary and ternary platinum(II) complexes of the type [Pt(L1-4)Cl2].xH2O and [Pt(L1-4)ox].xH2O where L = formamidine ligands and ox = oxalate, have been synthesized and characterized by elemental analyses, magnetic susceptibility, UV-vis, infrared (IR), mass spectroscopy, thermal analysis and theoretical calculations. The spectroscopic data indicated that the formamidine ligands act as bidentate N2 donors. The complexes (1-8) are diamagnetic and the optimization of their structures indicated that the geometry is distorted square planar with Cl-Pt-Cl, O-Pt-O and N-Pt-N bond angles ranged 81.73°-95.82° which is acceptable for the heteroleptic complexes. The electronic energies (a.u.) of the complexes (-893.53 to -1989.84) indicate that the complexes are more stable than the ligands. The energies of the HOMO (-0.218 to -0.244) and LUMO (-.0111to -0.134) orbitals of the complexes were negative which indicates that the complexes are stable compounds. The dipole moment of the complexes (6.23-19.89 Debye) indicates that the complexes are polarized. The complexes are thermally stable as shown from their relatively higher overall activation energies (889-2066 kJ mol-1). The complexes are proved to have a good cytotoxicity with IC50 (μM) against MCF-7 (0.040-0.117), HCT-116 (0.085-0.119) and HepG-2 (0.058-0.131) cell lines, which open the field for further application as antitumor compounds.

  14. Structural, spectroscopic and quantum chemical studies of acetyl hydrazone oxime and its palladium(II) and platinum(II) complexes

    Science.gov (United States)

    Kaya, Yunus; Icsel, Ceyda; Yilmaz, Veysel T.; Buyukgungor, Orhan

    2015-09-01

    Acetyl hydrazone oxime, [(1E,2E)-2-(hydroxyimino)-1-phenylethylidene]acetohydrazone (hipeahH2) and its palladium(II) and platinum(II) complexes, [M(hipeahH)2] (M = PdII and PtII), have been synthesized and characterized by elemental analysis, UV-vis IR, NMR and LC-MS techniques. X-ray diffraction analysis of [Pd(hipeahH)2] shows that the two hipeahH2 ligands are not equal; one of the ligands loses the hydrazone proton, while the other one loses the oxime proton, resulting in a different coordination behavior to form five- and six-membered chelate rings. The molecular geometries from X-ray experiments in the ground state were compared using the density functional theory (DFT) with the B3LYP method combined with the 6-311++G(d,p) basis set for the ligand and the LanL2DZ basis set for the complexes. Comprehensive theoretical and experimental structural studies on the molecule have been carried out by FT-IR, NMR and UV-vis spectrometry. In addition, the isomer studies of ligand and its complexes were made by DFT.

  15. Synthesis, Characterization and in Vitro Antitumor Activity of Platinum(II Oxalato Complexes Involving 7-Azaindole Derivatives as Coligands

    Directory of Open Access Journals (Sweden)

    Pavel Štarha

    2014-07-01

    Full Text Available The platinum(II oxalato complexes [Pt(ox(naza2] (1–3 were synthesized and characterized by elemental analysis (C, H, N, multinuclear NMR spectroscopy (1H, 13C, 15N, 195Pt and electrospray ionization mass spectrometry (ESI-MS; naza = 4-chloro-7-azaindole (4Claza; 1, 3-bromo-7-azaindole (3Braza; 2 or 4-bromo-7-azaindole (4Braza; 3. The prepared substances were screened for their in vitro antitumor activity on the osteosarcoma (HOS and breast adenocarcinoma (MCF7 human cancer cell lines, where 2 showed moderate antitumor effect (IC50 = 27.5 μM, and 18.3 μM, respectively. The complex 2 was further tested on a panel of six others human cancer cell lines, including the malignant melanoma (G361, cervix carcinoma (HeLa, ovarian carcinoma (A2780, cisplatin-resistant ovarian carcinoma (A2780R, lung carcinoma (A549 and prostate adenocarcinoma (LNCaP. This substance was found to be moderate antitumor effective against G361 (IC50 = 17.3 μM, HeLa (IC50 = 31.8 μM and A2780 (IC50 = 19.2 μM cell lines. The complex 2 was also studied by NMR for its solution stability and by ESI-MS experiments for its ability to interact with biomolecules, such as cysteine, glutathione or guanosine 5'-monophosphate.

  16. Surfactant gel adsorption of platinum(II), (IV) and palladium(II) as chloro-complexes and kinetic separation of palladium from platinum using EDTA.

    Science.gov (United States)

    Murakami, Yoshiko; Hiraiwa, Kaoru; Sasaki, Yoshiaki; Fujiwara, Isamu; Tagashira, Shoji

    2007-09-01

    A micellar solution of cetylpyridinium chloride (CPC) can separate into two phases due to a temperature change or to the addition of salts. Platinum(II), (IV) and palladium(II) reacted with chloride ions to form stable anionic complexes of PtCl4(2-), PtCl6(2-) and PdCl4(2-), respectively, and were adsorbed onto the CPC gel phase. The CPC phase plays the role of an ion-exchange adsorbent for the anionic complexes. By such a procedure, the precious metals of platinum and palladium could be separated from base metals such as copper, zinc and iron. The kinetic separation was performed by a ligand exchange reaction of the palladium(II) chloro-complex with EDTA at 60 degrees C. The anionic palladium(II)-EDTA complex could not bind the opposite charged CP+ and was desorbed from the CPC phase. In the aqueous phase, the recovery of palladium(II) by the double-desorption was 101.1 +/- 1.2%. The platinum(II) and (IV) chloro-complexes were stable for at least 30 min and remained in the CPC phase.

  17. Characteristic effect of an anticancer dinuclear platinum(II) complex on the higher-order structure of DNA.

    Science.gov (United States)

    Kida, Naoko; Katsuda, Yousuke; Yoshikawa, Yuko; Komeda, Seiji; Sato, Takaji; Saito, Yoshihiro; Chikuma, Masahiko; Suzuki, Mari; Imanaka, Tadayuki; Yoshikawa, Kenichi

    2010-06-01

    It is known that a 1,2,3-triazolato-bridged dinuclear platinum(II) complex, [{cis-Pt(NH(3))(2)}(2)(micro-OH)(micro-1,2,3-ta-N (1),N (2))](NO(3))(2) (AMTA), shows high in vitro cytotoxicity against several human tumor cell lines and circumvents cross-resistance to cisplatin. In the present study, we examined a dose- and time-dependent effect of AMTA on the higher-order structure of a large DNA, T4 phage DNA (166 kbp), by adapting single-molecule observation with fluorescence microscopy. It was found that AMTA induces the shrinking of DNA into a compact state with a much higher potency than cisplatin. From a quantitative analysis of the Brownian motion of individual DNA molecules in solution, it became clear that the density of a DNA segment in the compact state is about 2,000 times greater than that in the absence of AMTA. Circular dichroism spectra suggested that AMTA causes a transition from the B to the C form in the secondary structure of DNA, which is characterized by fast and slow processes. Electrophoretic measurements indicated that the binding of AMTA to supercoiled DNA induces unwinding of the double helix. Our results indicate that AMTA acts on DNA through both electrostatic interaction and coordination binding; the former causes a fast change in the secondary structure from the B to the C form, whereas the latter promotes shrinking in the higher-order structure as a relatively slow kinetic process. The shrinking effect of AMTA on DNA is attributable to the possible increase in the number of bridges along a DNA molecule. It is concluded that AMTA interacts with DNA in a manner markedly different from that of cisplatin.

  18. Study on the cytotoxic activity of platinum(II) complexes of (1R,2R)-N(1)-cyclopentyl-1,2-cyclohexanediamine with substituted malonate derivatives.

    Science.gov (United States)

    Zhou, Zhiping; Chen, Feihong; Xu, Gang; Gou, Shaohua

    2016-01-15

    Three platinum(II) complexes of (1R,2R)-N(1)-cyclopentyl-1,2-cyclohexanediamine with malonate derivatives were designed, synthesized and spectrally characterized. MTT assay showed that the complexes possessed positive cytotoxic effect on the four human solid tumor cell lines. Among the complexes, complex 2 demonstrated the strongest cytotoxic activity compared to cisplatin and oxaliplatin against HepG2 cell line (IC50=3.04μM). Furthermore, the results of gel electrophoresis revealed that complex 2 interacted with DNA in a different mode from that of cisplatin. Mechanism studies of cell proliferation inhibition and cellular uptake indicated that complex 2 entered HepG2 cell more efficiently than cisplatin, exhibited massive G2 accumulation and then induced apoptosis.

  19. Kinetics of the methylation of a platinum(II) diimine dithiolate complex

    Energy Technology Data Exchange (ETDEWEB)

    Stace, Justin J.; Ball, P. J.; Shingade, Vikas; Chatterjee, Sayandev; Shiveley, Amber; Fleeman, Wendi L.; Staniszewski, Aaron J.; Krause, Jeanette A.; Connick, William B.

    2016-06-01

    Pt(dbbpy)(bdt) and Pt(tmphen)(bdt) (dbbpy = 4,4'-di-t-butyl-2,2'-bipyridine; tmphen = 3,4,7,8-tetramethyl-1,10-phenanthroline; bdt2- = 1,2-benzenedithiolate) are reported. Pt(dbbpy)(bdt) reacts with one equivalent of methyl iodide to give the S-methylated product, [Pt(dbbpy)(CH3bdt)]I. The reaction follows second order kinetics with a rate constant of 1.3×10 2 M-1s-1 at 311 K. The accumulated data are consistent with direct nucleophilic attack by the coordinated bdt2- ligand sulfur atom on the carbon atom of the methyl iodide. Variable-temperature experiments yield an Arrhenius activation energy of 51 ± 3 kJ/mol. Activated complex reaction theory yields an enthalpy and entropy of activation of 48 ± 2 kJ/mol and 125 ± 7 J/(mol K), respectively, consistent with an SN2 reaction mechanism. The structure of the monosulfinate adduct, Pt(dbbpy)(bdtO2), also is reported. The fluid-solution luminescence of Pt(tmphen)(bdt) is concentration dependent and characterized by a 1591 ± 41 ns lifetime and 2.6 ± 0.2% quantum yield at infinite dilution.

  20. The synthesis and characterization of complexes of zinc(II, cadmium(II, platinum(II and palladium(II with potassium 3-dithiocarboxy-3-aza-5-aminopentanoate

    Directory of Open Access Journals (Sweden)

    SRECKO TRIFUNOVIC

    2004-02-01

    Full Text Available Complexes of zinc(II, cadmium(II, platinum(II and palladium(II with a new polydentate dithiocarbamate ligand, 3-dithiocarboxy-3-aza-5-aminopentanoate (daap-, of the type M(daap2·nH2O (M = Zn(II, Cd(II, n = 2, or M = Pt(II, Pd(II, n = 0, have been prepared and characterized by elemental analysis, IR and UV/VIS spectroscopy, as well as magnetic measurements. The spectra of the complexes suggest a bidentate coordination of the daap- ligand to the metal ions via the sulfur atoms of the deprotonated dithiocarbamato group. The fact that under the same experimental conditions its S-methyl ester does not form complexes could be taken as proof of the suggested coordination mode.

  1. Diamino-ligated platinum(II) and platinum(IV) phenoxide complexes; syntheses and crystal structures

    NARCIS (Netherlands)

    Koten, G. van; Kapteijn, G.M.; Meijer, M.D.; Grove, D.M.; Veldman, N.; Spek, A.L.

    1997-01-01

    The reaction of the diamino-ligated dimethylplatinum(II) complex [Pt(Me){2}(bpy)] (bpy=2, 2'-bipyridyl) with phenol affords the new complex [Pt(Me)(OPh)(bpy)] (1). The X-ray crystal structure of square-planar 1 is reported: orthorhombic, space group P2{1}2{1}2{1} (No. 19), a = 9.1625(12), b =

  2. Cytotoxicity and DNA interactions of some platinum(II) complexes with substituted benzimidazole ligands.

    Science.gov (United States)

    Ozçelik, Azime Berna; Utku, Semra; Gümüş, Fatma; Keskin, Ayten Çelebi; Açık, Leyla; Yılmaz, Sükran; Ozgüngör, Adeviye

    2012-06-01

    In the present study, four Pt(II) complexes with 2-ethyl (1)/or benzyl (2)/or p-chlorobenzyl (3)/or 2-phenoxymethyl (4) benzimidazole carrier ligands were evaluated for their in vitro cytotoxic activities against the human HeLa cervix, oestrogen receptor-positive MCF-7 breast, and oestrogen receptor-negative MDA-MB 231 breast cancer cell lines. The plasmid DNA interactions and inhibition of the BamHI restriction enzyme activities of the complexes were also studied. Complex 3 was found to be more active than carboplatin for all examined cell lines and comparable with cisplatin, except for the HeLa cell line.

  3. Diamino-ligated platinum(II) and platinum(IV) phenoxide complexes; syntheses and crystal structures

    NARCIS (Netherlands)

    Koten, G. van; Kapteijn, G.M.; Meijer, M.D.; Grove, D.M.; Veldman, N.; Spek, A.L.

    1997-01-01

    The reaction of the diamino-ligated dimethylplatinum(II) complex [Pt(Me){2}(bpy)] (bpy=2, 2'-bipyridyl) with phenol affords the new complex [Pt(Me)(OPh)(bpy)] (1). The X-ray crystal structure of square-planar 1 is reported: orthorhombic, space group P2{1}2{1}2{1} (No. 19), a = 9.1625(12), b = 12.392

  4. DNA Interaction Studies of a New Platinum(II) Complex Containing Different Aromatic Dinitrogen Ligands.

    Science.gov (United States)

    Shahabadi, Nahid; Mohammadi, Somaye; Alizadeh, Robabeh

    2011-01-01

    A new mononuclear Pt(II) complex, [Pt(DMP)(DIP)]Cl(2).H(2)O, in which DMP is 4,4-dimethyl-2,2-bipyridine and DIP is 4,7-diphenyl-1,10-phenantroline, has been synthesized and characterized by physicochemical and spectroscopic methods. The binding interaction of this complex with calf thymus DNA (CT-DNA) was investigated using fluorimetry, spectrophotometry, circular dichroism, viscosimetry and cyclic voltametry (CV). UV-VIS spectrum showed 4 nm bathochromic shift of the absorption band at 280 nm along with significant hypochromicity for the absorption band of the complex. The intrnisic binding constant (K(b) = 2 × 10(4) M(-1)) is more in keeping with intercalators and suggests this binding mode. The viscosity measurements showed that the complex-DNA interaction can be hydrophobic and confirm intercalation. Moreover, the complex induced detectable changes in the CD spectrum of CT-DNA. The fluorescence studies revealed that the probable quenching mechanism of fluorescence of the complex by CT-DNA is static quenching. The thermodynamic parameters (ΔH > 0 and ΔS > 0) showed that main interaction with hydrogenic forces occurred that is intercalation mode. Also, CV results confirm this mode because, with increasing the CT-DNA concentration, shift to higher potential was observed.

  5. Photodynamic killing of cancer cells by a Platinum(II) complex with cyclometallating ligand

    Science.gov (United States)

    Doherty, Rachel E.; Sazanovich, Igor V.; McKenzie, Luke K.; Stasheuski, Alexander S.; Coyle, Rachel; Baggaley, Elizabeth; Bottomley, Sarah; Weinstein, Julia A.; Bryant, Helen E.

    2016-03-01

    Photodynamic therapy that uses photosensitizers which only become toxic upon light-irradiation provides a strong alternative to conventional cancer treatment due to its ability to selectively target tumour material without affecting healthy tissue. Transition metal complexes are highly promising PDT agents due to intense visible light absorption, yet the majority are toxic even without light. This study introduces a small, photostable, charge-neutral platinum-based compound, Pt(II) 2,6-dipyrido-4-methyl-benzenechloride, complex 1, as a photosensitizer, which works under visible light. Activation of the new photosensitizer at low concentrations (0.1-1 μM) by comparatively low dose of 405 nm light (3.6 J cm-2) causes significant cell death of cervical, colorectal and bladder cancer cell lines, and, importantly, a cisplatin resistant cell line EJ-R. The photo-index of the complex is 8. We demonstrate that complex 1 induces irreversible DNA single strand breaks following irradiation, and that oxygen is essential for the photoinduced action. Neither light, nor compound alone led to cell death. The key advantages of the new drug include a remarkably fast accumulation time (diffusion-controlled, minutes), and photostability. This study demonstrates a highly promising new agent for photodynamic therapy, and attracts attention to photostable metal complexes as viable alternatives to conventional chemotherapeutics, such as cisplatin.

  6. Photodynamic killing of cancer cells by a Platinum(II) complex with cyclometallating ligand.

    Science.gov (United States)

    Doherty, Rachel E; Sazanovich, Igor V; McKenzie, Luke K; Stasheuski, Alexander S; Coyle, Rachel; Baggaley, Elizabeth; Bottomley, Sarah; Weinstein, Julia A; Bryant, Helen E

    2016-03-04

    Photodynamic therapy that uses photosensitizers which only become toxic upon light-irradiation provides a strong alternative to conventional cancer treatment due to its ability to selectively target tumour material without affecting healthy tissue. Transition metal complexes are highly promising PDT agents due to intense visible light absorption, yet the majority are toxic even without light. This study introduces a small, photostable, charge-neutral platinum-based compound, Pt(II) 2,6-dipyrido-4-methyl-benzenechloride, complex 1, as a photosensitizer, which works under visible light. Activation of the new photosensitizer at low concentrations (0.1-1 μM) by comparatively low dose of 405 nm light (3.6 J cm(-2)) causes significant cell death of cervical, colorectal and bladder cancer cell lines, and, importantly, a cisplatin resistant cell line EJ-R. The photo-index of the complex is 8. We demonstrate that complex 1 induces irreversible DNA single strand breaks following irradiation, and that oxygen is essential for the photoinduced action. Neither light, nor compound alone led to cell death. The key advantages of the new drug include a remarkably fast accumulation time (diffusion-controlled, minutes), and photostability. This study demonstrates a highly promising new agent for photodynamic therapy, and attracts attention to photostable metal complexes as viable alternatives to conventional chemotherapeutics, such as cisplatin.

  7. A platinum(II) complex of liriodenine from traditional Chinese medicine (TCM): Cell cycle arrest, cell apoptosis induction and telomerase inhibition activity via G-quadruplex DNA stabilization.

    Science.gov (United States)

    Li, Yu-Lan; Qin, Qi-Pin; Liu, Yan-Cheng; Chen, Zhen-Feng; Liang, Hong

    2014-08-01

    Liriodenine (L), an antitumor active ingredient from the traditional Chinese medicine (TCM), Zanthoxylum nitidum, afforded a platinum(II) complex (1) of L, cis-[PtCl2(L)(DMSO)], which previously reported for its in vitro antitumor activity and intercalative binding with DNA. In this study, complex 1 was further discussed for its antitumor mechanism and structure-activity relationship, comparing with L and cisplatin. Towards the most sensitive BEL-7404 human hepatoma cells, complex 1 significantly induced cell cycle arrest at both G2/M phase and S phase. It suggests that double helix DNA is not the simplex intracellular target for 1. On the other hand, the BEL-7404 cells incubated with 1 and stained by Hoechst 33258 and AO/EB showed typical cell apoptosis in dose-dependent manner. The BEL-7404 cells incubated with 1 and stained by JC-1 were also characteristic for cell apoptosis on the loss of mitochondrial membrane potential. Furthermore, the G-quadruplex DNA binding property of complex 1 was also investigated by spectroscopic analyses, fluorescent indicator displacement (FID) assay and fluorescence resonance energy transfer (FRET) assay. The results indicated that 1 stabilized the human telomeric G4-HTG21 DNA better than L. The telomerase inhibition ratio of 1 ((62.50±0.03)%), which was examined by telomerase polymerase chain reaction-enzyme-linked immunosorbent assay (PCR-ELISA), was much higher than L ((21.77±0.01)%). It can be ascribed to the better G4-HTG21 DNA stabilization of 1 than L. The results suggested that the nuclei, mitochondria and telomerase via G-quadruplex DNA stabilization all should be key targets for the antitumor mechanism of 1, in which the central platinum(II) played a key role.

  8. C [bond] H activation by cationic platinum(II) complexes: ligand electronic and steric effects.

    Science.gov (United States)

    Zhong, H Annita; Labinger, Jay A; Bercaw, John E

    2002-02-20

    A series of bis(aryl)diimine-ligated methyl complexes of Pt(II) with various substituted aryl groups has been prepared. The cationic complexes [(ArN=CR [bond] CR=NAr)PtMe(L)](+)[BF(4)](-) (Ar = aryl; R = H, CH(3); L = water, trifluoroethanol) react smoothly with benzene at approximately room temperature in trifluoroethanol solvent to yield methane and the corresponding phenyl Pt(II) cations, via Pt(IV)-methyl-phenyl-hydrido intermediates. The reaction products of methyl-substituted benzenes suggest an inherent reactivity preference for aromatic over benzylic C [bond] H activation, which can however be overridden by steric effects. For the reaction of benzene with cationic Pt(II) complexes bearing 3,5-disubstituted aryl diimine ligands, the rate-determining step is C [bond] H activation, whereas for the more sterically crowded analogues with 2,6-dimethyl-substituted aryl groups, benzene coordination becomes rate-determining. This switch is manifested in distinctly different isotope scrambling and kinetic deuterium isotope effect patterns. The more electron-rich the ligand is, as assayed by the CO stretching frequency of the corresponding carbonyl cationic complex, the faster the rate of C [bond] H activation. Although at first sight this trend appears to be at odds with the common description of this class of reaction as electrophilic, the fact that the same trend is observed for the two different series of complexes, which have different rate-determining steps, suggests that this finding does not reflect the actual C [bond] H activation process, but rather reflects only the relative ease of benzene displacing a ligand to initiate the reaction; that is, the change in rates is mostly due to a ground-state effect. The stability of the aquo complex ground state in equilibrium with the solvento complex increases as the diimine ligand is made more electron-withdrawing. Several lines of evidence, including the mechanism of degenerate acetonitrile exchange for the methyl

  9. Synthesis, characterization and cytotoxic activity of novel platinum(II) iodido complexes.

    Science.gov (United States)

    Savić, Aleksandar; Filipović, Lana; Aranđelović, Sandra; Dojčinović, Biljana; Radulović, Siniša; Sabo, Tibor J; Grgurić-Šipka, Sanja

    2014-07-23

    Novel Pt(II) complexes of general formula [PtI2(L(1-3))], (C1-C3): where L(1-3) are isobutyl, n-pentyl and isopentyl esters of (S,S)-1,3-propanediamine-N,N'-di-2-(3-cyclohexyl)propanoic acid has been synthesized and characterized by elemental analysis, UV/Vis, IR, ((1)H, (13)C and HSQC, Pt) NMR spectroscopy and ESI mass spectrometry. Spectroscopic data and computational studies have shown the usual square planar coordination geometry of synthesized complexes, with coordination of ligands via nitrogen donor atoms. The cytotoxic activity of novel ligands and corresponding complexes were investigated on a palette of different cells line. Complexes C1-C3 exhibited activity comparable to cisplatin, with IC50 values (μM) ranging from 4.6 ± 0.6 to 17.2 ± 2, and showed the highest potential in HeLa, LS-174 and EA.hy.926 cells. Ligands L1-L3 exhibited two- to four-times less activity than corresponding complexes. Analysis of the mode of action in HeLa cells, by ICP-MS study, showed markedly higher intracellular accumulation and DNA binding affinity of C1-C3 versus cisplatin, after 4 h and 20 h post-treatment. Annexin-V-FITC assay, flow cytometry and fluorescence microscopy study demonstrated occurrence of cell death through both apoptotic and necrotic changes. Tested complexes, at corresponding IC50 concentrations, caused considerable "sub-G1" peak, without other substantial alterations of cell cycle, while only C1 induced higher level of phosphatidylserine externalization (11.7%), comparing to ligand L1 (4.9%) and cisplatin (8.4%). Structure-activity comparison indicated variations of C1-C3 cytotoxicity, related to the drug/ligand lipophilicity (C log P value), while intracellular platinum content and DNA platination increased on increase of length and branching of ester chain, in sequence: C1 (isobutyl) < C2 (n-pentyl) < C3 (isopentyl).

  10. Highly luminescent half-lantern cyclometalated platinum(II) complex: synthesis, structure, luminescence studies, and reactivity.

    Science.gov (United States)

    Sicilia, Violeta; Forniés, Juan; Casas, José Ma; Martín, Antonio; López, José A; Larraz, Carmen; Borja, Pilar; Ovejero, Carmen; Tordera, Daniel; Bolink, Henk

    2012-03-19

    The half-lantern compound [{Pt(bzq)(μ-C(7)H(4)NS(2)-κN,S)}(2)]·Me(2)CO (1) was obtained by reaction of equimolar amounts of potassium 2-mercaptobenzothiazolate (KC(7)H(4)NS(2)) and [Pt(bzq)(NCMe)(2)]ClO(4). The Pt(II)···Pt(II) separation in the neutral complex [{Pt(bzq)(μ-C(7)H(4)NS(2)-κN,S)}(2)] is 2.910 (2) Å, this being among the shortest observed in half-lantern divalent platinum complexes. Within the complex, the benzo[h]quinoline (bzq) groups lie in close proximity with most C···C distances being between 3.3 and 3.7 Å, which is indicative of significant π-π interactions. The reaction of 1 with halogens X(2) (X(2) = Cl(2), Br(2), or I(2)) proceeds with a two-electron oxidation to give the corresponding dihalodiplatinum(III) complexes [{Pt(bzq)(μ-C(7)H(4)NS(2)-κN,S)X}(2)] (X = Cl 2, Br 3, I 4). Their X-ray structures confirm the retention of the half-lantern structure and the coordination mode of the bzq and the bridging ligand μ-C(7)H(4)NS(2)-κN,S. The Pt-Pt distances (Pt-Pt = 2.6420(3) Å 2, 2.6435(4) Å 3, 2.6690(3) Å 4) are shorter than that in 1 because of the Pt-Pt bond formation. Time dependent-density functional theory (TD-DFT) studies performed on 1 show a formal bond order of 0 between the metal atoms, with the 6p(z) contribution diminishing the antibonding character of the highest occupied molecular orbital (HOMO) and being responsible for an attractive intermetallic interaction. A shortening of the Pt-Pt distance from 2.959 Å in the ground state S(0) to 2.760 Å in the optimized first excited state (T(1)) is consistent with an increase in the Pt-Pt bond order to 0.5. In agreement with TD-DFT calculations, the intense, structureless, red emission of 1 in the solid state and in solution can be mainly attributed to triplet metal-metal-to-ligand charge transfer ((3)MMLCT) [dσ*(Pt-Pt) → π*(bzq)] excited states. The high quantum yields of this emission measured in toluene (44%) and solid state (62%) at room temperature indicate

  11. Platinum(II Complexes with Tetradentate Schiff Bases as Ligands: Synthesis, Characterization and Detection of DNA Interaction by Differential Pulse Voltammetry

    Directory of Open Access Journals (Sweden)

    Lijun Li

    2012-01-01

    Full Text Available Five sterically hindered platinum(II complexes with tetradentate schiff bases as ligands, [Pt(L] (L= N,N′-bisalicylidene-1,2-ethylenediamine (L1, N,N′-bisalicylidene-1,2-cyclohexanediamine (L2, N,N′-bis(5-hydroxyl-salicylidene-1,2-cyclohexanediamine (L3, N,N′-bisalicylidene-1,2-diphenyl-ethylenediamine (L4 and N,N′-bis(3-tert-butyl-5-methyl-salicylidene-1,2-diphenylethylenediamine (L5 have been synthesized and characterized by IR spectroscopy and elemental analysis. The sterical hindrance of antitumor drug candidates potentially makes them less susceptible to deactivation by sulphur containing proteins and helping to overcome resistance mechanisms. The interaction of these metal complexes with fish sperm single-stranded DNA (ssDNA was studied electrochemically based on the oxidation signals of guanine and adenine. Differential pulse voltammetry was employed to monitor the DNA interaction in solution by using renewable pencil graphite electrode. The results indicate that ligands with different groups can strongly affect the interaction between [Pt(L] complexes and ssDNA due to sterical hindrances and complex [Pt(L1] has the best interaction with DNA among the five complexes.

  12. Shedding light on the photophysical properties of newly designed platinum(II) complexes by adding substituents on functionalized ligands as highly efficient OLED emitters from a theoretical viewpoint

    Energy Technology Data Exchange (ETDEWEB)

    Li, Jieqiong [Institute of Environmental and Analytical Sciences, College of Chemistry and Chemical Engineering, Henan University, Kaifeng, Henan 475004 (China); Wang, Li, E-mail: chemwangl@henu.edu.cn [Institute of Environmental and Analytical Sciences, College of Chemistry and Chemical Engineering, Henan University, Kaifeng, Henan 475004 (China); Wang, Xin [Institute of Environmental and Analytical Sciences, College of Chemistry and Chemical Engineering, Henan University, Kaifeng, Henan 475004 (China); He, Chaozheng, E-mail: hecz2013@nynu.edu.cn [College of Physics and Electronic Engineering, Nanyang Normal University, Nanyang 473061 (China); Zhang, Jinglai, E-mail: zhangjinglai@henu.edu.cn [Institute of Environmental and Analytical Sciences, College of Chemistry and Chemical Engineering, Henan University, Kaifeng, Henan 475004 (China)

    2015-08-01

    The phosphorescent properties of three synthesized and three new designed platinum(II) complexes are focused on in this work. To reveal their structure–property relationships, a density functional theory/time-dependent density functional theory (DFT/TDDFT) investigation is performed on the geometric and electronic structures, absorption and emission spectra. The electroluminescent (EL) properties are evaluated by the ionization potential (IP), electron affinity (EA), and reorganization energy (λ). Furthermore, the radiative rate constant (k{sub r}) is qualitatively elucidated by various factors including the strength of the SOC interaction between the higher-lying singlet excited states (S{sub n}) and the T{sub 1} state, the oscillator strength (f) of the S{sub n} states that can couple with the T{sub 1} state, and the energy separation between the coupled states. A combined analysis of various elements that could affect the phosphorescent efficiency is beneficial to exploring efficient triplet phosphors in OLEDs. Consequently, complexes Pt-1 and 1 would be more suitable blue-emitting phosphorescent materials with balance of EL properties and acceptable quantum yields. - Graphical abstract: Display Omitted - Highlights: • The absorption and phosphorescence spectra of Pt(II) complexes are investigated. • Their Φ{sub em}, IP, EA, and reorganization energy are compared. • Three new Pt(II) complexes are designed.

  13. Synthesis of diorganoplatinum(IV) complexes by the Ssbnd S bond cleavage with platinum(II) complexes

    Science.gov (United States)

    Niroomand Hosseini, Fatemeh; Rashidi, Mehdi; Nabavizadeh, S. Masoud

    2016-12-01

    Reaction of [PtR2(NN)] (R = Me, p-MeC6H4 or p-MeOC6H4; NN = 2,2‧-bipyridine, 4,4‧-dimethyl-2,2‧-bipyridine, 1,10-phenanthroline or 2,9-dimethyl-1,10-phenanthroline) with MeSSMe gives the platinum(IV) complexes cis,trans-[PtR2(SMe)2(NN)]. They are characterized by NMR spectroscopy and elemental analysis. The geometries and the nature of the frontier molecular orbitals of Pt(IV) complexes containing Ptsbnd S bonds are studied by means of the density functional theory.

  14. DNA studies of newly synthesized heteroleptic platinum(II) complexes [Pt(bpy)(iip)](2+) and [Pt(bpy)(miip)](2.).

    Science.gov (United States)

    Coban, Burak; Tekin, Ishak Ozel; Sengul, Abdurrahman; Yildiz, Ufuk; Kocak, Izzet; Sevinc, Nergis

    2016-04-01

    Two new mono-nuclear heteroleptic platinum(II) complexes, [Pt(bpy)(iip)](PF6)2 (1) and [Pt(bpy)(miip)](PF6)2·2H2O (2) (bpy is 2,2'-bipyridine; iip is 2-(imidazo-4-yl)-1H-imidazo[4,5-f] [1,10] phenanthroline; miip is 2-(1-methylimidazo-2-yl)-1H-imidazo[4,5-f] [1, 10] phenanthroline), have been synthesized and fully characterized by CHN analysis, electrospray ionization and MALDI-TOF mass spectrometry, (1)H NMR, FT-IR (ATR), and UV-Vis spectrophotometer. Cytotoxicity, ability to inhibit DNA transcription and DNAse activity of the complexes were studied. The DNA-binding behaviors of both complexes have also been studied by spectroscopic methods, cyclic voltammetry and viscosity measurements. Both complexes showed cytotoxic properties and 2 was more cytotoxic than 1. DNA transcription was inhibited upon increasing concentrations of both complexes. The complex 2 was found to be a better inhibitor than 1. The same pattern can be seen in the DNAse profile of the complexes. In addition, 2 was found to promote cleavage of pBR322 DNA at a lower concentration than 1. The spectroscopic, electrochemical and viscometric results indicate that both complexes show some degree of binding to DNA in an intercalative mode, resulting in intrinsic binding constants K b = 3.55 ± 0.6 × 10(4) M(-1) and 7.01 ± 0.9 × 10(4) M(-1) for 1 and 2, respectively. The difference in the DNA-binding affinities of 1 and 2 may presumably be explained by the methylated imidazole nitrogen atom that makes the compound more hydrophobic and gives better intercalative binding ability to DNA's hydrophobic environment.

  15. Selective turn-off phosphorescent and colorimetric detection of mercury(II) in water by half-lantern platinum(II) complexes.

    Science.gov (United States)

    Sicilia, Violeta; Borja, Pilar; Baya, Miguel; Casas, José M

    2015-04-21

    The platinum(ii) half-lantern dinuclear complexes [{Pt(bzq)(μ-C7H4NS2-κN,S)}2] () and [{Pt(bzq)(μ-C7H4NOS-κN,S)}2] () [bzq = benzo[h]quinolinate, C7H4NS2 = 2-mercaptobenzothiazolate, C7H4NOS = 2-mercaptobenzoxazolate] in solution of DMSO-H2O undergo a dramatic color change from yellowish-orange to purple and turn-off phosphorescence in the presence of a small amount of Hg(2+), being discernible by the naked-eye and by spectroscopic methods. Other metal ions as Ag(+), Li(+), Na(+), K(+), Ca(2+), Mg(2+), Ba(2+), Pb(2+), Cd(2+), Zn(2+) and Tl(+) were tested and, even in a big excess, showed no interference in the selective detection of Hg(2+) in water. Job's plot analysis indicated a 1 : 1 stoichiometry in the complexation mode of Hg(2+) by /. The phosphorescence quenching attributed to the formation of [/ : Hg(2+)] complexes showed binding constants of K = 1.13 × 10(5) M(-1) () and K = 1.99 × 10(4) M(-1) (). The limit of detection has been also evaluated. In addition, dried paper test strips impregnated in DMSO solutions of and can detect concentration of Hg(2+) in water as low as 1 × 10(-5) M for and 5 × 10(-5) M for , making these complexes good candidates to be used as real-time Hg(2+) detectors. The nature of the interaction of the Pt2 half-lantern complex with the Hg(2+) cation, has been investigated by theoretical calculations.

  16. bis-Nitrile and bis-Dialkylcyanamide Platinum(II) Complexes as Efficient Catalysts for Hydrosilylation Cross-Linking of Siloxane Polymers.

    Science.gov (United States)

    Islamova, Regina M; Dobrynin, Mikhail V; Ivanov, Daniil M; Vlasov, Andrey V; Kaganova, Elena V; Grigoryan, Galina V; Kukushkin, Vadim Yu

    2016-03-05

    cis- and trans-Isomers of the platinum(II) nitrile complexes [PtCl2(NCR)2] (R = NMe2, N(C₅H10), Ph, CH2Ph) were examined as catalysts for hydrosilylation cross-linking of vinyl-terminated polydimethylsiloxane and trimethylsilyl-terminated poly(dimethylsiloxane-co-ethylhydrosiloxane) producing high quality silicone rubbers. Among the tested platinum species the cis-complexes are much more active catalysts than their trans-congeners and for all studied platinum complexes cis-[PtCl2(NCCH2Ph)2] exhibits the best catalytic activity (room temperature, c = 1.0 × 10(-4) mol/L, τpot-life 60 min, τcuring 6 h). Although cis-[PtCl₂(NCCH2Ph)2] is less active than the widely used Karstedt's catalyst, its application for the cross-linking can be performed not only at room temperature (c = 1.0 × 10(-4) mol/L), but also, more efficiently, at 80 °C (c = 1.0 × 10(-4)-1.0 × 10(-5) mol/L) and it prevents adherence of the formed silicone rubbers to equipment. The usage of the cis- and trans-[PtCl2(NCR)2] complexes as the hydrosilylation catalysts do not require any inhibitors and, moreover, the complexes and their mixtures with vinyl- and trimethylsilyl terminated polysiloxanes are shelf-stable in air. Tested catalysts do not form colloid platinum particles after the cross-linking.

  17. Synthesis, Characterization, and Interaction with Biomolecules of Platinum(II Complexes with Shikimic Acid-Based Ligands

    Directory of Open Access Journals (Sweden)

    Yan Peng

    2013-01-01

    Full Text Available Starting from the active ingredient shikimic acid (SA of traditional Chinese medicine and NH2(CH2nOH, (n=2–6, we have synthesized a series of new water-soluble Pt(II complexes PtLa–eCl2, where La–e are chelating diamine ligands with carbon chain covalently attached to SA (La–e = SA-NH(CH2nNHCH2CH2NH2; La, n=2; Lb, n=3; Lc, n=4; Ld, n=5; Le, n=6. The results of the elemental analysis, LC-MS, capillary electrophoresis, and 1H, 13C NMR indicated that there was only one product (isomer formed under the present experimental conditions, in which the coordinate mode of PtLa–eCl2 was two-amine bidentate. Their in vitro cytotoxic activities were evaluated by MTT method, where these compounds only exhibited low cytotoxicity towards BEL7404, which should correlate their low lipophilicity. The interactions of the five Pt(II complexes with DNA were investigated by agarose gel electrophoresis, which suggests that the Pt(II complexes could induce DNA alteration. We also studied the interactions of the Pt(II complexes with 5′-GMP with ESI-MS and 1H NMR and found that PtLbCl2, PtLcCl2, and PtLdCl2 could react with 5′-GMP to form mono-GMP and bis-GMP adducts. Furthermore, the cell-cycle analysis revealed that PtLbCl2, PtLcCl2 cause cell G2-phase arrest after incubation for 72 h. Overall, these water-soluble Pt(II complexes interact with DNA mainly through covalent binding, which blocks the DNA synthesis and replication and thus induces cytotoxicity that weakens as the length of carbon chain increases.

  18. Synthesis and characterization of electron donor-acceptor platinum(II) complexes composed of N,N-diphenylpyridineamine and triphenylamine ligands.

    Science.gov (United States)

    Dai, Zhi; Metta-Magaña, Alejandro J; Nuñez, Jose E

    2014-07-21

    The synthesis and electronic properties of a series of platinum(II) complexes composed of electron-donor and electron-acceptor components as potential photovoltaic materials is reported. The complexes are composed of triphenylamines (TPA) and pyridine-derivatized TPAs as the electron-donating components, and alkynyl derivatives of 2,1,3-benzothiadiazole and cyclopentadithiophenone as the electron acceptors. The complexes containing the pyridine-derivatized ligands were prepared to examine the effect that direct coordination of a heteroatom-modified TPA may have on the electronic properties of donor-acceptor (D-A) complexes. Four complexes composed of meta- and para- pyridine-derivatized TPAs were prepared, and their electronic properties were compared with three structurally similar complexes composed of TPA, as well as with purely organic D-A compounds. Data collected from UV-vis and cyclic voltammetry show minor differences on the properties of the complexes containing the pyridine-derivatized ligands when compared to the TPA analogs, exhibiting similar highest occupied molecular orbital-lowest unoccupied molecular orbital bandgaps ranging from 2.156 to 2.705 eV for the pyridine-derivatized complexes (6a,b and 7a,b), 2.038-2.320 eV for the TPA complexes (8a,b and 9a), 2.301 eV for organic molecule 10a, and 1.997 eV for 10b. All compounds are stable, exhibiting no decomposition in the solid indefinitely, and only minor decomposition in solution. All compounds were characterized by (1)H and (13)C nuclear magnetic resonance, infrared spectroscopy, and electrospray mass spectrometry. All complexes were also characterized by (31)P nuclear magnetic resonance and elemental analysis of CHN; determination of Ag content for 6a,b and 7a,b (carried through the synthetic steps) was determined by inductively coupled plasma optical emission spectrometry. The para-pyridine-derivatized complex of 2,1,3-benzothiadiazole (6a) was further characterized by X-ray crystallography as a

  19. Substituted 4,4′-stilbenoid NCN-pincer platinum(II) complexes : luminescence and tuning of the electronic and NLO properties and the application in an OLED

    NARCIS (Netherlands)

    Batema, G.D.; Lutz, M.; van Walree, C.A.; de Mello Donega, C.; Meijerink, A.; Havenith, R.W.A.; Pérez-Moreno, J.; Clays, K.; Büchel, M.; van Dijken, A.; Bryce, D.L.; van Klink, G.P.M.; van Koten, G.

    2008-01-01

    A series of 4,4′-disubstituted organic−organometallic stilbenes, i.e., the 4′-substituted stilbenoid-NCN-pincer platinum(II) complexes [PtCl(NCN-R-4)] (NCN-R-4 = [C6H2(CH2NMe2)2-2,6-R-4]− in which R = C2H2C6H4-R′-4′ with R′ = NPh2, NMe2, OMe, SiMe3 H, I, CN, NO2) (1−8), were studied for their

  20. Substituted 4,4′-stilbenoid NCN-pincer platinum(II) complexes : luminescence and tuning of the electronic and NLO properties and the application in an OLED

    NARCIS (Netherlands)

    Batema, G.D.; Lutz, M.; van Walree, C.A.; de Mello Donega, C.; Meijerink, A.; Havenith, R.W.A.; Pérez-Moreno, J.; Clays, K.; Büchel, M.; van Dijken, A.; Bryce, D.L.; van Klink, G.P.M.; van Koten, G.

    2008-01-01

    A series of 4,4′-disubstituted organic−organometallic stilbenes, i.e., the 4′-substituted stilbenoid-NCN-pincer platinum(II) complexes [PtCl(NCN-R-4)] (NCN-R-4 = [C6H2(CH2NMe2)2-2,6-R-4]− in which R = C2H2C6H4-R′-4′ with R′ = NPh2, NMe2, OMe, SiMe3 H, I, CN, NO2) (1−8), were studied for their electr

  1. The conformation effect of the diamine bridge on the stability of dinuclear platinum(II) complexes and their hydrolysis.

    Science.gov (United States)

    Esteves, Lucas F; Dos Santos, Hélio F; Costa, Luiz Antônio S

    2015-09-01

    In this paper, the hydrolysis process of a bisplatinum complex containing the flexible chain 1,6-hexanediamine between the two metal centers was investigated through the use of density functional theory (DFT) with the analysis of the role of the spacing group arrangement on the values of free energy activation barrier. All structures were fully optimized in aqueous solution using implicit model for solvent at DFT level. The energy profiles for the hydrolysis reaction were determined by using the supermolecule approach. Five transition states were proposed differing by the conformation of the bridge group, and the activation free energy calculated as a weighted average within the selected forms. The Gibbs population for reactant was used as a statistical weight leading to the predicted value of 23.1kcalmol(-1), in good accordance with experiment, 23.8kcalmol(-1). Our results suggests that for 1,6-hexanediamine bridge ligand, the extend forms with average torsional angle over the carbon chain larger than 130° have the greatest contribution to the hydrolysis kinetics. The results presented here point out that the hydrolysis mechanism might follow different paths for each conformation and each of these contributes to the observed energy barrier.

  2. Synthesis, structural, spectral, thermal and antimicrobial studies of palladium(II), platinum(II), ruthenium(III) and iridium(III) complexes derived from N,N,N,N-tetradentate macrocyclic ligand.

    Science.gov (United States)

    Rani, Soni; Kumar, Sumit; Chandra, Sulekh

    2011-05-01

    Palladium(II), platinum(II), ruthenium(III) and iridium(III) complexes of general stoichiometry [PdL]Cl(2), [PtL]Cl(2), [Ru(L)Cl(2)]Cl and [Ir(L)Cl(2)]Cl are synthesized with a tetradentate macrocyclic ligand, derived from 2,6-diaminopyridine with 3-ethyl 2,4-pentanedione. Ligand was characterized on the basis of elemental analyses, IR, mass, and (1)H NMR and (13)C NMR spectral studies. All the complexes were characterized by elemental analyses, molar conductance measurements, magnetic susceptibility measurements, IR, mass, electronic spectral techniques and thermal studies. The value of magnetic moments indicates that all the complexes are diamagnetic except Ru(III) complex which shows magnetic moments corresponding its one unpaired electron. The macrocyclic ligand and all its metal complexes were also evaluated in vitro against some plant pathogenic fungi and bacteria to assess their biocidal properties.

  3. In vitro and in vivo anti-tumor effects of selected platinum(IV) and dinuclear platinum(II) complexes against lung cancer cells.

    Science.gov (United States)

    Arsenijevic, Milos; Milovanovic, Marija; Jovanovic, Snezana; Arsenijevic, Natalija; Markovic, Bojana Simovic; Gazdic, Marina; Volarevic, Vladislav

    2017-08-01

    In the present study, cytotoxic effects of cisplatin, the most usually used chemotherapeutic agent, were compared with new designed platinum(IV) ([PtCl4(en)] (en = ethylenediamine) and [PtCl4(dach)]) (dach = (±)-trans-1,2-diaminocyclohexane) and platinum(II) complexes ([{trans-Pt(NH3)2Cl}2(μ-pyrazine)](ClO4)2 (Pt1), [{trans-Pt(NH3)2Cl}2(μ-4,4'-bipyridyl)](ClO4)2DMF(Pt2),[{trans-Pt(NH3)2Cl}2(μ-1,2-bis(4pyridyl)ethane)](ClO4)2 (Pt3)), in vitro and in vivo against human and murine lung cancer cells, to determine anti-tumor potential of newly synthesized platinum-based drugs in the therapy of lung cancer. Results obtained by MTT [3-(4,5-dimethylthiazol-2-yl)-2,5-diphenyltetrazolium bromide], Lactate dehydrogenase and Annexin V/Propidium Iodide assays showed that, among all tested complexes, [PtCl4(en)] had the highest cytotoxicity against human and murine lung carcinoma cells in vitro. [PtCl4(en)] showed significantly higher cytotoxicity then cisplatin in all tested concentrations, mainly by inducing apoptosis in lung cancer cells. [PtCl4(en)] was well tolerated in vivo. Clinical signs of [PtCl4(en)]-induced toxicity, such as changes in food, water consumption or body weight, nephrotoxicity or hepatotoxicity was not observed in [PtCl4(en)]-treated mice. [PtCl4(en)] managed to increase presence of CD45+ leukocytes, including F4/80+ macrophages, CD11c+ dendritic cells, CD4+ helper and CD8+ cytotoxic T cells (CTLs) in the lungs, cytotoxic NK, NKT and CTLs in the spleens of tumor bearing mice, resulting with reduction of metastatic lesions in the lungs, indicating its potential to stimulate anti-tumor immune response in vivo. Due to its anti-tumor cytotoxicity, biocompatibility, and potential for stimulation of anti-tumor immune response, [PtCl4(en)] may be a good candidate for further testing in the field of medicinal chemistry.

  4. Identification of a (H2O)8 cluster in a supramolecular host of a charge transfer platinum(II) complex

    Indian Academy of Sciences (India)

    Sutanuva Mandal; Ipsita Chatterjee; Alfonso Castiñeirs; Sreebrata Goswami

    2014-09-01

    The chemical reaction of PtII(L1)Cl2 [L1 = 2-(phenylazo)pyridine] with a bidentate N,S-donor atom ligand, 2-phenylthioaniline, (HL2) in alkaline acetonitrile yielded a mixed ligand donor acceptor complex, [PtII(L1)(L2)−]Cl, [1]Cl. The complex has been characterized by using a host of physical methods: X-ray crystallography, nuclear magnetic resonance, cyclic voltammetry, absorption spectroscopy, electron paramagnetic resonance. The complex showed intense interligand charge transfer (ILCT) transition in the long wavelength region of UV-vis spectrum at 785 nm. The single-crystal X-ray structure of complex, [1]Cl·2.6H2O is reported. The cationic complex upon crystallization from aqueous methanol solvent produces an assembly of three dimensional (H2O)8 guest moiety within the host lattice of reference Pt-complex. The water assembly showed a unique type of aggregation of two trigonal pyramids hydrogen bonded with three chloride anions. The complex displayed two reversible responses at −0.34 and −1.05 V along with one irreversible anodic response at 0.91 V versus Ag/AgCl reference electrode. The redox processes are characterized by examination of EPR spectra of the electrogenerated complexes.

  5. Mechanistic studies on the reactions of platinum(II) complexes with nitrogen- and sulfur-donor biomolecules.

    Science.gov (United States)

    Bugarčić, Živadin D; Bogojeski, Jovana; Petrović, Biljana; Hochreuther, Stephanie; van Eldik, Rudi

    2012-10-28

    A brief overview of mechanistic studies on the reactions of different Pt(II) complexes with nitrogen- and sulfur-donor biomolecules is presented. The first part describes the results obtained for substitution reactions of mono-functional Pt(II) complexes with different biomolecules, under various experimental conditions (temperature, pH and ionic strength). In addition, an overview of the results obtained for the substitution reactions of bi-functional Pt(II) complexes, analogous to cisplatin, with biomolecules is given. The last part of this report deals with different polynuclear Pt(II) complexes and their substitution behaviour with different biomolecules. The purpose of this perspective is to improve the understanding of the mechanism of action of Pt(II) complexes as potential anti-tumour drugs in the human body.

  6. DNA interaction studies of a platinum(II) complex containing L-histidine and 1,10-phenanthroline ligands.

    Science.gov (United States)

    Shahabadi, Nahid; Nemati, Leila

    2012-05-01

    The aim of this study was developing coordination complexes that can be used as inorganic medicinal agents. The water soluble [Pt(phen)(His)]NO(3)·3H(2)O complex in which phen=1,10-phenantheroline and His=L-histidine was synthesized and characterized using physicochemical methods. Binding interaction of this complex with calf thymus (CT) DNA was investigated by emission, absorption, circular dichroism, and viscosity measurement techniques. Upon addition of CT-DNA, changes were observed in the characteristic ultraviolet-visible (UV-Vis) bands (hypochromism) of the complex. The complex binds to CT-DNA in an intercalative mode. The calculated binding constant, K(b), was 8 ± 0.2 × 10(4) M(-1). In addition, circular dichroism (CD) study showed that the phenanthroline ligand was inserted between the base pair stack of the double-helical structure of DNA. Also, the fluorescence spectral characteristics showed an increase in fluorescence intensity of the platinum complex in the presence of increasing amounts of DNA solution. The experimental results showed that the platinum complex binds to DNA via intercalative and hydrogen bonding mode.

  7. Preparation and Biological Evaluation of Two Novel Platinum(II Complexes Based on the Ligands of Dipicolyamine Bisphosphonate Esters

    Directory of Open Access Journals (Sweden)

    Ling Qiu

    2016-02-01

    Full Text Available Two new platinum(II-based complexes bearing a bone-targeting group were synthesized and characterized. They both have excellent affinity for hydroxyapatite (HA, which is abundant in human bone tissues. Their antitumor activities against five human cancer cell lines (U2OS, A549, HCT116, MDA-MB-231 and HepG2 were evaluated and compared with cisplatin (CDDP. Though the antitumor efficacies of new complexes are lower than that of CDDP, they show higher selectivity against the HepG2 hepatoma cell line than the L02 normal liver cell line. Morphology studies exhibited typical characteristics of cell apoptosis and the cell cycle distribution analysis indicated that the complexes can inhibit cancer cells by inducing cell cycle arrest at the G2/M phase, a similar mechanism of action to CDDP.

  8. Comparative Studies with Zwitterionic Platinum(II) Bis(pyrazolyl)borate and 2,2‘-Bipyridylborate Complexes

    OpenAIRE

    Thomas, Christine M.; Peters, Jonas C.

    2005-01-01

    A comparison between the mononuclear platinum complexes of three structurally different monoanionic borato ligands is presented:  [Ph_2B(pyrazolyl)_2]- ([Ph_2B(pz)_2], 1), [4-Ph_3B(2,2‘-bipyridine)]- ([(4-BPh_3)bpy], 2), and [Ph_2B(CH_2PPh_2)_2]- ([Ph_2BP_2], 3). The new bipyridylborate ligand 2 is introduced in this study. The relative trans influence of these ligands has been assessed by comparison of the structural and spectroscopic (NMR) data of the platinum dimethyl complexes [[Ph_2B(pz)...

  9. Palladium(II) and platinum(II) complexes containing benzimidazole ligands: Molecular structures, vibrational frequencies and cytotoxicity

    Science.gov (United States)

    Abdel Ghani, Nour T.; Mansour, Ahmed M.

    2011-04-01

    (1H-benzimidazol-2-ylmethyl)-(4-methoxyl-phenyl)-amine (L 1), (1H-benzimidazol-2-ylmethyl)-(4-methyl-phenyl)-amine (L 2) and their Pd(II) and Pt(II) complexes have been synthesized as potential anticancer compounds and their structures were elucidated using a variety of physico-chemical techniques. Theoretical calculations invoking geometry optimization, vibrational assignments, 1H NMR, charge distribution and molecular orbital description HOMO and LUMO were done using density functional theory. Natural bond orbital analysis (NBO) method was performed to provide details about the type of hybridization and the nature of bonding in the studied complexes. Strong coordination bonds (LP(1)N11 → σ *(M sbnd Cl22)) and (LP(1)N21 → σ *(M sbnd Cl23)) (M = Pd or Pt) result from donation of electron density from a lone pair orbital on the nitrogen atoms to the acceptor metal molecular orbitals. The experimental results and the calculated molecular parameters revealed square-planar geometries around the metallic centre through the pyridine-type nitrogen of the benzimidazole ring and secondary amino group and two chlorine atoms. The activation thermodynamic parameters were calculated using non-isothermal methods. The synthesized ligands, in comparison to their metal complexes were screened for their antibacterial activity. In addition, the studied complexes showed activity against three cell lines of different origin, breast cancer (MCF-7), Colon Carcinoma (HCT) and human heptacellular carcinoma (Hep-G2) comparable to cis-platin.

  10. Tunable and Efficient White Light Phosphorescent Emission Based on Single Component N-Heterocyclic Carbene Platinum(II) Complexes.

    Science.gov (United States)

    Bachmann, Michael; Suter, Dominik; Blacque, Olivier; Venkatesan, Koushik

    2016-05-16

    A new class of cyclometalated pyridine N-heterocyclic carbene (NHC) Pt(II) complexes with electronically different alkyne derivatives (C≡CR; R = C6H4C(CH3)3 (1), C6H5 (2), C6H4F (3), C6H3(CF3)2 (4)) as ancillary ligands were synthesized, and the consequences of the electronic properties of the different substituted phenylacetylene ligands on the phosphorescent emission efficiencies were studied, where C≡CC6H4C(CH3)3 = 4-tert-butylphenylacetylene, C≡CC6H5 = phenylacetylene, C≡CC6H4F = 4-fluorophenylacetylene, and C≡CC6H3(CF3)2 = 3,5-bis(trifluoromethyl)phenylacetylene. Structural characterization, electrochemistry, and photophysical investigations were performed for all four compounds. Moreover, the emission quantum efficiencies and wavelength emission intensities of the complexes were also recorded in different weight percents in poly(methyl methacrylate) films (PMMA) and evaluated in the CIE-1931 chromaticity diagram. The square planar coordination geometry with the alkynyl ligands was corroborated for complexes 1, 2, and 3 by single crystal X-ray diffraction studies. These complexes show tunable monomeric high energy triplet emission and an additional concentration-dependent low-energy excimer-based phosphorescence. While adopting weight percent concentrations between 15 and 25%, the two emission bands covering the entire visible spectrum were obtained with these particular complexes displaying the properties of an efficient white light triplet emitter with excellent CIE-1931 coordinates (0.31, 0.33). On the basis of the high luminescent quantum efficiency of over 50% for white light emission, these compounds could be potentially useful for white organic light-emitting diodes (WOLEDs) based applications.

  11. Activity of phosphino palladium(II) and platinum(II) complexes against HIV-1 and Mycobacterium tuberculosis.

    Science.gov (United States)

    Gama, Ntombenhle H; Elkhadir, Afag Y F; Gordhan, Bhavna G; Kana, Bavesh D; Darkwa, James; Meyer, Debra

    2016-08-01

    Treatment of human immunodeficiency virus (HIV) is currently complicated by increased prevalence of co-infection with Mycobacterium tuberculosis. The development of drug candidates that offer the simultaneous management of HIV and tuberculosis (TB) would be of great benefit in the holistic treatment of HIV/AIDS, especially in sub-Saharan Africa which has the highest global prevalence of HIV-TB coinfection. Bis(diphenylphosphino)-2-pyridylpalladium(II) chloride (1), bis(diphenylphosphino)-2-pyridylplatinum(II) chloride (2), bis(diphenylphosphino)-2-ethylpyridylpalladium(II) chloride (3) and bis(diphenylphosphino)-2-ethylpyridylplatinum(II) (4) were investigated for the inhibition of HIV-1 through interactions with the viral protease. The complexes were subsequently assessed for biological potency against Mycobacterium tuberculosis H37Rv by determining the minimal inhibitory concentration (MIC) using broth microdilution. Complex (3) showed the most significant and competitive inhibition of HIV-1 protease (p = 0.014 at 100 µM). Further studies on its in vitro effects on whole virus showed reduced viral infectivity by over 80 % at 63 µM (p < 0.05). In addition, the complex inhibited the growth of Mycobacterium tuberculosis at an MIC of 5 µM and was non-toxic to host cells at all active concentrations (assessed by tetrazolium dye and real time cell electronic sensing). In vitro evidence is provided here for the possibility of utilizing a single metal-based compound for the treatment of HIV/AIDS and TB.

  12. Cytotoxicity of platinum(IV) and platinum(II) complexes containing 1R,2R-cyclohexanediamine as a ligand.

    Science.gov (United States)

    Yamashita, T; Hirose, J; Noji, M; Saito, R; Tomida, H; Kidani, Y

    1993-10-01

    Several Pt(IV) and Pt(II) complexes containing 1R,2R-cyclohexanediamine (1R,2R-dach) as a carrier ligand were synthesized. The cytotoxicities and the uptake of the platinum complexes by leukemia L1210 cells were compared in order to study the correlation between their structures and cytotoxicities. [Pt(II)Cl2(1R,2R-dach)], [(Pt(II)(oxalato)(1R,2R-dach)], and [Pt(II)(malonato)(1R,2R-dach)], which have excellent anticancer properties, exhibited very high cytotoxicities and were easily taken up by leukemia L1210 cells. [Pt(IV)Cl4(1R,2R-dach)], trans(Cl)-[Pt(IV)Cl2(oxalato)(1R,2R-dach)], and trans(Cl)-[Pt(IV)Cl2(malonato)(1R,2R-dach)] also had high cytotoxicities. After a short incubation time, the uptake of [Pt(II)Cl2(1R,2R-dach)], [Pt(II)(oxalato)(1R,2R-dach)], and [Pt(II)(malonato)(1R,2R-dach)] by leukemia L1210 cells were respectively very similar to those of [Pt(IV)Cl4(1R,2R-dach)], trans(Cl)-[Pt(IV)Cl2(oxalato)(1R,2R-dach)], and trans(Cl)-[Pt(IV)Cl2(malonato)(1R,2R-dach)]. In addition, trans(OH)-[Pt(IV)(OH)2Y2(1R,2R-dach)] (Y2: oxalato or malonato) did not exhibit cytotoxicity towards leukemia L1210 cells, whereas trans(Cl)-[Pt(IV)Cl2Y2(1R,2R-dach)] (Y2: oxalato or malonato) were highly cytotoxic. The accumulation of trans(OH)-[Pt(IV)(OH)2Y2(1R,2R-dach)] in leukemia L1210 cells was much lower than that of trans(Cl)-[Pt(IV)Cl2Y2(1R,2R-dach)]. Platinum(IV) complexes, in which leaving groups are replaced by hydroxide groups, have decreased cytotoxic activity, because the hydroxide groups of the platinum(IV) complex reduce the uptake of platinum by the cells. trans(OH),cis(Cl)-[Pt(IV)(OH)2Cl2(1R,2R-dach)], which has hydroxide and chloride groups, was easily incorporated into the cells and exhibited the high cytotoxic activity. This behavior indicates that the chloride group apparently overcomes the ameliorating effect of the hydroxide group.

  13. Blue-emitting platinum(II) complexes bearing both pyridylpyrazolate chelate and bridging pyrazolate ligands: synthesis, structures, and photophysical properties.

    Science.gov (United States)

    Chang, Sheng-Yuan; Chen, Jing-Lin; Chi, Yun; Cheng, Yi-Ming; Lee, Gene-Hsiang; Jiang, Chang-Ming; Chou, Pi-Tai

    2007-12-24

    A new Pt(II) dichloride complex [Pt(fppzH)Cl2] (1), in which fppzH = 3-(trifluoromethyl)-5-(2-pyridyl)pyrazole, was prepared by the treatment of a pyridylpyrazole chelate fppzH with K2PtCl4 in aqueous HCl solution. Complex 1 could further react with its parent pyrazole (pzH), 3,5-dimethylpyrazole (dmpzH), or 3,5-di-tert-butylpyrazole (dbpzH) to afford the monometallic [Pt(fppz)(pzH)Cl] (2), [Pt(fppz)(dmpzH)Cl] (3), [Pt(fppz)(dmpzH)2]Cl (4), or two structural isomers with formula [Pt(fppz)(dbpzH)Cl] (5a,b). Single-crystal X-ray diffraction studies of 2, 4, and 5a,b revealed a square planar Pt(II) framework, among which a strong interligand hydrogen bonding occurred between fppz and pzH ligands in 2. This interligand H-bonding is replaced by dual N-H...Cl interaction in 4 and both intermolecular N-H...O (with THF solvate) and N-H...Cl interaction in 5a,b, respectively; the latter are attributed to the bulky tert-butyl substituents that force the dbpzH ligand to adopt the perpendicular arrangement. Furthermore, complex 2 underwent rapid deprotonation in basic media to afford two isomeric complexes with formula [Pt(fppz)(mu-pz)]2 (6a,b), which are related to each other according to the spatial orientation of the fppz chelates, i.e., trans- and cis-isomerism. Similar reaction exerted on 3 afforded isomers 7a,b. Both 6a,b (7a,b) are essentially nonemissive in room-temperature fluid state but afford strong blue phosphorescence in solid state prepared via either vacuum-deposited thin film or 77 K CH2Cl2 matrix. As also supported by the computational approaches, the nature of emission has been assigned to be ligand-centered triplet pipi* mixed with certain metal-to-ligand charge-transfer character.

  14. Antitumor activity of platinum(II) complexes with histamine and radioiodinated histamine in a transplantable murine adenocarcinoma model

    Energy Technology Data Exchange (ETDEWEB)

    Garnuszek, Piotr [Department of Radiopharmaceuticals, National Medicines Institute, 00-725 Warsaw (Poland)], E-mail: pgarnuszek@il.waw.pl; Karczmarczyk, Urszula; Maurin, Michal [Department of Radiopharmaceuticals, National Medicines Institute, 00-725 Warsaw (Poland)

    2008-07-15

    Purpose: Antitumor activity of the dichloroplatinum(II)-histamine complexes labeled with I-125 or I-131 was investigated in a transplantable murine adenocarcinoma (MA) model. Methods: The tumor model was obtained in C3H/W female mice after subcutaneous inoculation of the tumor cells derived from the mice bearing a mammary tumor of spontaneous origin. Antitumor activities of the platinum-histamine complexes were investigated in three independent experiments, which differed in applied doses of preparations (PtCl{sub 2}Hist, PtCl{sub 2}[{sup 125}I]Hist, PtCl{sub 2}[{sup 131}I]Hist, PtCl{sub 2}Hist/PtCl{sub 2}[{sup 125}I]Hist and PtCl{sub 2}Hist/PtCl{sub 2}[{sup 131}I]Hist), treatment schedules as well as stages of the disease progress in the animals used. Experiment 1 included long-term, multidose treatment with low single doses (treatment duration 31-32 days; 8-10 doses of ca. 0.25{center_dot}MTD{sub Pt} each). Experiment 2 included short-term, multidose treatment with higher single doses (4xca. 0.5{center_dot}MTD{sub Pt} up to Day 13 of the treatment). Experiment 3 included long-term concomitant multidose treatment with higher single doses (9x0.9-0.4{center_dot}MTD{sub Pt} up to Day 33). Results: The long-term treatment with the platinum-histamine preparations revealed inhibiting activity on the tumor growth and size in comparison to control groups. The most intensive and significant antitumor effects were observed for the radioactive complexes. The tumor growth delay factors (GDFs) observed in Experiment 1 were 0.4, 0.7, and 1.2 for PtCl{sub 2}Hist, PtCl{sub 2}Hist/PtCl{sub 2}[{sup 131}I]Hist, and PtCl{sub 2}Hist/PtCl{sub 2}[{sup 125}I]Hist, respectively. Significant (P<.05) prolongations of median survivals (MS) were found in Experiment 2 following the treatment with higher single doses of PtCl{sub 2}Hist and PtCl{sub 2}His/PtCl{sub 2}[{sup 125}I]Hist (Ratio MS{sub tr}/MS{sub con} ca. 1.4). A slightly less potent activity was observed for PtCl{sub 2}Hist

  15. Studying the interactions of a platinum(II) 9-aminoacridine complex with proteins and oligonucleotides by ESI-TOF MS.

    Science.gov (United States)

    Samper, Katia G; Vicente, Consuelo; Rodríguez, Venancio; Atrian, Sílvia; Cutillas, Natalia; Capdevila, Mercè; Ruiz, José; Palacios, Òscar

    2012-01-07

    The interaction of a novel Pt complex, [Pt(dmba)(N9-9AA)(PPh(3))](+)1 (dmba = N,N-dimethylbenzylamine-κN,κC; 9AA = 9-aminoacridine), which exhibits anti-tumor activity, with certain key proteins has been monitored by ESI-MS. Also, the interaction of 1 with a designed double-stranded oligonucleotide containing the GG motif has been followed by mass spectrometry as well as by fluorimetry. The results obtained show the low interaction of 1 with the considered proteins and the absence of covalent interaction with the oligonucleotides, but the fluorimetric data confirm the π-π interaction of 1 with the double-stranded DNA, which is probably the reason of the previously reported activity of 1 in several tumor cell lines.

  16. Computational studies on the photophysical properties and NMR fluxionality of dinuclear platinum(II) A-frame alkynyl diphosphine complexes.

    Science.gov (United States)

    Lam, Wai Han; Yam, Vivian Wing-Wah

    2010-12-06

    The structural geometry, electronic structure, photophysical properties, and the fluxional behavior of a series of A-frame diplatinum alkynyl complexes, [Pt(2)(μ-dppm)(2)(μ-C≡CR)(C≡CR)(2)](+) [R = (t)Bu (1), C(6)H(5) (2), C(6)H(4)Ph-p (3), C(6)H(4)Et-p (4), C(6)H(4)OMe-p (5); dppm = bis(diphenylphosphino)methane], have been studied by density functional theory (DFT) and time-dependent TD-DFT associated with conductor-like polarizable continuum model (CPCM) calculations. The results show that the Pt···Pt distance strongly depends on the binding mode of the alkynyl ligands. A significantly shorter Pt···Pt distance is found in the symmetrical form, in which the bridging alkynyl ligand is σ-bound to the two metal centers, than in the unsymmetrical form where the alkynyl ligand is σ-bound to one metal and π-bound to another. For the two structural forms in 1-5, both the highest occupied molecular orbital (HOMO) and the lowest unoccupied molecular orbital (LUMO) energy levels show a dependence on the nature of the substituents attached to the alkynyl ligand. The energies of the HOMO and LUMO are found to increase and decrease, respectively, from R = (t)Bu to R = Ph and to R = C(6)H(4)Ph-p, because of the increase of the π- conjugation of the alkynyl ligand. On the basis of the TDDFT/CPCM calculations, the low-energy absorption band consists of two types of transitions, which are ligand-to-ligand charge-transfer (LLCT) [π(alkynyl) → σ*(dppm)]/metal-centered MC [dσ*(Pt(2)) → pσ(Pt(2))] transitions as well as interligand π → π* transition from the terminal alkynyl ligands to the bridging alkynyl ligand mixed with metal-metal-to-ligand charge transfer MMLCT [dσ*(Pt(2)) → π*(bridging alkynyl)] transition. The latter transition is lower in energy than the former. The calculation also indicates that the emission for the complexes originates from the triplet interligand π(terminal alkynyls) → π*(bridging alkynyl)/MMLCT [dσ*(Pt(2)) →

  17. Synthesis, characterization, cytotoxicity, and DNA binding of some new platinum(II) and platinum(IV) complexes with benzimidazole ligands.

    Science.gov (United States)

    Utku, Semra; Gumus, Fatma; Tezcan, Seda; Serin, Mehmet Sami; Ozkul, Aykut

    2010-08-01

    In this study, two Pt(II) and three Pt(IV) complexes with the structures of [PtL(2)Cl(2)] (1), [PtL(2)I(2)] (2), [PtL(2)Cl(2)(OH)(2)] (3), [PtL(2)Cl(2)(OCOCH(3))(2)] (4), and [PtL(2)Cl(4)] (5) (L = benzimidazole as carrier ligand) were synthesized and evaluated for their in vitro antiproliferative activities against the human MCF-7, HeLa, and HEp-2 cancer cell lines. The influence of compounds 1-5 on the tertiary structure of DNA was determined by their ability to modify the electrophoretic mobility of the form I and II bands of pBR322 plasmid DNA. The inhibition of BamH1 restriction enzyme activity of compounds 1-5 was also determined. In general, it was found that compounds 1-5 were less active than cisplatin and carboplatin against MCF-7 and HeLa cell lines (except for 1, which was found to be more active than carboplatin against the MCF-7 cell line). Compounds 1 and 3 were found to be significantly more active than cisplatin and carboplatin against the HEp-2 cell line.

  18. New palladium(II) and platinum(II) 5,5-diethylbarbiturate complexes with 2-phenylpyridine, 2,2'-bipyridine and 2,2'-dipyridylamine: synthesis, structures, DNA binding, molecular docking, cellular uptake, antioxidant activity and cytotoxicity.

    Science.gov (United States)

    Icsel, Ceyda; Yilmaz, Veysel T; Kaya, Yunus; Samli, Hale; Harrison, William T A; Buyukgungor, Orhan

    2015-04-21

    Novel palladium(ii) and platinum(ii) complexes of 5,5-diethylbarbiturate (barb) with 2-phenylpyridine (Hppy), 2,2'-bipyridine (bpy) and 2,2'-dipyridylamine (dpya) have been prepared and characterized by elemental analysis, IR, UV-Vis, NMR and ESI-MS. Single-crystal diffraction measurements show that complex consists of binuclear [Pd2(μ-barb-κN,O)2(ppy-κN,C)2] moieties, while complexes are mononuclear, [M(barb-κN)2(L-κN,N')] (L = bpy or dpya). has a composition of [Pt(dpya-κN,N')2][Ag(barb-κN)2]2·4H2O and was assumed to have a structure of [Pt(barb-κN)(Hppy-κN)(ppy-κN,C)]·3H2O. The complexes were found to exhibit significant DNA binding affinity by a non-covalent binding mode, in accordance with molecular docking studies. In addition, complexes and displayed strong binding with supercoiled pUC19 plasmid DNA. Cellular uptake studies were performed to assess the subcellular localization of the selected complexes. A moderate radical scavenging activity of and was confirmed by DPPH and ABTS tests. Complexes , , and showed selectivity against HT-29 (colon) cell line.

  19. Permafrost-carbon complexities

    NARCIS (Netherlands)

    Vonk, J.E.; Gustafsson, Ö.

    2013-01-01

    The thawing and decomposition of carbon stored in permafrost generates greenhouse gases that could further intensify global warming. Currently, most of the thawed carbon is assumed to be converted to greenhouse gases, such as carbon dioxide and methane, and carbon decomposition is thought

  20. Mechanistic and conformational studies on the interaction of a platinum(II) complex containing an antiepileptic drug, levetiracetam, with bovine serum albumin by optical spectroscopic techniques in aqueous solution.

    Science.gov (United States)

    Shahabadi, Nahid; Hadidi, Saba

    2015-02-01

    Fluorescence spectroscopy in combination with circular dichroism (CD) and ultraviolet-visible (UV-vis) absorption spectroscopy were employed to investigate the binding of a new platinum(II) complex containing an antiepileptic drug "Levetiracetam" to bovine serum albumin (BSA) under the physiological conditions. In the mechanism discussion, it was proved that the fluorescence quenching of BSA by Pt(II) complex is a result of the formation of Pt(II) complex-BSA complex. The thermodynamic parameters ΔG, ΔH, and ΔS at different temperatures (283, 298, and 310 K) were calculated, and the negative value for ΔH and ΔS indicate that the hydrogen bonds and van der Waals interactions play major roles in Pt(II) complex-BSA association. Binding studies concerning the number of binding sites (n~1) and apparent binding constant K b were performed by fluorescence quenching method. The site marker competitive experiments indicated that the binding of Pt(II) complex to BSA primarily took place in site II. Based on the Förster's theory, the average binding distance between Pt(II) complex and BSA was obtained (r = 5.29 nm). Furthermore, UV-vis, CD, and synchronous fluorescence spectrum were used to investigate the structural change of BSA molecules with addition of Pt(II) complex. These results indicate that the binding of Pt(II) complex to BSA causes apparent change in the secondary structure of BSA and do affect the microenvironment around the tryptophan residue.

  1. Biological activity of palladium(II) and platinum(II) complexes of the acetone Schiff bases of S-methyl- and S-benzyldithiocarbazate and the X-ray crystal structure of the [Pd(asme)2] (asme=anionic form of the acetone Schiff base of S-methyldithiocarbazate) complex.

    Science.gov (United States)

    Akbar Ali, Mohammad; Mirza, Aminul Huq; Butcher, Raymond J; Tarafder, M T H; Keat, Tan Boon; Ali, A Manaf

    2002-11-25

    Palladium(II) and platinum(II) complexes of general empirical formula, [M(NS)(2)] (NS=uninegatively charged acetone Schiff bases of S-methyl- and S-benzyldithiocarbazate; M=Pt(II) and Pd(II)) have been prepared and characterized by a variety of physicochemical techniques. Based on conductance, IR and electronic spectral evidence, a square-planar structure is assigned to these complexes. The crystal and molecular structure of the [Pd(asme)(2)] complex (asme=anionic form of the acetone Schiff base of S-methyldithiocarbazate) has been determined by X-ray diffraction. The complex has a distorted cis-square planar structure with the ligands coordinated to the palladium(II) ions as uninegatively charged bidentate NS chelating agents via the azomethine nitrogen and the mercaptide sulfur atoms. The distortion from a regular square-planar geometry is attributed to the restricted bite angles of the ligands. Antimicrobial tests indicate that the Schiff bases exhibit strong activities against the pathogenic bacteria, Bacillus subtilis (mutant defective DNA repair), methicillin-resistant Staphylococcus aureus, B. subtilis (wild type) and Pseudomonas aeruginosa and the fungi, Candida albicans (CA), Candida lypotica (2075), Saccharomyces cerevisiae (20341) and Aspergillus ochraceous (398)-the activities exhibited by these compounds being greater than that of the standard antibacterial and antifungal drugs, streptomycin and nystatin, respectively. The palladium(II) and platinum(II) complexes are inactive against most of these organisms but, the microbe, Pseudomonas aeruginosa shows strong sensitivity to the platinum(II) complexes. Screening of the compounds for their cytotoxicities against T-lymphoblastic leukemia cancer cells has shown that the acetone Schiff base of S-methyldithiocarbazate (Hasme) exhibits a very weak activity, whereas the S-benzyl derivative (Hasbz) is inactive. However, the palladium(II) complexes exhibit strong cytotoxicities against this cancer; their

  2. New platinum(II) complexes conjugated at position 7α of 17β-acetyl-testosterone as new combi-molecules against prostate cancer: design, synthesis, structure-activity relationships and biological evaluation.

    Science.gov (United States)

    Fortin, Sébastien; Brasseur, Kevin; Morin, Nathalie; Asselin, Éric; Bérubé, Gervais

    2013-10-01

    Prostate cancer is a major public health problem worldwide and, more specifically, new treatments for hormone-refractory cancers are highly sought by several research groups. Although platinum(II)-based chemotherapy and other strategies grow in interest to treat castration-resistant prostate cancer (CRPC), they still exhibit modest activity on CRPC and overall patient survival. In this study, we designed and prepared new combi-molecules using 17β-acetyl-testosterone and amino acid platinum(II) complexes linked at the position 7α to target and to improve the antiproliferative activity of platinum(II)-based chemotherapy on prostate cancer cells. Twelve chemical intermediates and six new combi-molecules were prepared and characterized. Structure-activity relationships studies show that the platinum complex moiety is essential for an optimal cytocidal activity. Moreover, stereochemistry of the amino acid involved in the platinum complexes had only minor effects on the antiproliferative activity whereas pyridinyl (10a and b) and thiazolyl (10f) complexes exhibited the highest cytocidal activities that are significantly superior to that of cisplatin used as control on human prostate adenocarcinoma LNCaP (AR+), PC3 (AR-) and DU145 (AR-). Compounds 10a, b and f arrested the cell cycle progression in S-phase and induced double strand breaks as confirmed by the phosphorylation of histone H2AX into γH2AX. Compounds 10a and f showed 33 and 30% inhibition, respectively of the growth of HT-1080 tumors grafted onto chick chorioallantoic membranes. Finally, compounds 10a and 10f exhibited low toxicity on the chick embryos (18 and 21% of death, respectively), indicating that these new combi-molecules might be a promising new class of anticancer agents for prostate cancer.

  3. Crystallization experiments with the dinuclear chelate ring complex di-μ-chlorido-bis[(η(2)-2-allyl-4-methoxy-5-{[(propan-2-yloxy)carbonyl]methoxy}phenyl-κC(1))platinum(II)].

    Science.gov (United States)

    Nguyen Thi Thanh, Chi; Pham Van, Thong; Le Thi Hong, Hai; Van Meervelt, Luc

    2016-10-01

    Crystallization experiments with the dinuclear chelate ring complex di-μ-chlorido-bis[(η(2)-2-allyl-4-methoxy-5-{[(propan-2-yloxy)carbonyl]methoxy}phenyl-κC(1))platinum(II)], [Pt2(C15H19O4)2Cl2], containing a derivative of the natural compound eugenol as ligand, have been performed. Using five different sets of crystallization conditions resulted in four different complexes which can be further used as starting compounds for the synthesis of Pt complexes with promising anticancer activities. In the case of vapour diffusion with the binary chloroform-diethyl ether or methylene chloride-diethyl ether systems, no change of the molecular structure was observed. Using evaporation from acetonitrile (at room temperature), dimethylformamide (DMF, at 313 K) or dimethyl sulfoxide (DMSO, at 313 K), however, resulted in the displacement of a chloride ligand by the solvent, giving, respectively, the mononuclear complexes (acetonitrile-κN)(η(2)-2-allyl-4-methoxy-5-{[(propan-2-yloxy)carbonyl]methoxy}phenyl-κC(1))chloridoplatinum(II) monohydrate, [Pt(C15H19O4)Cl(CH3CN)]·H2O, (η(2)-2-allyl-4-methoxy-5-{[(propan-2-yloxy)carbonyl]methoxy}phenyl-κC(1))chlorido(dimethylformamide-κO)platinum(II), [Pt(C15H19O4)Cl(C2H7NO)], and (η(2)-2-allyl-4-methoxy-5-{[(propan-2-yloxy)carbonyl]methoxy}phenyl-κC(1))chlorido(dimethyl sulfoxide-κS)platinum(II), determined as the analogue {η(2)-2-allyl-4-methoxy-5-[(ethoxycarbonyl)methoxy]phenyl-κC(1)}chlorido(dimethyl sulfoxide-κS)platinum(II), [Pt(C14H17O4)Cl(C2H6OS)]. The crystal structures confirm that acetonitrile interacts with the Pt(II) atom via its N atom, while for DMSO, the S atom is the coordinating atom. For the replacement, the longest of the two Pt-Cl bonds is cleaved, leading to a cis position of the solvent ligand with respect to the allyl group. The crystal packing of the complexes is characterized by dimer formation via C-H...O and C-H...π interactions, but no π-π interactions are observed despite the presence of

  4. Cytotoxic malonate platinum(II) complexes with 1,2,4-triazolo[1,5-a]pyrimidine derivatives: structural characterization and mechanism of the suppression of tumor cell growth.

    Science.gov (United States)

    Łakomska, Iwona; Hoffmann, Kamil; Wojtczak, Andrzej; Sitkowski, Jerzy; Maj, Ewa; Wietrzyk, Joanna

    2014-12-01

    A series of malonate (mal) platinum(II) complexes of the general formula [Pt(mal)(L)2], where L=5,7-dimethyl-1,2,4-triazolo[1,5-a]pyrimidine (dmtp) (1), 7-isobutyl-5-methyl-1,2,4-triazolo[1,5-a]pyrimidine (ibmtp) (2) or 5,7-ditertbutyl-1,2,4-triazolo[1,5-a]pyrimidine (dbtp) (3), has been prepared and characterized using multinuclear ((1)H, (13)C, (15)N, (195)Pt) NMR, IR and electrospray ionization mass spectrometry (ESIMS). Furthermore, the crystal structures of [Pt(mal)(dmtp)2]∙4H2O (1a) and [Pt(mal)(dbtp)2]∙CHCl3 (3a) have been determined using single-crystal X-ray diffraction. The spectroscopic characterization unambiguously confirmed the square-planar geometry of Pt(II) with two monodentate N3-bonded 5,7-disubstituted-1,2,4-triazolo[1,5-a]pyrimidines and one O-chelating malonate. The antiproliferative activities of the compounds against the human cell lines T47D (cisplatin-resistant human ductal breast epithelial tumor cell line) and A549 (lung adenocarcinoma epithelial cell line) and the mouse cell line 4T1 (mouse breast tumor model) were assessed using an in vitro screening assay. Compounds (2) and (3) exhibited substantial antigrowth properties against T47D cells, whereas only (3) exhibited an IC50 value that was lower than cisplatin and carboplatin against the 4T1 cell line. Additionally, compounds (2, 3) are capable of arresting the cell cycle of A549 cells at the G0/G1 phase, whereas cisplatin and carboplatin arrested the cells at the G2/M phase, indicating differences in the mechanism of the suppression of tumor cell growth. Finally, in the quest for low toxicity platinum drugs, the in vitro antiproliferative activity against normal mouse fibroblast cells (BALB/3T3) was evaluated. The inhibition of BALB/3T3 cell proliferation by the evaluated Pt(II) complexes increased in the order (1)<(2)

  5. Kinetics and mechanism for reversible chloride transfer between mercury(II) and square-planar platinum(II) chloro ammine, aqua, and sulfoxide complexes. Stabilities, spectra, and reactivities of transient metal-metal bonded platinum-mercury adducts.

    Science.gov (United States)

    Gröning, O; Sargeson, A M; Deeth, R J; Elding, L I

    2000-09-18

    The Hg2+aq- and HgCl+aq-assisted aquations of [PtCl4]2- (1), [PtCl3(H2O)]- (2), cis-[PtCl2(H2O)2] (3), trans-[PtCl2(H2O)2] (4), [PtCl(H2O)3]+ (5), [PtCl3Me2SO]- (6), trans-[PtCl2(H2O)Me2SO] (7), cis-[PtCl(H2O)2Me2SO]+ (8), trans-[PtCl(H2O)2M32SO]+ (9), trans-[PtCl2(NH3)2] (10), and cis-[PtCl2(NH3)2] (11) have been studied at 25.0 degrees C in a 1.00 M HClO4 medium buffered with chloride, using stopped-flow and conventional spectrophotometry. Saturation kinetics and instantaneous, large UV/vis spectral changes on mixing solutions of platinum complex and mercury are ascribed to formation of transient adducts between Hg2+ and several of the platinum complexes. Depending on the limiting rate constants, these adducts are observed for a few milliseconds to a few minutes. Thermodynamic and kinetics data together with the UV/vis spectral changes and DFT calculations indicate that their structures are characterized by axial coordination of Hg to Pt with remarkably short metal-metal bonds. Stability constants for the Hg2+ adducts with complexes 1-6, 10, and 11 are (2.1 +/- 0.4) x 10(4), (8 +/- 1) x 10(2), 94 +/- 6, 13 +/- 2, 5 +/- 2, 60 +/- 6, 387 +/- 2, and 190 +/- 3 M-1, respectively, whereas adduct formation with the sulfoxide complexes 7-9 is too weak to be observed. For analogous platinum(II) complexes, the stabilities of the Pt-Hg adducts increase in the order sulfoxide < aqua < ammine complex, reflecting a sensitivity to the pi-acid strength of the Pt ligands. Rate constants for chloride transfer from HgCl+ and HgCl2 to complexes 1-11 have been determined. Second-order rate constants for activation by Hg2+ are practically the same as those for activation by HgCl+ for each of the platinum complexes studied, yet resolved contributions for Hg2+ and HgCl+ reveal that the latter does not form dinuclear adducts of any significant stability. The overall experimental evidence is consistent with a mechanism in which the accumulated Pt(II)-Hg2+ adducts are not reactive

  6. Highly water-soluble platinum(II) complexes as GLUT substrates for targeted therapy: improved anticancer efficacy and transporter-mediated cytotoxic properties.

    Science.gov (United States)

    Liu, Pengxing; Lu, Yanhui; Gao, Xiangqian; Liu, Ran; Zhang-Negrerie, Daisy; Shi, Ying; Wang, Yiqiang; Wang, Songqing; Gao, Qingzhi

    2013-03-25

    Glucose-conjugated malonato-platinum(II) complexes are designed and synthesized to target tumor-specific active transporters, namely, glucose transporters (GLUTs); the complexes exhibit much higher aqueous solubility by 150 times, improved potency in cytotoxicities by 10 times, and increased therapeutic index by over 30 fold compared to the newest generation of clinical drugs oxaliplatin.

  7. An unusual (H(2)O)(20) discrete water cluster in the supramolecular host of a charge transfer platinum(ii) complex: cytotoxicity and DNA cleavage activities.

    Science.gov (United States)

    Mandal, Sutanuva; Castiñeiras, Alfonso; Mondal, Tapan K; Mondal, Arindam; Chattopadhyay, Dhrubajyoti; Goswami, Sreebrata

    2010-10-28

    The chemical reaction of Pt(II)(L(1))Cl(2) [L(1) = N-4-tolylpyridine-2-aldimine] with a bidentate N,S-donor atom ligand, 2-methylthioaniline, (HL(2)) in alkaline methanolic medium yielded a mixed ligand donor-acceptor complex, [Pt(II)(L(1))(L(2))]Cl, [1]Cl. The complex has been characterized by different spectroscopic and electrochemical techniques. The complex showed intense interligand charge transfer (ILCT) transition in the long wavelength region of UV-vis spectrum (>600 nm). The single-crystal X-ray structure of complex, [1]Cl·3.3H(2)O is reported. The cationic complex upon crystallization from aqueous methanol solvent produces an assembly of discrete, three dimensional (H(2)O)(20) guest moiety within the reference Pt-complex host lattice. The water assembly showed a unique type of aggregation of a distorted cube encapsulated by hydrogen bonded network of a twelve-water ring. The complex displayed one reversible cathodic response at -0.75 V and two irreversible anodic responses at 0.42 and 0.79 V versus Ag/AgCl reference electrode. The redox processes are characterized by EPR and spectroelectrochemistry. Density-functional theory calculations were employed to confirm the structural features and to support the spectral and redox properties of the complex. The square-planar complex has been found to intercalate DNA. Fluorescence spectroscopy, circular dichroism, cyclic voltammetry, viscosity measurements, together with DNA melting studies have been employed to characterize the binding of [1]Cl with calf thymus DNA. Agarose gel electrophoresis indicates that the complex cleaves supercoiled (SC) pUC19 plasmid DNA to its nicked circular (NC) form via singlet oxygen. As determined by a MTT assay, [1]Cl exhibits significant cytotoxicity with IC(50) value 58 μM.

  8. Multi-Nuclear NMR Investigation of Nickel(II), Palladium(II), Platinum(II) and Ruthenium(II) Complexes of an Asymmetrical Ditertiary Phosphine

    Energy Technology Data Exchange (ETDEWEB)

    Raj, Joe Gerald Jesu [Institut National de la Recherche Scientifique, Quebec (China); Pathak, Devendra Deo [Indian School of Mines, Dhanbad (India); Kapoor, Pramesh N. [Univ. of Delhi, Delhi (India)

    2013-12-15

    Complexes synthesized by reacting alkyl and aryl phosphines with different transition metals are of great interest due to their catalytic properties. Many of the phosphine complexes are soluble in polar solvents as a result they find applications in homogeneous catalysis. In our present work we report, four transition metal complexes of Ni(II), Pd(II), Pt(II) and Ru(II) with an asymmetrical ditertiaryphosphine ligand. The synthesized ligand bears a less electronegative substituent such as methyl group on the aromatic nucleus hence makes it a strong σ-donor to form stable complexes and thus could effectively used in catalytic reactions. The complexes have been completely characterized by elemental analyses, FTIR, {sup 1}HNMR, {sup 31}PNMR and FAB Mass Spectrometry methods. Based on the spectroscopic evidences it has been confirmed that Ni(II), Pd(II) and Pt(II) complexes with the ditertiaryphosphine ligand showed cis whereas the Ru(II) complex showed trans geometry in their molecular structure.

  9. Zwitterionic and Cationic Bis(phosphine) Platinum(II) Complexes:  Structural, Electronic, and Mechanistic Comparisons Relevant to Ligand Exchange and Benzene C−H Activation Processes

    OpenAIRE

    Thomas, J. Christopher; Peters, Jonas C.

    2003-01-01

    Structurally similar but charge-differentiated platinum complexes have been prepared using the bidentate phosphine ligands [Ph_(2)B(CH_(2)PPh_(2))_(2)], ([Ph_(2)BP_(2)], [1]), Ph_(2)Si(CH_(2)PPh_(2))_(2), (Ph_(2)SiP_(2), 2), and H_(2)C(CH_(2)PPh_(2))_(2), (dppp, 3). The relative electronic impact of each ligand with respect to a coordinated metal center's electron-richness has been examined using comparative molybdenum and platinum model carbonyl and alkyl complexes. Complexes supported by an...

  10. Electronic spectra and photophysics of platinum(II) complexes with alpha-diimine ligands - Solid-state effects. I - Monomers and ligand pi dimers

    Science.gov (United States)

    Miskowski, Vincent M.; Houlding, Virginia H.

    1989-01-01

    Two types of emission behavior for Pt(II) complexes containing alpha-diimine ligands have been observed in dilute solution. If the complex also has weak field ligands such as chloride, ligand field (d-d) excited states become the lowest energy excited states. If only strong field ligands are present, a diimine 3(pi-pi/asterisk/) state becomes the lowest. In none of the cases studied did metal-to-ligand charge transfer excited state lie lowest.

  11. Design, synthesis and anticancer activity of diam(m)ine platinum(II) complexes bearing a small-molecular cell apoptosis inducer dichloroacetate.

    Science.gov (United States)

    Liu, Weiping; Jiang, Jing; Xu, Yongping; Hou, Shuqian; Sun, Liping; Ye, Qingsong; Lou, Liguang

    2015-05-01

    Four new diam(m)ine platinum complexes containing the dichloroacetate moiety in 3-dichoroacetoxylcyclobutane-1,1-dicarboxylate as the leaving group were synthesized, characterized by elemental analysis as well as by ESI(+)-MS (electrospray ionization mass spectrometry in positive mode), FT-IR, (1)H- and (13)C-NMR, and evaluated for their in vitro anticancer activity against human lung cancer cell line (A549) and ovarian cancer cell lines (SK-OV-3, SK-OV-3/DDP). Diam(m)ines used in the present study belong to the carriers of six clinically approved platinum drugs. Among the complexes synthesized, complex 2, cis-[Pt(II)(1R,2R-diaminocyclohexane)·(3-dichoroacetoxylcyclobutane-1,1-dicarboxylate)] is the most promising in terms of water solubility and potential of being totally devoid of cross-drug resistance with cisplatin. Therefore, complex 2 was selected for the dichloroacetate release test. The test shows dichloroacetate can be efficiently released from complex 2 under physiological conditions via the hydrolysis of an ester bond bridging the dichloroacetate moiety and platinum pharmacophores together. Our study supports the further evaluation of this complex as a drug candidate.

  12. DNA-based aptamer fails as a simultaneous cancer targeting agent and drug delivery vehicle for a phenanthroline-based platinum(II) complex.

    Science.gov (United States)

    McGinely, Nicola L; Plumb, Jane A; Wheate, Nial J

    2013-11-01

    The sgc8c aptamer is a 41-base DNA oligonucleotide that binds to leukaemia cells with high affinity and specificity. In this work we examined the utility of this aptamer as both a delivery vehicle and an active targeting agent for an inert platinum complex [(1,10-phenathroline)(ethylenediamine)platinum(II)](2+). The aptamer forms a stem-and-loop confirmation as determined by circular dichroism. This conformation is adopted in both water and phosphate buffered saline solutions. The metal complex binds through intercalation into the aptamer's double helical stem with a binding constant of approximately 4.3 × 10(4) M(-1). Binding of the metal complex to the aptamer had a significant effect on the aptamer's global conformation, and increased its melting temperature by 28°C possibly through lengthening and stiffening of the aptamer stem. The effect of the aptamer on the metal complex's cytotoxicity and cellular uptake was determined using in vitro assays with the target leukaemia cell line CCRF-CEM and the off-target ovarian cancer cell lines A2780 and A2780cp70. The aptamer has little inherent cytotoxicity and when used to deliver the metal complex results in a significant decrease in the metal complex's cytotoxicity and uptake. The reason(s) for the poor uptake and activity may be due to the change in aptamer conformation which affects its ability to recognise leukaemia cells.

  13. Higher fluorescence in platinum(iv) orthometallated complexes of perylene imine compared with their platinum(ii) or palladium(ii) analogues.

    Science.gov (United States)

    Expósito, J Emilio; Álvarez-Paíno, Marta; Aullón, Gabriel; Miguel, Jesús A; Espinet, Pablo

    2015-09-28

    The reaction of 3-perylenylmethylen-4'-ethylaniline () with [Pt2Me4(μ-SMe2)2] (and subsequent addition of PPh3) or with [Pt2(η(3)-C4H7)2(μ-Cl)2] produced cyclometallated Pt(II) complexes [Pt(C^N)Me(PPh3)] () and, respectively, [Pt2(C^N)2(μ-Cl)2] () (HC^N = 3-C20H11CH[double bond, length as m-dash]NC6H4-p-C2H5), with Pt bound to the ortho site of the perylenyl fragment. From the mononuclear complexes [Pt(C^N)L2] (L2 = acac (); S2COMe (); S2CNEt2 () are easily formed. Oxidative addition of methyl iodide to the square-planar Pt(II) complexes , , and gave the corresponding cyclometallated Pt(IV) compounds [Pt(C^N)L2MeI] , and . The X-ray structures of , , and show that the perylenyl fragment remains essentially flat in and and slightly twisted in . Comparison of the optical properties of these Pt(II) complexes with those reported for similar Pd(II) derivatives reveals that the change of metal exerts a notable influence on the UV-vis spectra. In solution at room temperature, all the Pt complexes exhibit fluorescence associated with the perylene fragment with low emission quantum yields for the Pt(II) complexes (IV) complexes: up to 29%, with emission lifetimes of 1-5 ns. Time-dependent density functional theory (TD-DFT) calculations were performed on the perylene imine and on representative complexes [M(C^N)(acac)] (M = Pd, Pt) and [Pt(C^N)(acac)MeI] to analyse the absorption spectra. These calculations support a perylene-dominated intraligand π-π*emissive state based on the HOMO and LUMO orbitals of the perylene chromophore, and a ligand-to-ligand charge-transfer (more intense for the Pt(II) complex) that explains the observed influence of the metal on the absorption properties.

  14. Synthesis of antitumor azolato-bridged dinuclear platinum(ii) complexes with in vivo antitumor efficacy and unique in vitro cytotoxicity profiles.

    Science.gov (United States)

    Komeda, Seiji; Takayama, Hiroshi; Suzuki, Toshihiro; Odani, Akira; Yamori, Takao; Chikuma, Masahiko

    2013-05-01

    We synthesised four tetrazolato-bridged dinuclear Pt(ii) complexes, [{cis-Pt(NH3)2}2(μ-OH)(μ-5-R-tetrazolato-N2,N3)](n+), where R is CH3 (1), C6H5 (2), CH2COOC2H5 (3), or CH2COO(-) (4) and n = 2 (1-3) or 1 (4). Their structures were characterised by (1)H, (13)C, and (195)Pt NMR spectroscopy, mass spectrometry, and elemental analysis, and the crystal structure of 1 was determined by X-ray crystallography. The cytotoxicities of the complexes to human non-small-cell lung cancer (NSCLC) cell lines sensitive and resistant to cisplatin were assayed. Complex 1 was more cytotoxic than cisplatin in both PC-9 and PC-14 NSCLC cell lines, and cross-resistance to 1 in the cisplatin-resistant cells was largely circumvented. Complex 3 was moderately cytotoxic, whereas 2 and 4 were only marginally cytotoxic. We also determined the growth inhibitory activities of 1 and 3, as well as prototype azolato-bridged complexes [{cis-Pt(NH3)2}2(μ-OH)(μ-pyrazolato)](2+) (AMPZ), [{cis-Pt(NH3)2}2(μ-OH)(μ-1,2,3-triazolato-N1,N2)](2+) (AMTA), [{cis-Pt(NH3)2}2(μ-OH)(μ-tetrazolato-N1,N2)](2+) (5-H-X), and [{cis-Pt(NH3)2}2(μ-OH)(μ-tetrazolato-N2,N3)](2+) (5-H-Y), against a panel of 39 human cancer cell lines (JFCR39). The average 50% growth inhibition concentrations of the complexes against the JFCR39 cell lines ranged from 0.933 to 23.4 μM. The cytotoxicity fingerprints of the complexes based on the JFCR39 cytotoxicity data were similar to one another but completely different from the fingerprints of clinical platinum-based anticancer drugs. Complex 3 exhibited marked antitumor efficiency when tested in vivo on xenografts of PANC-1 pancreatic cancer in nude mice. The high potency of 3 confirmed that the tetrazolato-bridged structure exhibits high in vivo antitumor efficacy.

  15. Prophage induction and mutagenicity of a series of anti-tumour platinum(II) and platinum(IV) co-ordination complexes

    NARCIS (Netherlands)

    Mattern, I.E.; Cocchiarella, L.; Kralingen, C.G. van; Lohman, P.H.M.

    1982-01-01

    Eleven platinum compounds with nitrogen donor ligands, previously tested for anti-tumour activity were studied for induction of prophage lambda and for mutagenicity in the Ames assay, with various strains of Salmonella. The compounds included cis and trans isomers of Pt(II) and Pt(IV) complexes and

  16. Luminescent pincer platinum(II) complexes with emission quantum yields up to almost unity: photophysics, photoreductive C-C bond formation, and materials applications.

    Science.gov (United States)

    Chow, Pui-Keong; Cheng, Gang; Tong, Glenna So Ming; To, Wai-Pong; Kwong, Wai-Lun; Low, Kam-Hung; Kwok, Chi-Chung; Ma, Chensheng; Che, Chi-Ming

    2015-02-09

    Luminescent pincer-type Pt(II)  complexes supported by C-deprotonated π-extended tridentate RC^N^NR' ligands and pentafluorophenylacetylide ligands show emission quantum yields up to almost unity. Femtosecond time-resolved fluorescence measurements and time-dependent DFT calculations together reveal the dependence of excited-state structural distortions of [Pt(RC^N^NR')(CC-C6 F5 )] on the positional isomers of the tridentate ligand. Pt complexes [Pt(R-C^N^NR')(CC-Ar)] are efficient photocatalysts for visible-light-induced reductive CC bond formation. The [Pt(R-C^N^NR')(CC-C6 F5 )] complexes perform strongly as phosphorescent dopants for green- and red-emitting organic light-emitting diodes (OLEDs) with external quantum efficiency values over 22.1 %. These complexes are also applied in two-photon cellular imaging when incorporated into mesoporous silica nanoparticles (MSNs).

  17. Design, Synthesis of Novel Platinum(II) Glycoconjugates, and Evaluation of Their Antitumor Effects.

    Science.gov (United States)

    Han, Jianbin; Gao, Xiangqian; Liu, Ran; Yang, Jinna; Zhang, Menghua; Mi, Yi; Shi, Ying; Gao, Qingzhi

    2016-06-01

    A new series of sugar-conjugated (trans-R, R-cyclohexane-1, 2-diamine)-2-halo-malonato-platinum(II) complexes were designed and synthesized to target tumor-specific glucose transporters (GLUTs). The water solubility of the sugar-conjugated platinum (II) complexes was greatly improved by average of 570-fold, 33-fold, and 94-fold, respectively, compared to cisplatin (1.0 mg/mL), carboplatin (17.1 mg/mL), and the newest generation of clinical drug oxaliplatin (6.0 mg/mL). Despite the high water solubility, the platinum(II) glycoconjugates exhibited a notable increase in cytotoxicity by a margin of 1.5- to 6.0-fold in six different human cancer cell lines with respect to oxaliplatin. The potential GLUT1 transportability of the complexes was investigated through a molecular docking study and was confirmed with GLUT1 inhibitor-mediated cytotoxicity dependency evaluation. The results showed that the sugar-conjugated platinum(II) complexes can be recognized by the glucose recognition binding site of GLUT1 and their cell killing effect depends highly on the GLUT1 inhibitor, quercetin. The research presenting a prospective concept for targeted therapy anticancer drug design, and with the analysis of the synthesis, water solubility, antitumor activity, and the transportability of the platinum(II) glycoconjugates, this study provides fundamental data supporting the inherent potential of these designed conjugates as lead compounds for GLUT-mediated tumor targeting.

  18. Synthesis and antitumor activity of platinum(II) complexes with trans-3,4-diamino-2,2,6,6-tetramethylpiperidine-1-oxyl.

    Science.gov (United States)

    Sen', V D; Golubev, V A; Volkova, L M; Konovalova, N P

    1996-10-01

    Platinum complexes PtII(DAPO)X2 with diaminonitroxyl radical-trans-3,4-diamino-2,2,6,6-tetramethylpiperidine-1-oxyl (DAPO)-were synthesized by the direct reaction of DAPO with K2PtX4 (X = Cl, I) or by the replacement of chloro ligands in PtII(DAPO)Cl2 by bromo, nitrato, oxalato, malonato, and 1,1-cyclobutanedicarboxylato ligands. The complexes thus obtained were characterized by elemental analysis, infrared,electronic, electron paramagnetic resonance spectroscopic techniques, and high-performance liquid chromatography. The toxicity of compounds in terms of LD50 strongly depends on the nature of X-ligands, and varies between 11 mg/kg (X = NO3) and 400 mg/kg (X2 = 1,1-cyclobutanedicarboxylate). Up to 66% of mice bearing leukemia L1210 survive after the administration of these complexes. This effect is comparable to the effect of cisplatin (50% survive). An increase in the life span of the rest of the animals ranges from 158 to 383%. Complex PtII(DAPO)Cl2 appears to be more efficient than cisplatin against adenocarcinoma 755. Cisplatin, cis-diamminedichloroplatinum(II); CBDCA, 1,1-cyclobutanedicarboxylic acid; DAPO, trans-3,4-diamino-2,2,6,6-tetramethylpiperidine-1-oxyl; Mal, malonic acid; Ox, oxalic acid; IR, infrared; EPR, electron paramagnetic resonance; HPLC, high-performance liquid chromatography; Ca755, adenocarcinoma 755; LD50 and LD100, dose of compounds (mg/kg), causing a death of 50 or 100% or treated animals; ILS, increase in life span of mice.

  19. Pseudo-rotation mechanism for fast olefin exchange and substitution processes at orthometalated C,N-complexes of platinum(II).

    Science.gov (United States)

    Otto, Stefanus; Samuleev, Pavel V; Polyakov, Vladimir A; Ryabov, Alexander D; Elding, Lars I

    2004-11-07

    Bridge splitting in chloroform of the orthometalated chloro-bridged complex [Pt(micro-Cl)(2-Me(2)NCH(2)C(6)H(4))](2)(1), with ethene, cyclooctene, allyl alcohol and phosphine according to 1+ 2L --> 2[PtCl(2-Me(2)NCH(2)C(6)H(4))(L)], where L = C(2)H(4)(3a), C(8)H(14), (3b), CH(2)CHCH(2)OH (3c), and PPh(3)(4a and 4b) gives monomeric species with L coordinated trans or cis to aryl. With olefins the thermodynamically stable isomer with L coordinated cis to aryl is formed directly without an observable intermediate. With phosphine and pyridine, the kinetically controlled trans-product isomerizes slowly to the more stable cis-isomer. Bridge splitting by olefins is slow and first-order in 1 and L, with largely negative DeltaS(++). Substitution of ethene cis to aryl by cyclooctene and allyl alcohol to form 3b and 3c, and substitution of cot from 3b by allyl alcohol to form 3c are first order in olefin and complex, ca. six orders of magnitude faster than bridge cleavage due to a large decrease in DeltaH(++), and with largely negative DeltaS(++). Cyclooctene exchange at 3b is first-order with respect to free cyclooctene and platinum complex. All experimental data for olefin substitution and exchange are compatible with a concerted substitution/isomerization process via a turnstile twist pseudo-rotation in a short-lived labile five-coordinated intermediate, involving initial attack on the labile coordination position trans to the sigma-bonded aryl. Bridge-cleavage reactions of the analogous bridged complexes occur similarly, but are much slower because of their ground-state stabilization and steric hindrance.

  20. Platinum(II) complexes with 5,7-disubstituted-1,2,4-triazolo [1,5-a]pyrimidines: Spectroscopical characterization and cytotoxic activity in vitro

    Science.gov (United States)

    Łakomska, Iwona; Fandzloch, Marzena; Popławska, Beata; Sitkowski, Jerzy

    2012-06-01

    Complexes of the types: cis-[PtI2(dptp)2] (1), cis-[PtI2(NH3)(dptp)] (2), trans-[PtI2(dptp)(dmso)] (3) and trans-[PtI2(dbtp)(dmso)] (4), where dptp = 5,7-diphenyl-1,2,4-triazolo[1,5-a]pyrimidine (dptp), dbtp = 5,7-ditertbutyl-1,2,4-triazolo[1,5-a]pyrimidine have been synthesized and characterized by infrared and multinuclear magnetic resonance spectroscopic techniques (1H, 13C, 15N, 195Pt). In 195Pt NMR, the cis-diiodo complexes were observed between -2601 ppm and -3261 ppm, while the trans coordination compounds were found at higher field (ca. -4389 ppm). In all cases significant 15N NMR shielding (92-95 ppm) were observed for N(3) atom indicating this nitrogen atom as a coordination site. The cis complexes have been assayed for antitumor activity in vitro against two human cell lines: A549 (non-small cell lung carcinoma) and T47D (breast cancer). The results indicate a moderate antiproliferative activity of (2) against human cancer lines.

  1. Novel palladium(II) and platinum(II) complexes with 1H-benzimidazol-2-ylmethyl-N-(4-bromo-phenyl)-amine: structural studies and anticancer activity.

    Science.gov (United States)

    Abdel Ghani, Nour T; Mansour, Ahmed M

    2012-01-01

    [MLCl(2)] (L = (1H-benzimidazol-2-ylmethyl)-N-(4-bromo-phenyl)-amine; M = Pd & Pt) and [PdL(OH(2))(2)]∙2X∙zH(2)O (X = Br, I, z = 2; X = SCN, z = 1; X = NO(3), z = 0) complexes have been synthesized as potential anticancer compounds and their structures were elucidated using elemental analysis, spectral, thermal analysis and X-ray powder diffraction. The benzimidazole (L) crystallizes in the space group P2(1)/c with a = 8.6660(3) Å, b = 16.6739(7) Å, c = 9.8611(4) Å and β = 113.505(3) ° and forms an infinite chain structure with a trans-zigzag type along the crystallographic axis "a", through the intermolecular H-bond. FT-IR and (1)H NMR studies revealed that the ligand L is coordinated to the metal ion via the pyridine-type nitrogen (N(py)) of the benzimidazole ring and secondary amino group (NH(sec)). Quantum mechanical calculations of energies, geometries, vibrational wavenumbers, and (1)H NMR of the benzimidazole L and its complexes were carried out by DFT/B3LYP method combined with 6-31G(d) and LANL2DZ basis sets. Natural bond orbital (NBO) analysis and frontier molecular orbitals (FMO) were performed at B3LYP/LANL2DZ level of theory. The benzimidazole L, in comparison to its metal complexes was screened for its antibacterial activity. The complexes showed cyctotoxic effects against human breast cancer (MCF7), hepatocarcinoma (HepG(2)) and colon carcinoma cells (HCT). The platinum complex (6) exhibited a moderate antitumor activity against MCF7 with IC(50) = 10.2 μM comparing to that reported for cis-platin 9.91 μM.

  2. Highly fluorescent platinum(II) organometallic complexes of perylene and perylene monoimide, with Pt σ-bonded directly to the perylene core.

    Science.gov (United States)

    Lentijo, Sergio; Miguel, Jesús A; Espinet, Pablo

    2010-10-18

    3-Bromoperylene (BrPer) or N-(2,5-di-tert-butylphenyl)-9-bromo-perylene-3,4-dicarboximide (BrPMI) react with [Pt(PEt(3))(4)] to yield trans-[PtR(PEt(3))(2)Br] (R = Per, 1a; R = PMI, 1b). Neutral and cationic perylenyl complexes containing a Pt(PEt(3))X group have been prepared from 1a,b by substitution of the Br ligand by a variety of other ligands (NCS, CN, NO(3), CN(t)Bu, PyMe). The X-ray structures of trans-[PtR(PEt(3))(2)X] (R = Per, X = NCS (2a); R = PMI, X = NO(3) (4b); R = Per, X = CN(t)Bu (5a)) show that the perylenyl fragment remains nearly planar and is arranged almost orthogonal to the coordination plane: The three molecules appear as individual entities in the solid state, with no π-π stacking of perylenyl rings. Each platinum complex exhibits fluorescence associated to the perylene or PMI fragments with emission quantum yields, in solution at room temperature, in the range 0.30-0.80 and emission lifetimes ∼4 ns, but with significantly different emission maxima, by influence of the X ligands on Pt. The similarity of the overall luminescence spectra of these metalated complexes with the perylene or PMI strongly suggests a perylene-dominated intraligand π-π*emissive state, metal-perturbed by interaction of the platinum fragment mostly via polarization of the Ar-Pt bond.

  3. Highly Selective Colorimetric and Luminescence Response of a Square-Planar Platinum(II) Terpyridyl Complex to Aqueous TcO4-

    Energy Technology Data Exchange (ETDEWEB)

    Chatterjee, Sayandev; Norton, Amie E.; Edwards, Matthew K.; Peterson, James M.; Taylor, Stephen D.; Bryan, Samuel A.; Andersen, Amity; Govind, Niranjan; Albrecht-Schmitt, Thomas E.; Connick, William; Levitskaia, Tatiana G.

    2015-10-08

    In an effort to address the need for a rapid, selective and economical detection technique for aqueous pertechnetate (TcO4-) anion based on recognition at the molecular level, simple salts of transition metal complexes that undergo a distinct spectroscopic change upon exposure to aqueous anions were explored. The Pt(II) complex [Pt(tpy)Br]SbF6 (tpy=2,2';6',2"-terpyridine) undergoes a dramatic color change and intense luminescence response upon TcO4- uptake due to concomitant enhancement of Pt•••Pt interactions. The spectroscopic response was highly selective and quantitative for aqueous TcO4- among other competing anions. Complimentary Raman spectroscopy and microscopy techniques, structural determination and theoretical methods were employed to achieve molecular-level understanding of the mechanism of the response to aqueous TcO4-.

  4. Monofunctional platinum(II) complexes with potent tumor cell growth inhibitory activity: the effect of a hydrogen-bond donor/acceptor N-heterocyclic ligand.

    Science.gov (United States)

    Margiotta, Nicola; Savino, Salvatore; Gandin, Valentina; Marzano, Christine; Natile, Giovanni

    2014-06-01

    In this paper we investigate the possibility of further increase the role of the N-donor aromatic base in antitumor Hollis-type compounds by conferring the possibility to act as a hydrogen-bond donor/acceptor. Therefore, we synthesized the Pt(II) complex cis-[PtCl(NH3 )2 (naph)]NO3 (1) containing the 1,8-naphthyridine (naph) ligand. The naphthyridine ligand is generally monodentate, and the second nitrogen atom can act as H-bond donor/acceptor depending upon its protonation state. The possibility of forming such an H-bond could be crucial in the interaction of the drug with DNA or proteins. Apart from the synthesis of the compound, in this study we evaluated its in vitro antitumor activity in a wide panel of tumor cell lines, also including cells selected for their sensitivity/resistance to oxaliplatin, which was compared with that of previously reported complex 2 ([PtI(2,9-dimethyl-1,10-phenanthroline)(1-methyl-cytosine)]I) and oxaliplatin and cisplatin as reference compounds. The cytotoxicity data were correlated with the cellular uptake and the DNA platination levels. Finally, the reactivity of 1 towards guanosine 5'-monophosphate (5'-GMP) and glutathione was investigated to provide insights into its mechanism of action.

  5. Zwitterionic and cationic bis(phosphine) platinum(II) complexes: structural, electronic, and mechanistic comparisons relevant to ligand exchange and benzene C-H activation processes.

    Science.gov (United States)

    Thomas, J Christopher; Peters, Jonas C

    2003-07-23

    Structurally similar but charge-differentiated platinum complexes have been prepared using the bidentate phosphine ligands [Ph(2)B(CH(2)PPh(2))(2)], ([Ph(2)BP(2)], [1]), Ph(2)Si(CH(2)PPh(2))(2), (Ph(2)SiP(2), 2), and H(2)C(CH(2)PPh(2))(2), (dppp, 3). The relative electronic impact of each ligand with respect to a coordinated metal center's electron-richness has been examined using comparative molybdenum and platinum model carbonyl and alkyl complexes. Complexes supported by anionic [1] are shown to be more electron-rich than those supported by 2 and 3. A study of the temperature and THF dependence of the rate of THF self-exchange between neutral, formally zwitterionic [Ph(2)BP(2)]Pt(Me)(THF) (13) and its cationic relative [(Ph(2)SiP(2))Pt(Me)(THF)][B(C(6)F(5))(4)] (14) demonstrates that different exchange mechanisms are operative for the two systems. Whereas cationic 14 displays THF-dependent, associative THF exchange in benzene, the mechanism of THF exchange for neutral 13 appears to be a THF independent, ligand-assisted process involving an anchimeric, eta(3)-binding mode of the [Ph(2)BP(2)] ligand. The methyl solvento species 13, 14, and [(dppp)Pt(Me)(THF)][B(C(6)F(5))(4)] (15), each undergo a C-H bond activation reaction with benzene that generates their corresponding phenyl solvento complexes [Ph(2)BP(2)]Pt(Ph)(THF) (16), [(Ph(2)SiP(2))Pt(Ph)(THF)][B(C(6)F(5))(4)] (17), and [(dppp)Pt(Ph)(THF)][B(C(6)F(5))(4)] (18). Examination of the kinetics of each C-H bond activation process shows that neutral 13 reacts faster than both of the cations 14 and 15. The magnitude of the primary kinetic isotope effect measured for the neutral versus the cationic systems also differs markedly (k(C(6)H(6))/k(C(6)D(6)): 13 = 1.26; 14 = 6.52; 15 approximately 6). THF inhibits the rate of the thermolysis reaction in all three cases. Extended thermolysis of 17 and 18 results in an aryl coupling process that produces the dicationic, biphenyl-bridged platinum dimers [[(Ph(2)SiP(2))Pt](2

  6. Preparation of Platinum(II) Complexes with 1-b-D-Ribofuranosyl-1,2,4-triazole-3-carboxamide and its Deoxy-analogue

    Institute of Scientific and Technical Information of China (English)

    2001-01-01

    The platinum (II) complexes of the [Pt (N4,N7-Ribavirin) (DMSO) Cl], [Pt (N4,N7-De-oxyribavirin) (DMSO) Cl] were obtained by the reactions of cis-[Pt (DMSO)2 Cl2] and K[Pt (DMSO) Cl3] with 1-b -D-ribofuranosyl-1,2,4-triazole-3-carboxamide (Ribavirin) and its deoxy-analogue (deoxyribavirin). The preparation of 1-(2'-deoxy-b-D-ribofuranosyl) -1,2,4-triazole-3-carboxamide was also performed through a four-step procedure, protection of 3', 5'-dihydroxyl group of Ribavirin with 1,3-dichloro-1,1,3,3-tetraisopropyldisiloxane (TPDS-Cl), phenoxythio-carbonylation of the 2'-hydroxyl group of 3', 5'-O-TPDS-Ribavirin with phenoxythiocarbonyl-chloride (PTC-Cl), reduction of 2′-O-phenoxythiocarbonyl ester of 3', 5'-O-TPDS-Ribavirin with tri-n-butyltin hydride and AIBN, deprotection of 3', 5'-O-TPDS-Ribavirin with tetrabutylammon-ium fluoride in THF.

  7. Galactose conjugated platinum(II) complex targeting the Warburg effect for treatment of non-small cell lung cancer and colon cancer.

    Science.gov (United States)

    Wu, Meng; Li, Hong; Liu, Ran; Gao, Xiangqian; Zhang, Menghua; Liu, Pengxing; Fu, Zheng; Yang, Jinna; Zhang-Negrerie, Daisy; Gao, Qingzhi

    2016-03-03

    Malignant neoplasms exhibit a higher rate of glycolysis than normal cells; this is known as the Warburg effect. To target it, a galactose-conjugated (trans-R,R-cyclohexane-1,2-diamine)-2-chloromalonato-platinum(II) complex (Gal-Pt) was designed, synthesized, and evaluated in five human cancer cell lines and against two different xenograft tumour models. Gal-Pt exhibits much higher aqueous solubility (over 25 times) and improved cytotoxicity than oxaliplatin, especially in human colon (HT29) and lung (H460) cancer cell lines. The safety profile of Gal-Pt was investigated in vivo by exploring the maximum tolerated dose (MTD) and animal mortality rate. The ratios of the animal lethal dosage values to the cytotoxicity in HT29 (LD50/IC50) showed that Gal-Pt was associated with an increased therapeutic index by over 30-fold compared to cisplatin and oxaliplatin. We evaluated in vivo antitumor activity by single agent intravenous treatment comparison studies of Gal-Pt (50 mg/kg as 65% MTD) and cisplatin (3 mg/kg, as 80% MTD) in a H460 lung cancer xenograft model, and with oxaliplatin (7 mg/kg, as 90% MTD) in a HT29 colon cancer xenograft model. The results show that Gal-Pt was more efficacious against H460 than cisplatin, and had superior potency in HT29 cells compared to oxaliplatin under nontoxic dosage conditions. The dependency between cytotoxicity of Gal-Pt and glucose transporters (GLUTs) was investigated by using quercetin as an inhibitor of GLUTs in HT29 cells. The cytotoxic potency of Gal-Pt was highly reduced by the inhibitor, suggesting that the uptake of Gal-Pt was regulated by glucose transporters. The GLUT mediated transportability and cellular uptake of Gal-Pt was also demonstrated using a fluorescent glucose bioprobe in HT29 competition assay.

  8. Liposome encapsulation of lipophilic N-alkyl-propanediamine platinum complexes: impact on their cytotoxic activity and influence of the carbon chain length

    Energy Technology Data Exchange (ETDEWEB)

    Silva, Heveline; Fontes, Ana Paula S. [Universidade Federal de Juiz de Fora (UFJF), MG (Brazil). Dept. de Quimica; Lopes, Miriam Teresa P. [Universidade Federal de Minas Gerais (UFMG), Belo Horizonte, MG (Brazil). Dept. de Farmacologia; Frezard, Frederic, E-mail: frezard@icb.ufmg.b [Universidade Federal de Minas Gerais (UFMG), Belo Horizonte, MG (Brazil). Dept. de Fisiologia e Biofisica

    2010-07-01

    Antitumor platinum(II) complexes derived from N-alkyl-propanediamine differing in the length of their carbon chain (C8, C10, C12 and C14) were incorporated in liposomes and the cytotoxic activity of these formulations was evaluated against tumor (A{sub 549}, MDA-MB-231, B16-F1 and B16-F10) and non-tumor (BHK-21 and CHO) cell lines. Stable and monodisperse liposome suspensions incorporating the platinum complexes were obtained from the lipid composition consisting of distearoyl-sn-glycero-3-phosphocholine, cholesterol and 1,2-distearoyl-sn-glycero- 3-phosphoethanolamine-N-(methoxy(polyethylene glycol)-2000) at 5:3:0.3 molar ratio. The entrapment efficiency (EE%) of the platinum complexes in liposomes increased with the carbon chain length. EE% was higher than 80% in C12- and C14-derivatives. The effect of liposome encapsulation on the cytotoxic activity of the complexes was found to depend on the carbon chain length. These data indicate that the highest drug bioavailability from liposome formulations was achieved with the complex showing intermediate carbon chain length and partition between the liposome membrane and aqueous phase. (author)

  9. Ion exchange equilibria in simultaneous extraction of platinum(II, IV) and rhodium(III) from hydrochloric solutions

    Science.gov (United States)

    Mel'nikov, A. M.; Kononova, O. N.; Pavlenko, N. I.; Krylov, A. S.

    2012-06-01

    Regularities of sorption extraction of platinum(II, IV) and rhodium(III) by anion exchangers of various physical and chemical structure in the presence of hydrochloric media were studied. It is established that AM-2B, Purolite A 500, and Purolite S 985 ionites adsorb complex anions of platinum metals employing mixed mechanism. A high affinity of the studied anionites for the studied complex anions of platinum and rhodium is established.

  10. Solid-state materials for anion sensing in aqueous solution: highly selective colorimetric and luminescence-based detection of perchlorate using a platinum(II) salt.

    Science.gov (United States)

    Taylor, Stephen D; Howard, Whitney; Kaval, Necati; Hart, Robert; Krause, Jeanette A; Connick, William B

    2010-02-21

    The PF(6)(-) salt of a platinum(II) complex changes from yellow to red and becomes intensely luminescent upon exposure to aqueous ClO(4)(-). The response is remarkably selective. Spectroscopic changes are consistent with anion exchange resulting in shortening of the intramolecular PtPt distances between the square planar cations.

  11. Solid-state materials for anion sensing in aqueous solution: highly selective colorimetric and luminescence-based detection of perchlorate using a platinum(II) salt

    Energy Technology Data Exchange (ETDEWEB)

    Taylor, Stephen D.; Howard, Whitney; Kaval, Necati; Hart, Robert; Krause, Jeanette A.; Connick, William B. (UCIN); (Shepherd)

    2010-07-23

    The PF{sub 6}{sup -} salt of a platinum(II) complex changes from yellow to red and becomes intensely luminescent upon exposure to aqueous ClO{sub 4}{sup -}. The response is remarkably selective. Spectroscopic changes are consistent with anion exchange resulting in shortening of the intramolecular Pt***Pt distances between the square planar cations.

  12. Protonolysis of Dialkyl- and Alkylarylplatinum(II) Complexes and Geometrical Isomerization of the Derived Monoorgano-Solvento Complexes: Clear-Cut Examples of Associative and Dissociative Pathways in Platinum(II) Chemistry.

    Science.gov (United States)

    Romeo, Raffaello; Plutino, Maria Rosaria; Elding, Lars I.

    1997-12-03

    Protonolysis of the complexes cis-[PtR(2)(PEt(3))(2)] (R = Me, Et, Pr(n)(), Bu(n)(), CH(2)C(Me)(3), CH(2)Si(Me)(3)) and cis-[Pt(R)(R')(PEt(3))(2)] (R = Ph, 2-MeC(6)H(4), 2,4,6-Me(3)C(6)H(2); R' = Me) in methanol selectively cleaves one alkyl group, yielding cis-[Pt(R)(PEt(3))(2)(MeOH)](+) and alkanes. The reactions occur as single-stage conversions from the substrate to the product. There is no evidence by UV and by low-temperature (1)H and (31)P NMR spectroscopy for the presence of significant amounts of Pt(II) or Pt(IV) intermediate species. Reactions are first order with respect to complex and proton concentrations and are strongly retarded by steric congestion at the Pt-C bond, varying from k(2) = (2.65 +/- 0.08) x 10(5) M(-)(1) s(-)(1) for R = R' = Et to k(2) = 9.80 +/- 0.44 M(-)(1)s(-)(1) for R = R'= CH(2)Si(Me)(3). Low enthalpies of activation and largely negative volumes of activation are associated with the process. The mechanism involves a rate-determining proton transfer either to the metal-carbon sigma bond (S(E)2 mechanism) or to the metal center (S(E)(oxidative) mechanism), followed by fast extrusion of the alkane and simultaneous blocking of the vacant coordination site by the solvent to generate cis-[Pt(R)(PEt(3))(2)(MeOH)](+) species. The subsequent slower process, cis to trans isomerization of cis-[Pt(R)(PEt(3))(2)(MeOH)](+), is characterized by high values of enthalpies of activation, positive entropies of activation, and largely positive volumes of activation. The reaction is shown to proceed through the dissociative loss of the weakly bonded molecule of solvent and the interconversion of two geometrically distinct T-shaped 14-electron 3-coordinate intermediates. The presence of beta-hydrogens on the residual alkyl chain produces a great acceleration of the rate (R = Me, k(i) = 0.0026 s(-)(1); R = Et, k(i) = 44.9 s(-)(1)) as a consequence of the stabilization of the 3-coordinate [Pt(R)(PEt(3))(2)](+) transition state through an incipient agostic

  13. Cyclometalated platinum(II) with ethynyl-linked azobenzene ligands: an original switching mode.

    Science.gov (United States)

    Savel, Paul; Latouche, Camille; Roisnel, Thierry; Akdas-Kilig, Huriye; Boucekkine, Abdou; Fillaut, Jean-Luc

    2013-12-28

    The photophysical properties of 6-phenyl-2,2'-bipyridyl platinum(ii) complexes bearing different σ-alkynyl-linked azobenzene ancillary ligands were investigated. These complexes exhibited strong, broad, structureless charge-transfer bands in the visible region, which were red-shifted when the electron-donating ability of the para substituent on the azo-acetylide ligand increased. When excited at the charge-transfer absorption band, the complexes exhibited weak green emission, which was assigned to a triplet metal-to-ligand charge transfer/interligand charge transfer emission ((3)MLCT/(3)L'LCT). The presence of an amino substituent in the azobenzene moiety opened the possibility of protonation, which led to the formation of an azonium based derivative and resulted in drastic perturbations of the molecular orbitals and photophysical properties of the Pt-acetylide complex. These studies are fully supported by DFT and TD-DFT calculations.

  14. Complex Multifunctional Polymer/Carbon-Nanotube Composites

    Science.gov (United States)

    Patel, Pritesh; Balasubramaniyam, Gobinath; Chen, Jian

    2009-01-01

    A methodology for developing complex multifunctional materials that consist of or contain polymer/carbon-nanotube composites has been conceived. As used here, "multifunctional" signifies having additional and/or enhanced physical properties that polymers or polymer-matrix composites would not ordinarily be expected to have. Such properties include useful amounts of electrical conductivity, increased thermal conductivity, and/or increased strength. In the present methodology, these properties are imparted to a given composite through the choice and processing of its polymeric and CNT constituents.

  15. Evidence for Carbonate Surface Complexation during Forsterite Carbonation in Wet Supercritical Carbon Dioxide

    Energy Technology Data Exchange (ETDEWEB)

    Loring, John S.; Chen, Jeffrey; Benezeth Ep Gisquet, Pascale; Qafoku, Odeta; Ilton, Eugene S.; Washton, Nancy M.; Thompson, Christopher J.; Martin, Paul F.; McGrail, B. Peter; Rosso, Kevin M.; Felmy, Andrew R.; Schaef, Herbert T.

    2015-07-14

    Continental flood basalts are attractive formations for geologic sequestration of carbon dioxide because of their reactive divalent-cation containing silicates, such as forsterite (Mg2SiO4), suitable for long-term trapping of CO2 mineralized as metal carbonates. The goal of this study was to investigate at a molecular level the carbonation products formed during the reaction of forsterite with supercritical CO2 (scCO2) as a function of the concentration of H2O adsorbed to the forsterite surface. Experiments were performed at 50 °C and 90 bar using an in situ IR titration capability, and post-reaction samples were examined by ex situ techniques, including SEM, XPS, FIB-TEM, TGA-MS, and MAS-NMR. Carbonation products and reaction extents varied greatly with adsorbed H2O. We show for the first time evidence of Mg-carbonate surface complexation under wet scCO2 conditions. Carbonate is found to be coordinated to Mg at the forsterite surface in a predominately bidentate fashion at adsorbed H2O concentrations below 27 µmol/m2. Above this concentration and up to 76 µmol/m2, monodentate coordinated complexes become dominant. Beyond a threshold adsorbed H2O concentration of 76 µmol/m2, crystalline carbonates continuously precipitate as magnesite, and the particles that form are hundreds of times larger than the estimated thicknesses of the adsorbed water films of about 7 to 15 Å. At an applied level, these results suggest that mineral carbonation in scCO2 dominated fluids near the wellbore and adjacent to caprocks will be insignificant and limited to surface complexation, unless adsorbed H2O concentrations are high enough to promote crystalline carbonate formation. At a fundamental level, the surface complexes and their dependence on adsorbed H2O concentration give insights regarding forsterite dissolution processes and magnesite nucleation and growth.

  16. Evidence for Carbonate Surface Complexation during Forsterite Carbonation in Wet Supercritical Carbon Dioxide

    Energy Technology Data Exchange (ETDEWEB)

    Loring, John S.; Chen, Jeffrey; Benezeth, Pascale; Qafoku, Odeta; Ilton, Eugene S.; Washton, Nancy M.; Thompson, Christopher J.; Martin, Paul F.; McGrail, B. Peter; Rosso, Kevin M.; Felmy, Andrew R.; Schaef, Herbert T.

    2015-06-16

    Continental flood basalts are attractive formations for geologic sequestration of carbon dioxide because of their reactive divalent-cation containing silicates, such as forsterite (Mg2SiO4), suitable for long-term trapping of CO2 mineralized as metal carbonates. The goal of this study was to investigate at a molecular level the carbonation products formed during the reaction of forsterite with supercritical CO2 (scCO2) as a function of the concentration of H2O adsorbed to the forsterite surface. Experiments were performed at 50 °C and 90 bar using an in situ IR titration capability, and post-reaction samples were examined by ex situ techniques, including SEM, XPS, FIB-TEM, TGA-MS, and MAS-NMR. Carbonation products and reaction extents varied greatly with adsorbed H2O. We show for the first time evidence of Mg-carbonate surface complexation under wet scCO2 conditions. Carbonate is found to be coordinated to Mg at the forsterite surface in a predominately bidentate fashion at adsorbed H2O concentrations below 27 µmol/m2. Above this concentration and up to 76 µmol/m2, monodentate coordinated complexes become dominant. Beyond a threshold adsorbed H2O concentration of 76 µmol/m2, crystalline carbonates continuously precipitate as magnesite, and the particles that form are hundreds of times larger than the estimated thicknesses of the adsorbed water films of about 7 to 15 Å. At an applied level, the implication of these results is that mineral trapping in scCO2 dominated fluids will be insignificant and limited to surface complexation unless adsorbed H2O concentrations are high enough to promote crystalline carbonate formation. At a fundamental level, the surface complexes and their dependence on adsorbed H2O concentration give insights regarding forsterite dissolution processes and magnesite nucleation and growth.

  17. Carbon Dioxide Exchange in Complex Topography

    Science.gov (United States)

    Reif, Matthias; Rotach, Mathias; Wohlfahrt, Georg; Gohm, Alexander

    2015-04-01

    On a global scale the budget of carbon dioxide (CO_2) bears a quite substantial uncertainty, which is commonly understood to be mainly due to land-surface exchange processes. In this project we investigate to what extent complex topography can amplify these land-surface exchange processes. The hypothesis is that, on the meso-scale, topography adds additional atmospheric mechanisms that drive the exchange of CO2 at the surface. This sensitivity model study investigates an idealized sine shaped valley with the atmospheric numerical model Weather Research and Forecasting (WRF) coupled to the community land model (CLM) to study the effect of complex topography on the CO2 budget compared to flat terrain. The experiment is designed to estimate the effect of the topography during maximum ecosystem exchange in summer using meteorological and ecosystem conditions at solstice, the 21. of June. Systematic variation of meteorological initial conditions, plant functional types and the topography creates an ensemble that unveils the fundamental factors that dominate the differences of CO2 between simulations with topography compared to plain surfaces in the model. The sign and magnitude of the difference between the CO2 exchange over topography and over a plain simulation are strongly dependent on the CLM plant functional type, the initial temperature, the initial relative humidity, the latitude and the area height distribution of the topography. However, in this model experiment the topography is, in the mean, a sink to the CO2 budget in the order of 5% per day.

  18. Different structural preference of Ag(I) and Au(I) in neutral and cationic luminescent heteropolynuclear platinum(II) complexes: Z (U)-shaped Pt2M2 type vs. trinuclear PtM2 type.

    Science.gov (United States)

    Nishihara, Kazuki; Ueda, Misa; Higashitani, Ami; Nakao, Yoshihide; Arikawa, Yasuhiro; Horiuchi, Shinnosuke; Sakuda, Eri; Umakoshi, Keisuke

    2016-03-28

    The reactions of monocationic Pt(II) complexes bearing N^C chelate ligands and Me2pzH, [Pt(N^C)(Me2pzH)2]PF6 (N^C = 2-phenylpyridinate (ppy(-)), 2-(2,4-difluorophenyl)pyridinate (dfppy(-)), benzo[h]quinolinate (bzq(-)); Me2pzH = 3,5-dimethylpyrazole), with Ag(I) ions gave Z (or U)-shaped neutral tetranuclear Pt2Ag2 complexes [Pt2Ag2(N^C)2(Me2pz)4], while those with Au(I) ions gave neutral trinuclear PtAu2 complexes [PtAu2(N^C)(Me2pz)3]. On the contrary, the reactions of the dicationic Pt(II) complex bearing a N^N chelate ligand and Me2pzH, [Pt(bpy)(Me2pzH)2](PF6)2 (bpy = 2,2'-bipyridine), with Ag(I) and Au(I) ions both gave Z (or U)-shaped dicationic tetranuclear Pt2M2 complexes, [Pt2M2(bpy)2(Me2pz)4](PF6)2 (M = Ag, Au). The structures of heteropolynuclear Pt(II) complexes were dominated by the nature of incorporated group 11 metal ions and the charge of complexes.

  19. Crystal packing and hydrogen bonding in platinum(II) nucleotide complexes: X-ray crystal structure of [Pt(MeSCH(2)CH(2)SMe)(5'-GMP-N7)(2)].6H(2)O.

    Science.gov (United States)

    Djuran, Milos I; Milinkovic, Snezana U; Habtemariam, Abraha; Parsons, Simon; Sadler, Peter J

    2002-02-01

    We have synthesised the complex [Pt(CH(3)SCH(2)CH(2)SCH(3))(5'-GMP-N7)(2)].6H(2)O (1), where 5'-GMP is 5'-guanosine monophosphate, and determined its X-ray crystal structure. Pt(II) adopts a square-planar geometry in which the bases are coordinated head-to-tail (HT) in the Delta configuration. The nucleotide conformation in this complex is almost identical to that in the previously reported complex [Pt(en)(5'-GMP-N7)(2)].9H(2)O (2), in which there is outer sphere macrochelation via intramolecular H-bonding between the monoanionic phosphate groups and the coordinated ethylenediamine (en) NH. It is therefore apparent that intermolecular interactions rather than intramolecular H-bonding determines the orientation of the sugar-phosphate side-chain in these Pt(II) bisnucleotide complexes in the solid state.

  20. Evidence for Carbonate Surface Complexation during Forsterite Carbonation in Wet Supercritical Carbon Dioxide.

    Science.gov (United States)

    Loring, John S; Chen, Jeffrey; Bénézeth, Pascale; Qafoku, Odeta; Ilton, Eugene S; Washton, Nancy M; Thompson, Christopher J; Martin, Paul F; McGrail, B Peter; Rosso, Kevin M; Felmy, Andrew R; Schaef, Herbert T

    2015-07-14

    Continental flood basalts are attractive formations for geologic sequestration of carbon dioxide because of their reactive divalent-cation containing silicates, such as forsterite (Mg2SiO4), suitable for long-term trapping of CO2 mineralized as metal carbonates. The goal of this study was to investigate at a molecular level the carbonation products formed during the reaction of forsterite with supercritical CO2 (scCO2) as a function of the concentration of H2O adsorbed to the forsterite surface. Experiments were performed at 50 °C and 90 bar using an in situ IR titration capability, and postreaction samples were examined by ex situ techniques, including scanning electron microscopy (SEM), X-ray photoelectron spectroscopy (XPS), focused ion beam transmission electron microscopy (FIB-TEM), thermal gravimetric analysis mass spectrometry (TGA-MS), and magic angle spinning nuclear magnetic resonance (MAS NMR). Carbonation products and reaction extents varied greatly with adsorbed H2O. We show for the first time evidence of Mg-carbonate surface complexation under wet scCO2 conditions. Carbonate is found to be coordinated to Mg at the forsterite surface in a predominately bidentate fashion at adsorbed H2O concentrations below 27 μmol/m(2). Above this concentration and up to 76 μmol/m(2), monodentate coordinated complexes become dominant. Beyond a threshold adsorbed H2O concentration of 76 μmol/m(2), crystalline carbonates continuously precipitate as magnesite, and the particles that form are hundreds of times larger than the estimated thicknesses of the adsorbed water films of about 7 to 15 Å. At an applied level, these results suggest that mineral carbonation in scCO2 dominated fluids near the wellbore and adjacent to caprocks will be insignificant and limited to surface complexation, unless adsorbed H2O concentrations are high enough to promote crystalline carbonate formation. At a fundamental level, the surface complexes and their dependence on adsorbed H2O

  1. Synthesis and characterization of zinc(II, palladium(II and platinum(II complex with 2’-[1-(2-pyridinylethylidene] oxamohydrazide. The crystal structure of bis{2’-[1-(2-pyridinylethylidene]oxamohydrazido}zinc(II trihydrate

    Directory of Open Access Journals (Sweden)

    ROLAND TELLGREN

    2004-09-01

    Full Text Available Complexes of Zn(II, Pd(II and Pt(II with 2’-[1-(2-pyridinylethylidene]oxamohydrazide (Hapsox were synthesized and their structures were determined. All the complexes are of a neutral type with two apsox ligands coordinated to Zn(II and one apsox ligand coordinated to Pd(II or Pt(II. In each case, the polydentate was coordinated via pyridine and hydrazone nitrogens and a-oxyazine oxygen, forming an octahedral geometry around Zn(II, and a square planar one around Pd(II and Pt(II. The structure determination was performed by IR, 1H-NMR and 13C-NMR spectroscopy, and for the Zn(II complex by X-ray structure analysis.

  2. An in vivo highly antitumor-active tetrazolato-bridged dinuclear platinum(II) complex largely circumvents in vitro cisplatin resistance: two linkage isomers yield the same product upon reaction with 9-ethylguanine but exhibit different cytotoxic profiles.

    Science.gov (United States)

    Uemura, Masako; Suzuki, Toshihiro; Nishio, Kazuto; Chikuma, Masahiko; Komeda, Seiji

    2012-07-01

    Cytotoxicity assays of azolato-bridged dinuclear Pt(II) complexes, [{cis-Pt(NH(3))(2)}(2)(μ-OH)(μ-azolato)](2+), where the azolato was pyrazolato (1), 1,2,3-triazolato-N1,N2 (2), tetrazolato-N1,N2 (3), or tetrazolato-N2,N3 (4), were performed in cisplatin-sensitive and -resistant human non-small-cell lung cancer cell lines (PC-9 and PC-14). These complexes largely circumvented the cisplatin resistance in both cell lines, with resistance factors for 1-4 in the range of 0.5-0.8 and 0.9-2.0 for PC-9 and PC-14 cells, respectively. Complex 4 exhibited approximately 10 times the cytotoxicity of 3. When 3 and 4 were reacted with 2 molar equiv. of 9-ethylguanine (9EtG), they yielded an identical product, [{cis-Pt(NH(3))(2)(9EtG-N7)}(2)(μ-tetrazolato-N1,N3)](3+), that had N1,N3 platinum coordination through a Pt(II) migration process on the tetrazolate ring. The second-order rate kinetics of these isomers were almost the same as each other and faster than those of 1 and 2. The cytotoxicity of azolato-bridged complexes, except for 3, increases as their kinetic rates in the 9EtG reaction increase.

  3. Linear homobimetallic 4-thioacetyl-substituted NCN pincer palladium(II) and platinum(II) complexes with N-bidentate connecting units (NCN = [C6H2(CH2NMe2)2-2,6-R-4]−)

    NARCIS (Netherlands)

    Döring, K.; Taher, D.; Walfort, B.; Lutz, M.; Spek, A.L.; van Klink, G.P.M.; van Koten, G.; Lang, H.

    2008-01-01

    The synthesis and characterization of homobimetallic palladium and platinum complexes of type [(Me(O)CS-4-NCN–M ← N∩N → M–NCN-4-SC(O)Me](OTf)2 (Me(O)CS-4-NCN = [C6H2(CH2NMe2)2-2,6-SC(O)Me-4]−; N∩N = 4,4′-bipyridine (bipy); M = Pd, 12; M = Pt, 13) is reported. The required bifunctional thio-acetyl NC

  4. Synthesis of platinum(II) and palladium(II) complexes with 9,9-dihexyl-4,5-diazafluorene and their in vivo antitumour activity against Hep3B xenografted mice.

    Science.gov (United States)

    Wang, Q-W; Lam, P-L; Wong, R S-M; Cheng, G Y-M; Lam, K-H; Bian, Z-X; Ho, C-L; Feng, Y-H; Gambari, R; Lo, Y-H; Wong, W-Y; Chui, C-H

    2016-11-29

    Two complexes dichloro(9,9-dihexyl-4,5-diazafluorene)platinum(II) (Pt-DHF) and dichloro(9,9-dihexyl-4,5-diazafluorene)palladium(II) (Pd-DHF) were synthesized and their in vivo antitumour activity was investigated using an athymic nude mice model xenografted with human Hep3B carcinoma cells. Pt-DHF- and Pd-DHF-treated groups showed significant tumour growth inhibition (with about 9-fold and 3-fold tumour growth retardation) when compared with the vehicle control group. The liver toxicology effects on the animals of the two compounds were investigated. Pt-DHF and Pd-DHF-treated groups had a lower alanine transaminase and aspartate transaminase values than those of the vehicle treated group as the animals from the vehicle control group had very heavy hepatoma burden. We assume that both complexes could be further investigated as effective antitumour agents and it is worthwhile to study their underlying working mechanism.

  5. Complexity of carbon market from multi-scale entropy analysis

    Science.gov (United States)

    Fan, Xinghua; Li, Shasha; Tian, Lixin

    2016-06-01

    Complexity of carbon market is the consequence of economic dynamics and extreme social political events in global carbon markets. The multi-scale entropy can measure the long-term structures in the daily price return time series. By using multi-scale entropy analysis, we explore the complexity of carbon market and mean reversion trend of daily price return. The logarithmic difference of data Dec16 from August 6, 2010 to May 22, 2015 is selected as the sample. The entropy is higher in small time scale, while lower in large. The dependence of the entropy on the time scale reveals the mean reversion of carbon prices return in the long run. A relatively great fluctuation over some short time period indicates that the complexity of carbon market evolves consistently with economic development track and the events of international climate conferences.

  6. Defect complexes in carbon and boron nitride nanotubes

    CSIR Research Space (South Africa)

    Mashapa, MG

    2012-05-01

    Full Text Available The effect of defect complexes on the stability, structural and electronic properties of single-walled carbon nanotubes and boron nitride nanotubes is investigated using the ab initio pseudopotential density functional method implemented...

  7. Raman and infrared spectroscopy, DFT calculations, and vibrational assignment of the anticancer agent picoplatin: performance of long-range corrected/hybrid functionals for a platinum(II) complex.

    Science.gov (United States)

    Malik, Magdalena; Wysokiński, Rafał; Zierkiewicz, Wiktor; Helios, Katarzyna; Michalska, Danuta

    2014-08-28

    Picoplatin, cis-[PtCl2(NH3)(2-picoline)], is a new promising anticancer agent undergoing clinical trials, which reveals high efficacy against many tumors and greatly reduced toxicity, in comparison to cisplatin. In this work, we present for the first time the Fourier-transform Raman and infrared spectra of picoplatin, in the region of 3500-50 cm(-1). The comprehensive theoretical studies on the molecular structure, the nature of Pt-ligand bonding, vibrational frequencies, and intensities were performed by employing different DFT methods, including hybrid (PBE0, mPW1PW, and B3LYP) and long-range-corrected hybrid density functionals (LC-ωPBE, CAM-B3LYP). Various effective core potentials (ECP) and basis sets have been used. In the prediction of the molecular structure of picoplatin, the best results have been obtained by LC-ωPBE, followed by PBE0, mPW1PW, and CAM-B3LYP density functionals, while the least accurate is B3LYP. The use of the LanL2TZ(f) ECP/basis set for Pt, in conjunction with all tested DFT methods, improves the calculated geometry of the title complex. The PBE0, mPW1PW, and CAM-B3LYP methods have shown the best performance in the calculations of the frequencies of Pt-ligand vibrations. A clear-cut assignment of all the bands in the IR and Raman spectra have been made on the basis of the calculated potential energy distribution (PED). The nature of the "vibrational signatures" of picoplatin have been determined. These results are indispensable for further investigation on drug-target interactions using vibrational spectroscopy.

  8. Post-column reaction detector for platinum(II) antieoplastic agents

    Energy Technology Data Exchange (ETDEWEB)

    Marsh, K.C.; Sternson, L.A.; Repta, A.J.

    1984-03-01

    The development and evaluation of a post-column reaction detector sensitive to platinum(II) complexes is presented in which sodium bisulfite is used as the derivatizing agent with potassium dichromate as an activating agent. The influences of mobile phase changes (i.e., pH, organic modifiers, electrolytes), oxygen, metal ions, and order of reagent addition on reaction kinetics and product yield are defined and used in optimization of detector response. Detection at lambda/sub max/ 290 nm results in an on-line post-column sensitivity of 40-60 ng/mL for selected cis-dichloroplatinum complexes and a sensitivity of 300-1200 ng/mL for four (substituted)-malonato-platinum complexes. The reaction detector is used to monitor the kinetics of aquation of cisplatin (CDDP) and to quantitate CDDP degradation in plasma. As the sensitivity for CDDP in plasma is comparable to that achieved from high pressure liquid chromatography (HPLC) effluent fractionation/off-line flameless atomic absorption (AAS) quantitation, significant utilitiy for this time-efficient post-column reactor in clinical analysis is suggested. 33 references, 8 figures, 2 tables.

  9. Structure and reactivity of a unique Y-shaped tricoordinate bis(silyl)platinum(II)-NHC complex

    NARCIS (Netherlands)

    Berthon-Gelloz, G.; de Bruin, B.; Tinant, B.; Markó, I.E.

    2009-01-01

    A unique, three-coordinate Y-shaped bis(silyl)platinum(II) complex was isolated and characterized. DFT studies on a model system shed light on the nature of this unusual coordination mode for platinum(II).

  10. Novel platinum(II) compounds with O,S bidentate ligands: synthesis, characterization, antiproliferative properties and biomolecular interactions.

    Science.gov (United States)

    Mügge, Carolin; Liu, Ruiqi; Görls, Helmar; Gabbiani, Chiara; Michelucci, Elena; Rüdiger, Nadine; Clement, Joachim H; Messori, Luigi; Weigand, Wolfgang

    2014-02-28

    Cisplatin and its analogues are first-line chemotherapeutic agents for the treatment of numerous human cancers. A major inconvenience in their clinical use is their strong tendency to link to sulfur compounds, especially in kidney, ultimately leading to severe nephrotoxicity. To overcome this drawback we prepared a variety of platinum complexes with sulfur ligands and analyzed their biological profiles. Here, a series of six platinum(II) compounds bearing a conserved O,S binding moiety have been synthesized and characterized as experimental anticancer agents. The six compounds differ in the nature of the O,S bidentate β-hydroxydithiocinnamic alkyl ester ligand where both the substituents on the aromatic ring and the length of the alkyl chain may be varied. The two remaining coordination positions at the square-planar platinum(II) center are occupied by a chloride ion and a DMSO molecule. These novel platinum compounds showed an acceptable solubility profile in mixed DMSO-buffer solutions and an appreciable stability at physiological pH as judged from analysis of their time-course UV-visible absorption spectra. Their anti-proliferative and pro-apoptotic activities were tested against the cisplatin-resistant lung cancer cell line A549. Assays revealed significant effects of the sample drugs at low concentrations (in the μmolar range); initial structure-activity-relationships are proposed. The activity of the apoptosis-promoting protein caspase 3/7 was determined; results proved that these novel platinum compounds, under the chosen experimental conditions, preferentially induce apoptosis over necrosis. Reactions with the model proteins cytochrome c, lysozyme and albumin were studied by ESI MS and ICP-OES to gain preliminary mechanistic information. The tested compounds turned out to metalate the mentioned proteins to a large extent. In view of the obtained results these novel platinum complexes qualify themselves as promising cytotoxic agents and merit, in our

  11. Interpreting effects of structure variations induced by temperature and pressure on luminescence spectra of platinum(II) bis(dithiocarbamate) compounds.

    Science.gov (United States)

    Poirier, Stéphanie; Roberts, Ryan J; Le, Debbie; Leznoff, Daniel B; Reber, Christian

    2015-04-20

    Luminescence spectra of two square-planar dithiocarbamate complexes of platinum(II) with different steric bulk, platinum(II) bis(dimethyldithiocarbamate) (Pt(MeDTC)2) and platinum(II) bis(di(o-pyridyl)dithiocarbamate) (Pt(dopDTC)2), are presented at variable temperature and pressure. The spectra show broad d-d luminescence transitions with maxima at approximately 13500 cm(-1) (740 nm). Variations of the solid-state spectra with temperature and pressure reveal intrinsic differences due to subtle variations of molecular and crystal structures, reported at 100 and 296 K for Pt(dopDTC)2. Luminescence maxima of Pt(MeDTC)2 shift to higher energy as temperature increases by +320 cm(-1) for an increase by 200 K, mainly caused by a bandwidth increase from 3065 to 4000 cm(-1) on the high-energy side of the band over the same temperature range. Luminescence maxima of Pt(dopDTC)2 shift in the opposite direction by -460 cm(-1) for a temperature increase by 200 K. The bandwidth of approximately 2900 cm(-1) does not vary with temperature. Both ground and emitting-state properties and subtle structural differences between the two compounds lead to this different behavior. Luminescence maxima measured at variable pressure show shifts to higher energy by +47 ± 3 and +11 ± 1 cm(-1)/kbar, for Pt(MeDTC)2 and Pt(dopDTC)2, respectively, a surprising difference by a factor of 4. The crystal structures indicate that decreasing intermolecular interactions with increasing pressure are likely to contribute to the exceptionally high shift for Pt(MeDTC)2.

  12. Activation volume measurement for C[bond]H activation. Evidence for associative benzene substitution at a platinum(II) center.

    Science.gov (United States)

    Procelewska, Joanna; Zahl, Achim; van Eldik, Rudi; Zhong, H Annita; Labinger, Jay A; Bercaw, John E

    2002-06-03

    The reaction of the platinum(II) methyl cation [(N-N)Pt(CH(3))(solv)](+) (N-N = ArN[double bond]C(Me)C(Me)[double bond]NAr, Ar = 2,6-(CH(3))(2)C(6)H(3), solv = H(2)O (1a) or TFE = CF(3)CH(2)OH (1b)) with benzene in TFE/H(2)O solutions cleanly affords the platinum(II) phenyl cation [(N-N)Pt(C(6)H(5))(solv)](+) (2). High-pressure kinetic studies were performed to resolve the mechanism for the entrance of benzene into the coordination sphere. The pressure dependence of the overall second-order rate constant for the reaction resulted in Delta V(++) = -(14.3 +/- 0.6) cm(3) mol(-1). Since the overall second order rate constant k = K(eq)k(2), Delta V(++) = Delta V degrees (K(eq)) + Delta V(++)(k(2)). The thermodynamic parameters for the equilibrium constant between 1a and 1b, K(eq) = [1b][H(2)O]/[1a][TFE] = 8.4 x 10(-4) at 25 degrees C, were found to be Delta H degrees = 13.6 +/- 0.5 kJ mol(-1), Delta S degrees = -10.4 +/- 1.4 J K(-1) mol(-1), and Delta V degrees = -4.8 +/- 0.7 cm(3) mol(-1). Thus DeltaV(++)(k(2)) for the activation of benzene by the TFE solvento complex equals -9.5 +/- 1.3 cm(3) mol(-1). This significantly negative activation volume, along with the negative activation entropy for the coordination of benzene, clearly supports the operation of an associative mechanism.

  13. Platinum Group Thiophenoxyimine Complexes: Syntheses,Crystallographic and Computational Studies of Structural Properties

    Energy Technology Data Exchange (ETDEWEB)

    Krinsky, Jamin L.; Arnold, John; Bergman, Robert G.

    2006-10-03

    Monomeric thiosalicylaldiminate complexes of rhodium(I) and iridium(I) were prepared by ligand transfer from the homoleptic zinc(II) species. In the presence of strongly donating ligands, the iridium complexes undergo insertion of the metal into the imine carbon-hydrogen bond. Thiophenoxyketimines were prepared by non-templated reaction of o-mercaptoacetophenone with anilines, and were complexed with rhodium(I), iridium(I), nickel(II) and platinum(II). X-ray crystallographic studies showed that while the thiosalicylaldiminate complexes display planar ligand conformations, those of the thiophenoxyketiminates are strongly distorted. Results of a computational study were consistent with a steric-strain interpretation of the difference in preferred ligand geometries.

  14. Electrochemical water oxidation with carbon-grafted iridium complexes.

    Science.gov (United States)

    deKrafft, Kathryn E; Wang, Cheng; Xie, Zhigang; Su, Xin; Hinds, Bruce J; Lin, Wenbin

    2012-02-01

    Hydrogen production from water splitting provides a potential solution to storing harvested solar energy in chemical fuels, but this process requires active and robust catalysts that can oxidize water to provide a source of electrons for proton reduction. Here we report the direct, covalent grafting of molecular Ir complexes onto carbon electrodes, with up to a monolayer coverage. Carbon-grafted Ir complexes electrochemically oxidize water with a turnover frequency of up to 3.3 s(-1) and a turnover number of 644 during the first hour. Electrochemical water oxidation with grafted catalysts gave enhanced rates and stability compared to chemically driven water oxidation with the corresponding molecular catalysts. This strategy provides a way to systematically evaluate catalysts under tunable conditions, potentially providing new insights into electrochemical water oxidation processes and water oxidation catalyst design.

  15. Yellow luminescence of gallium nitride generated by carbon defect complexes.

    Science.gov (United States)

    Demchenko, D O; Diallo, I C; Reshchikov, M A

    2013-02-22

    We demonstrate that yellow luminescence often observed in both carbon-doped and pristine GaN is the result of electronic transitions via the C(N)-O(N) complex. In contrast to common isolated defects, the C(N)-O(N) complex is energetically favorable, and its calculated optical properties, such as absorption and emission energies, a zero phonon line, and the thermodynamic transition level, all show excellent agreement with measured luminescence data. Thus, by combining hybrid density functional theory and experimental measurements, we propose a solution to a long-standing problem of the GaN yellow luminescence.

  16. Nanoporous carbon sorbent for molecular-sieve chromatography of lipoprotein complex

    Science.gov (United States)

    Kerimkulova, A. R.; Mansurova, B. B.; Gil'manov, M. K.; Mansurov, Z. A.

    2012-06-01

    The physicochemical characteristics of carbon sorbents are investigated. Electron microscopy data for the sorbent and separated lipoprotein complex are presented. It is found that the obtained carbon sorbent possess high porosity. Nanoporous carbon sorbents for the chromatography of molecular-sieve markers are obtained and tested. The applicability of nanoporous carbon sorbents for separation of lipoprotein complexes (LPC) is investigated.

  17. Comparison of Intracellular Stress Response of NCI-H526 Small Cell Lung Cancer (SCLC) Cells to Platinum(II) Cisplatin and Platinum(IV) Oxoplatin

    Energy Technology Data Exchange (ETDEWEB)

    Hamilton, Gerhard [Ludwig Boltzmann Cluster of Translational Oncology, A-1090 Vienna (Austria)

    2014-07-08

    In attempts to develop an orally applicable platinum-based drug, platinum(IV) drugs which exhibit higher in vivo stability compared to the platinum(II) drug cisplatin were formulated. The first such chemotherapeutic agent, namely satraplatin, failed to receive approval. In the present work, we checked the initial cellular stress response of the chemosensitive NCI-H526 small cell lung cancer (SCLC) cells by determination of the relative phosphorylation of 46 specific phosphorylation sites of 38 selected proteins in a six hours response to cisplatin (platinum(II)) or oxoplatin (platinum(IV)), respectively. Oxoplatin is considered as prodrug of cisplatin, although several findings point to differences in intracellular effects. Cisplatin induced hyperphosphorylation of p38α MAPK and AMPKα1, whereas oxoplatin treatment resulted in increased phosphorylation of a large number of signaling proteins involved in stress response/drug resistance, including JNK, GSK-3α, AMPKα1, src kinases, STATs, CHK-2 and especially focal adhesion kinase (FAK). Cisplatin exerts markedly higher cytotoxicity upon four hours short-term exposure in comparison to oxoplatin and, correspondingly, the extended initial stress response to the platinum(IV) drug oxoplatin thus is expected to increase clinical drug resistance. Induction of a substantial stress response to any prodrug of a platinum-based compound may likewise limit the effectivity of its active metabolite(s), such contributing to the failure of selected derivatized platinum complexes.

  18. Comparison of Intracellular Stress Response of NCI-H526 Small Cell Lung Cancer (SCLC Cells to Platinum(II Cisplatin and Platinum(IV Oxoplatin

    Directory of Open Access Journals (Sweden)

    Gerhard Hamilton

    2014-07-01

    Full Text Available In attempts to develop an orally applicable platinum-based drug, platinum(IV drugs which exhibit higher in vivo stability compared to the platinum(II drug cisplatin were formulated. The first such chemotherapeutic agent, namely satraplatin, failed to receive approval. In the present work, we checked the initial cellular stress response of the chemosensitive NCI-H526 small cell lung cancer (SCLC cells by determination of the relative phosphorylation of 46 specific phosphorylation sites of 38 selected proteins in a six hours response to cisplatin (platinum(II or oxoplatin (platinum(IV, respectively. Oxoplatin is considered as prodrug of cisplatin, although several findings point to differences in intracellular effects. Cisplatin induced hyperphosphorylation of p38α MAPK and AMPKα1, whereas oxoplatin treatment resulted in increased phosphorylation of a large number of signaling proteins involved in stress response/drug resistance, including JNK, GSK-3α, AMPKα1, src kinases, STATs, CHK-2 and especially focal adhesion kinase (FAK. Cisplatin exerts markedly higher cytotoxicity upon four hours short-term exposure in comparison to oxoplatin and, correspondingly, the extended initial stress response to the platinum(IV drug oxoplatin thus is expected to increase clinical drug resistance. Induction of a substantial stress response to any prodrug of a platinum-based compound may likewise limit the effectivity of its active metabolite(s, such contributing to the failure of selected derivatized platinum complexes.

  19. The complexity of carbon flux time series in Europe

    Science.gov (United States)

    Lange, Holger; Sippel, Sebastian

    2014-05-01

    Observed geophysical time series usually exhibit pronounced variability, part of which is process-related and deterministic ("signal"), another part is due to random fluctuations ("noise"). To discern these two sources for fluctuations is notoriously difficult using conventional analysis methods, unless sophisticated model assumptions are made. Here, we present an almost parameter-free innovative approach with the potential to draw a distinction between deterministic processes and structured noise, based on ordinal pattern statistics. The method determines one measure for the information content of time series (Shannon entropy) and two complexity measures, one based on global properties of the order pattern distribution (Jensen-Shannon complexity) and one based on local (derivative) properties (Fisher information or complexity). Each time series gets classified via its location in an entropy-complexity plane; using this representation, the method draws a qualitative distinction between different types of natural processes. As a case study, we investigate Gross Primary Productivity (GPP) and respiration which are key variables in terrestrial ecosystems quantifying carbon allocation and biomass growth of vegetation. Changes in GPP and ecosystem respiration can be induced by land use change, environmental disasters or extreme events, and changing climate. Numerous attempts to quantify these variables on larger spatial scales exist. Here, we investigate gridded time series at monthly resolution for the European continent either based on upscaled measurements ("observations") or modelled with two different process-based terrestrial ecosystem models ("simulations"). The complexity analysis is either visualized as maps of Europe showing "hotspots" of complexity for GPP and respiration, or used to provide a detailed observations-simulations and model-model comparison. Values found for information and complexity will be compared to known artificial reference processes

  20. Carbonate complexation of Np(IV) in alkaline solutions

    Energy Technology Data Exchange (ETDEWEB)

    Kitamura, Akira [Japan Nuclear Cycle Development Inst., Tokai Works, Tokai, Ibaraki (Japan); Kohara, Yukitoshi [Inspection Development Company Ltd., Tokai, Ibaraki (Japan)

    2002-12-01

    Reliable thermodynamic data for actinide (IV) have been required. The solubility of Np(IV) in carbonate media was studied for determination of thermodynamic data. The concentration of dissolved Np(IV) was measured with ionic strengths from 0.5 to 2.9 M (M {identical_to} mol{center_dot}dm{sup -3}), hydrogen-ion concentration exponent (pH{sub c} = -log[H{sup +}]) from 8 to 13 and with the total carbonate concentration (C{sub T}) from 5x10{sup -3} M to 7x10{sup -1} M by an oversaturation method. It was found that the solubility of Np(IV) decreased with increasing pH{sub c} and increased with increasing C{sub T}. On the basis of analysis of the solubility data, the dominant aqueous species of Np(IV) were expected to be Np(CO{sub 3}){sub 4}{sup 4-}, Np(CO{sub 3}){sub 2}(OH){sub 2}{sup 2-} and Np(CO{sub 3}){sub 2}(OH){sub 4}{sup 4-} in the present study. The apparent equilibrium constants of the carbonate and carbonatohydroxo complexes were obtained in the respective ionic strength and the equilibrium constants at the zero ionic strength were extrapolated. The obtained equilibrium constants supported the literature values strongly, and contributed to improve the reliability of the thermodynamic data. (author)

  1. A Bimetallic Aluminium(Salphen) Complex for the Synthesis of Cyclic Carbonates from Epoxides and Carbon Dioxide.

    Science.gov (United States)

    Wu, Xiao; North, Michael

    2017-01-10

    A bimetallic aluminium(salphen) complex is reported as a sustainable, efficient and inexpensive catalyst for the synthesis of cyclic carbonates from epoxides and carbon dioxide. In the presence of this complex and tetrabutylammonium bromide, terminal and internal epoxides reacted at 50 °C and 10 bar carbon dioxide pressure to afford their corresponding cyclic carbonates in yields of 50-94 % and 30-71 % for terminal and internal cyclic carbonates, respectively. Mechanistic studies using deuterated epoxides and an analogous monometallic aluminium(salphen) chloride complex support a mechanism for catalysis by the bimetallic complex, which involves intramolecular cooperative catalysis between the two aluminium centres. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  2. Cryogenic Origin for Mars Analog Carbonates in the Bockfjord Volcanic Complex Svalbard (Norway)

    Science.gov (United States)

    Amundsen, H. E. F.; Benning, L.; Blake, D. F.; Fogel, M.; Ming, D.; Skidmore, M.; Steele, A.

    2011-01-01

    The Sverrefjell and Sigurdfjell eruptive centers in the Bockfjord Volcanic Complex (BVC) on Svalbard (Norway) formed by subglacial eruptions ca. 1 Ma ago. These eruptive centers carry ubiquitous magnesian carbonate deposits including dolomitemagnesite globules similar to those in the Martian meteorite ALH84001. Carbonates in mantle xenoliths are dominated by ALH84001 type carbonate globules that formed during quenching of CO2-rich mantle fluids. Lava hosted carbonates include ALH84001 type carbonate globules occurring throughout lava vesicles and microfractures and massive carbonate deposits associated with vertical volcanic vents. Massive carbonates include < or equal 5 cm thick magnesite deposits protruding downwards into clear blue ice within volcanic vents and carbonate cemented lava breccias associated with volcanic vents. Carbonate cements comprise layered deposits of calcite, dolomite, huntite, magnesite and aragonite associated with ALH84001 type carbonate globules lining lava vesicles. Combined Mossbauer, XRD and VNIR data show that breccia carbonate cements at Sverrefjell are analog to Comanche carbonates at Gusev crater.

  3. Complexation of aromatic drugs with single-walled carbon nanotubes

    Science.gov (United States)

    Buchelnikov, Anatoly S.; Voronin, Dmitry P.; Kostjukov, Viktor V.; Deryabina, Tatyana A.; Khrapatiy, Sergii V.; Prylutskyy, Yuriy I.; Ritter, Uwe; Evstigneev, Maxim P.

    2014-07-01

    We report a detailed study of the complexation of aromatic molecules and drugs with the surface of single-walled carbon nanotubes (SWCNTs, the diameter and the length ranges are 0.5-2 nm and 1-5 μm, respectively) in terms of equilibrium binding constants, K. It is found that the binding constants have magnitudes of the order of 104-105 M-1 and that there is some ligand specificity to the SWCNT surface depending on the structure of the aromatic molecule. The observed specificity is strongly governed by the curvature of the ligand chromophore and the type of side chains, resulting in the highest K for methylene blue which closely matches the curvature of the SWCNT surface. Stabilization of the drug-SWCNT complexes is found to be mainly due to intermolecular van der Waals forces and to a lesser extent by hydrophobic interactions. The approach suggested for determination of the binding parameters may be used as an alternative, or complementary, to standard Langmuir analysis.

  4. Investigation of the configurational and conformational influences on the hormonal activity of 1,2-bis(2,6-dichloro-4-hydroxyphenyl)ethylenediamines and of their platinum(II) complexes. 1. Synthesis, estradiol receptor affinity, and estrogenic activity of diastereomeric [N-alkyl- and N,N'-dialkyl-1,2- bis(2,6-dichloro-4-hydroxyphenyl)ethylenediamine]dichloroplatinum(II) complexes.

    Science.gov (United States)

    Gust, R; Niebler, K; Schönenberger, H

    1995-06-09

    N-Monoalkylated (Et) and N,N'-dialkylated (Me and Et) 1,2-bis(2,6-dichloro-4-hydroxyphenyl)-ethylenediamines and their dichloroplatinum(II) complexes were synthesized, and their configuration and conformational behavior were 1H-NMR spectroscopically clarified. The latter was brought in relation to their relative binding affinity (RBA) to the estrogen receptor as well as to their estrogenic potency. In contrast to the RR/SS-configurated diamines, the R/S-configurated ones showed marked estrogenic properties which correlate with the RBA's. In the related R/S-configurated complexes the estrogenic activity is determined by the same structural requirements as in the diamine series. However, a correlation between RBA's and estrogenic potencies is missing. The connection between spatial structure and activity is discussed by use of a drug-receptor model recently proposed by Höltje and Dall.

  5. Theoretical investigation of hydrogen bonding between water and platinum(II): an atom in molecule (AIM) study

    Science.gov (United States)

    Li, Yan; Zhang, Guiqiu; Chen, Dezhan

    2012-02-01

    Recently, Rizzato et al. [Angew. Chem. Int. Ed. 49, 7440 (2010)] [1] reported a hydrogen-bonding-like interaction between a water molecule and a d8 metal ion (PtII) based on neutron diffraction, and provided the first crystallographic evidence for this interaction. We studied the hydrogen bonding of the O-H ... Pt interaction theoretically using atoms in molecule (AIM) and natural bond orbital analysis (NBO) in the crystallographic geometries. The method used density functional theory (DFT) with the hybrid B3LYP function. For platinum atoms, we used the Los Alamos National Laboratory 2-Double-Zeta (LANL2DZ) basis set, and for the other atoms we used 6-311++G(d,p) basis sets. Criteria based on a topological analysis of the electron density were used in order to characterize the nature of interactions in the complexes. The main purpose of the present work is to provide an answer to the following questions: Why can a filled d orbital of square-planar d8 metal ions such as platinum(II) also act as hydrogen-bond acceptors? Can a study based on the electron charge density answer this question? A good correlation between the density at the intermolecular bond critical point and the energy interaction was found. The interaction is mainly closed-shell and there is some charge transfer in this system.

  6. Multiphase carbon and its properties in complex mixtures

    Energy Technology Data Exchange (ETDEWEB)

    van Thiel, M.; Ree, F.H.

    1990-09-01

    We describe some key features of a carbon three-phase equation of state and a high-pressure high temperature mixture model in which it is used. Electronic terms in the carbon model have been investigated with INFERNO (atom in a cell model). The Lindeman criterion for melting is rederived for the anisotropic structure of the graphite lattice. The curvature of the graphite melting line is constrained by the evidence for the positive slope of the diamond melting line. The importance of carbon is apparent from various experiments on shock generated mixtures. The model allows us to estimate the energy of carbon clusters produced in a detonating mixture. A cluster model with specific surface structure is used to predict this energy. 41 refs., 7 figs., 4 tabs.

  7. Understanding the Carbon Isotopic Signature in Complex Environmental Matrices

    Directory of Open Access Journals (Sweden)

    Claudio Natali

    2014-12-01

    Full Text Available Elemental and isotopic analyses of carbon in environmental matrices usually integrate multiple sources having distinct concentration (wt% and 13C/12C isotopic ratio. Interpretation necessarily needs the characterization of the diverse end-members that usually are constituted by carbonate, organic and elemental components. In this view, we developed a routine protocol based on the analytical coupling of elementary and isotopic compositions that is able to discriminate the inorganic (TIC and organic (TOC contributions to the total carbon (TC content. The procedure is only based on thermal destabilization of the different carbon species and has been successfully applied on different environmental matrices (rocks, soils, biological samples with a mean C elemental and isotopic recovery of 99% (SD = 3% and -0.3‰ (SD = 0.3‰, respectively. The thermal speciation lead us to define precise isotopic end-members whose are unaffected by any chemical treatment of the samples. The approach allows accurate mass balance calculation that represents a powerful tool to quantify the distinct carbon species.

  8. Methylation of secondary amines with dialkyl carbonates and hydrosilanes catalysed by iron complexes.

    Science.gov (United States)

    Zheng, Jianxia; Darcel, Christophe; Sortais, Jean-Baptiste

    2014-11-25

    Methylation of secondary amines was achieved using dimethyl carbonate or diethyl carbonate as the C1 source under the catalysis of well-defined half-sandwich iron complexes bearing an N-heterocyclic carbene ligand. The reaction proceeded under mild conditions in the presence of hydrosilanes as the reductants, and the amines were obtained with good to excellent isolated yields.

  9. Interaction of carbon-vacancy complex with minor alloying elements of ferritic steels

    Science.gov (United States)

    Bakaev, A.; Terentyev, D.; He, X.; Zhurkin, E. E.; Van Neck, D.

    2014-08-01

    Interstitial carbon, dissolved in bcc matrix of ferritic steels, plays an important role in the evolution of radiation-induced microstructure since it exhibits strong interaction with vacancies. Frequent formation and break-up of carbon-vacancy pairs, occurring in the course of irradiation, affect both kinetics of the accumulation of point defect clusters and carbon spatial distribution. The interaction of typical alloying elements (Mn, Ni, Cu, Si, Cr and P) in ferritic steels used as structural materials in nuclear reactors with a carbon-vacancy complex is analyzed using ab initio techniques. It is found that all the considered solutes form stable triple clusters resulting in the increase of the total binding energy by 0.2-0.3 eV. As a result of the formation of energetically favourable solute-carbon-vacancy triplets, the dissociation energy for vacancy/carbon emission is also increased by ∼0.2-0.3 eV, suggesting that the solutes enhance thermal stability of carbon-vacancy complex. Association of carbon-vacancy pairs with multiple solute clusters is found to be favorable for Ni, Cu and P. The energetic stability of solute(s)-carbon-vacancy complexes was rationalized on the basis of pairwise interaction data and by analyzing the variation of local magnetic moments on atoms constituting the clusters.

  10. Complex permittivity of composites based on dielectric matrices with carbon nanotubes

    Science.gov (United States)

    Usanov, D. A.; Skripal', A. V.; Romanov, A. V.

    2011-01-01

    The transmission spectra of microwave electromagnetic radiation interacting with a sample are used to determine the complex permittivity of a composite material based on a two-component epoxy adhesive having a certain volume fraction of inclusions in the form of multilayer carbon nanotubes or fine graphite particles. An inverse problem is solved for the dependence of the complex permittivity of the composite material on the volume fraction of carbon nanotubes, and their permittivity and average bulk electrical conductivity are determined.

  11. Vacancy complexes in carbon and boron nitride nanotubes

    CSIR Research Space (South Africa)

    Mashapa, MG

    2012-10-01

    Full Text Available The effect of divacancies on the stability, structural and electronic properties of carbon and boron nitride nanotubes is studied using the ab initio density functional method. VBBN is more stable in the boron-rich and less stable in the nitrogen...

  12. New heteronuclear gold(I)-platinum(II) complexes with cytotoxic properties : Are two metals better than one?

    NARCIS (Netherlands)

    Wenzel, Margot; Bigaeva, Emilia; Richard, Philippe; Le Gendre, Pierre; Picquet, Michel; Casini, Angela; Bodio, Ewen

    2014-01-01

    A series of mono- and heterodinuclear gold(I) and platinum(II) complexes with a new bipyridylamine-phosphine ligand have been synthesized and characterized. The X-ray structures of the ligand precursor 4-iodo-N,N-di(pyridin-2-yl)benzamide, and of one gold derivative are reported. All the complexes d

  13. Computational studies on the excited states of luminescent platinum(II) alkynyl systems of tridentate pincer ligands in radiative and nonradiative processes.

    Science.gov (United States)

    Lam, Wai Han; Lam, Elizabeth Suk-Hang; Yam, Vivian Wing-Wah

    2013-10-09

    Platinum(II) alkynyl complexes of various tridentate pincer ligands, [Pt(trpy)(C≡CR)](+) (trpy = 2,2':6',2″-terpyridine), [Pt(R'-bzimpy)(C≡CR)](+) (R'-bzimpy = 2,6-bis(N-alkylbenzimidazol-2'-yl)pyridine and R' = alkyl), [Pt(R'-bzimb)(C≡CR)] (R'-bzimb = 1,3-bis(N-alkylbenzimidazol-2'-yl)benzene and R' = C4H9), have been found to possess rich photophysical properties. The emission in dilute solutions of [Pt(trpy)(C≡CR)](+) originated from a triplet alkynyl-to-tridentate pincer ligand-to-ligand charge transfer (LLCT) excited state, with mixing of a platinum-to-tridentate pincer ligand metal-to-ligand charge transfer (MLCT) excited state, while that of [Pt(R'-bzimb)(C≡CR)] originated from a triplet excited state of intraligand (IL) character of the tridentate ligand mixed with a platinum-to-tridentate ligand MLCT character. Interestingly, both emissions were observed in [Pt(R'-bzimpy)(C≡CR)](+) in some cases. In addition, [Pt(R'-bzimb)(C≡CR)] displayed a photoluminescence quantum yield higher than that of [Pt(R'-bzimpy)(C≡CR)](+). Computational studies have been performed on the representative complexes [Pt(trpy)(C≡CPh)](+) (1), [Pt(R'-bzimpy)(C≡CPh)](+) (2), and [Pt(R'-bzimb)(C≡CPh)] (3), where R' = CH3 and Ph = C6H5, to provide an in-depth understanding of the nature of their emissive origin as well as the radiative and nonradiative processes. In particular, the factors governing the ordering of the triplet excited states and radiative decay rate constants of the emissive state ((3)ES) have been examined. The potential energy profiles for the deactivation process from the (3)ES via triplet metal-centered ((3)MC) states have also been explored. This work reveals for the first time the potential energy profiles for the thermal deactivation pathway of square planar platinum(II) complexes.

  14. Anoxic carbon degradation in Arctic sediments: Microbial transformations of complex substrates

    DEFF Research Database (Denmark)

    2005-01-01

    Complex substrates are degraded in anoxic sediments by the concerted activities of diverse microbial communities. To explore the effects of substrate complexity on carbon transformations in permanently cold anoxic sediments, four substrates—Spirulina cells, Isochrysis cells, and soluble high...... of carbon degradation diverged, with an additional 43%, 32%, 33%, and 8% of Isochrysis, Iso-Ex, Spirulina, and Spir-Ex carbon respired to CO2 over the next 750 h of incubation. Somewhat surprisingly, the soluble, carbohydrate-rich extracts did not prove to be more labile substrates than the whole cells from...... which they were derived. Although Spirulina and Iso-Ex differed in physical and chemical characteristics (solid/soluble, C/N ratio, lipid and carbohydrate content), nearly identical quantities of carbon were respired to CO2. In contrast, only 15% of Spir-Ex carbon was respired, despite the initial burst...

  15. Complex Study of the Physical Properties of Reticulated Vitreous Carbon

    Science.gov (United States)

    Alifanov, O. M.; Cherepanov, V. V.; Morzhukhina, A. V.

    2015-01-01

    We give an example of using a two-level identifi cation system incorporating an augmented mathematical model covering the structure, the thermal, electrophysical, and optical properties of nonmetallic ultraporous reticulated materials. The model, when combined with a nonstationary thermal experiment and methods of the theory of inverse heat transfer problems, permits determining the little studied characteristics of the above materials. We present some of the results of investigations of reticulated vitreous carbon confirming the possibility of using it in a number of engineering applications.

  16. Treatment of metal-containing wastewater by adsorption of metal-chelate complexes onto activated carbon

    Energy Technology Data Exchange (ETDEWEB)

    Shay, M.A.

    1989-01-01

    To eliminate difficulties associated with interference of chelating or complexing agents on precipitation of heavy metals from wastewaters, the feasibility of a process which utilized chelating agents in the removal of the heavy metals was investigated. Heavy metal ions were removed from simulated metal plating wastewater by sorption of a heavy metal chelate complex onto activated carbon. In this process, a chelate which might be present in a wastewater could be used in removal of a heavy metal, rather than interfere with its removal. System development of a continuous flow process consisted of bench scale column tests to answer questions about key adsorption column operating parameters. The metals investigated were Cu(II), Ni(II) and Zn(II). Hydrogen ion concentration had the largest effect on removal of heavy metalchelate complexes, but contact time and heavy metal:chelate ratio were important. The normal contact time for activated carbon columns of 30 to 60 minutes was found adequate to achieve heavy metal-chelate removals of at least 90% for citrate or EDTA complexes. For citrate complexes better removals were achieved at heavy metal:chelate ratios greater than 1:1. For EDTA, there was no advantage to ratios greater than 1:1. Increasing pH, at least to pH 9.0, increased the heavy metal chelate removal; however, for EDTA, removals greater than 90% could be achieved at a pH as low as 3.0. The maximum amount of Cu(II)-citrate complex that could be removed was 2.8 mg per gram of carbon, the maximum amount for Zn(II)citrate complex was 1.2 mg per gram of carbon, and for Ni(II)-citrate, the maximum was 1.3 mg per gram of carbon. For the EDTA complexes, the maximum removal was 2.1 mg of Cu(II)-EDTA complex per gram of carbon, 6.9 mg of Zn(II)-EDTA complex per gram of carbon, and 3.2 mg of Ni(II)-EDTA complex per gram of carbon.

  17. The Versatile Behavior of Platinum Alkyne Complexes towards XeF2 : Formation of Fluorovinyl and Fluorido Complexes.

    Science.gov (United States)

    Berger, Josefine; Braun, Thomas; Ahrens, Theresia; Kläring, Paul; Laubenstein, Reik; Braun-Cula, Beatrice

    2017-07-03

    Reactions of platinum(0) tolane complexes, bearing a chelating ligand with P and N donor atoms, with the electrophilic fluorinating agent XeF2 give facile access to platinum(II) β-fluorovinyl fluorido complexes. A series of new platinum(II) β-fluorovinyl complexes have been synthesized and were structurally characterized. Further oxidation with XeF2 led to ortho-metalated platinum(IV) fluorido compounds. Additional reactions of platinum(0) tolane complexes, bearing a chelating P,P donor ligand, with XeF2 led to a variety of fluorido and fluorovinyl complexes. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  18. Electronic and electrochemical properties of platinum(II) and platinum-mercury-carboxylato complexes containing 2-Me2NCH2C6H4, 2,6-(Me2NCH2)2C6H3- and 2-Me2NC6H4CH2 - ligands

    NARCIS (Netherlands)

    Koten, G. van; Ploeg, A.F.M.J. van der; Schmitz, J.E.J.; Linden, J.G.M. van der

    1982-01-01

    The organoplatinum(II) compounds [{2, 6-(Me{2}NCH{2}){2}C{6}H{3}}PtBr] and cis-[(C-N){2}Pt] (C-N = 2-Me{2}NCH{2}C{6}H{4}, 2-Me{2}NC{6}H{4}CH{2}) can be chemically irreversibly oxidized in the potential range 1.00 to 1.35 V vs. an Ag/AgCl electrode, whereas the organoplatinum@?mercury complexes [{2,6

  19. Transient carbon isotope changes in complex systems: Finding the global signal, embracing the local signal

    Science.gov (United States)

    Bowen, G. J.; Schneider-Mor, A.; Filley, T. R.

    2008-12-01

    Global, transient carbon isotope excursions (CIEs) in the geological record are increasingly invoked as evidence of short-lived changes in carbon fluxes to/from the ocean-atmosphere-biosphere (exogenic) system. Reconstructing the dynamics of carbon cycle perturbation and response during such events requires that the global extent, magnitude, and temporal pattern of carbon isotope change are well understood. Unfortunately, no simple, globally integrated measure of exogenic δ13C change exists in the geological record: during major global perturbations even the best-case candidates such as deep-ocean carbonate δ13C values likely respond to a complex of factors including ocean carbonate chemistry and circulation. Here we consider the utility of organic carbon isotope records from two complex depositional systems common in the geological record, fossil soils and continental margin sediments, which are of interest in terms of their relationship to organic carbon cycling and records of past ecological change. Within both systems changes in ecology, climate, carbon source, residence time, and molecular composition have clear potential to modulate the preserved record of global exogenic δ13C change, compromising 1st-order interpretations of bulk or compound-specific isotopic records. Process-explicit eco- geochemical models, ideally combined with multi-substrate data, provide one approach to the isolation of global δ13C change and identification of local or regional processes reflected in such records. Examples from both systems drawn from ongoing work on the Paleocene-Eocene thermal maximum illustrate the potential pitfalls, as well as opportunities, afforded by coupled data/model assessment of transient δ13C changes in complex systems.

  20. Preparation of TiO2-activated carbon complex membranes and their photoelectrocatalytic activity

    Institute of Scientific and Technical Information of China (English)

    尤宏; 姚杰; 孙丽欣; 王强

    2003-01-01

    The experimental process of preparing TiO2-activated carbon complex membranes with activated carbon powder as main carrier, PTFE as binder and wire netting as matrix is described in detail, and both photo-catalysis and photo-electro-catalysis are measured to study the properties of complex membranes. Experimental results show that the photo-catalytic activity of the membranes is high and stable in the process of treating Rhodamine-B; the application of an electric field accelerates the speed of photo-catalysis, and the efficiency of photo-catalysis is increased 2.5 times when the applied voltage is 0.8 V; and the degradation of Rhodamine-B follows the dynamics of first order reaction. It is concluded from the discussion of experimental results that the preparation process of TiO2-activated carbon complex membranes is a simple low-cost process suitable for large scale application.

  1. COMPLEX COMPOST AND CIRCULATION OF NITROGEN AND CARBON AT THE AGROLANDSCAPE SYSTEMS

    Directory of Open Access Journals (Sweden)

    Belyuchenko I. S.

    2014-03-01

    Full Text Available Complex compost includes all elements of the periodic table and is valuable due to the complexity of its system. Among the elements forming a chemical composition of the complex compost we can identify two most important, which are distinguishing a specific character of the interaction with each other and defining the basic processes to ensure vegetation of living system - nitrogen and carbon. Nitrogen determines the rate of energy and connects with living forms of organic matter; it is included as the part of protein and is a major element in determining the productivity of ecosystems. At the cycle of carbon its organic forms and carbon dioxide take a part, presenting the main factors of the processes of respiration and photosynthesis

  2. Spontaneous Resolution and Carbonation of Chiral Benzyllithium Complexes

    DEFF Research Database (Denmark)

    Lennartson, Anders; Sundberg, Jonas; Wiklund, Tove

    2010-01-01

    In search for new examples of absolute asymmetric synthesis (AAS), chiral α-substituted benzyllithium complexes have been prepared. While [Li(phet)(pmdta)] (1) (phet = 1-phenylethyl, pmdta = N,N,N′,N″,N″-pentamethyldiethylenetriamine) affords only racemic crystals, a promising candidate for AAS...... was indeed found: [Li(phet)(tmpda)], α-2, (tmpda = N,N,N′,N′-tetramethylpropylenediamine) crystallises as a conglomerate. Although concomitant polymorphism was not observed, a racemic phase (β-2) could also be isolated. Chiral crystals of α-2 gave 2-phenylpropionic acid in high yield on reaction with gaseous...

  3. Competition between humic acid and carbonates for rare earth elements complexation.

    Science.gov (United States)

    Pourret, Olivier; Davranche, Mélanie; Gruau, Gérard; Dia, Aline

    2007-01-01

    The competitive binding of rare earth elements (REE) to humic acid (HA) and carbonates was studied experimentally at various pH and alkalinity values by combining ultrafiltration and inductively coupled plasma mass spectrometry techniques. The results show that the REE species occur as binary humate or carbonate complexes but not as ternary REE-carbonate-humate as previously proposed. The results also reveal the strong pH and alkalinity dependence of the competition as well as the existence of a systematic fractionation across the REE series. Specifically, carbonate complexation is at a maximum at pH 10 and increase with increasing alkalinity and with the atomic number of the REE (LuCO(3)>LaCO(3)). Modeling of the data using Model VI and recently published stability constants for complexation of REE by humic acid well reproduced the experimental data, confirming the ability of Model VI to accurately determine REE speciation in natural waters. This modeling also confirms the reliability of recently published stability constants. This work shed more light not only on the competition between carbonates and HA for REE complexation but also on the reliability of WHAM 6 and Model VI for calculating the speciation of REE with organic matter in alkaline organic-rich water.

  4. Oxidative addition of halogens to homoleptic perfluoromethyl or perfluorophenyl derivatives of platinum(II): a comparative study.

    Science.gov (United States)

    Menjón, Babil; Martínez-Salvador, Sonia; Gómez-Saso, Miguel A; Forniés, Juan; Falvello, Larry R; Martín, Antonio; Tsipis, Athanassios

    2009-06-22

    Chlorocarbon solvents (solv=CH(2)Cl(2), CHCl(3)) are suggested to play an active role in the oxidative addition of halogens, X(2) (X=Cl, Br, I), to homoleptic d(8) perfluoromethyl and -phenyl platinum(II) species [Pt(R(F))(4)](2-) (R(F)=CF(3), C(6)F(5)). The perfluoromethyl group, CF(3), has been found to be considerably less prone to undergo reductive elimination processes, and is, therefore, more suitable for stabilizing organoplatinum(IV) derivatives (see scheme).The equilibrium geometries of the homoleptic perfluorinated organoplatinate(II) anions [Pt(CF(3))(4)](2-) and [Pt(C(6)F(5))(4)](2-) have been computed at the B3P86/LANL2DZ level of theory. Remarkably good agreement with the experimentally determined structures has been obtained by X-ray diffraction methods. The reactivity of [NBu(4)](2)[Pt(CF(3))(4)] (1) towards halogens (Cl(2), Br(2), and I(2)) has been investigated by using a combined experimental and theoretical approach. The perfluoromethyl derivative 1 has been found to undergo clean oxidative addition of the three halogens under investigation, giving rise to [NBu(4)](2)[trans-Pt(CF(3))(4)X(2)] (X=Cl (7), Br (10), I (13)) in a quantitative and stereoselective way. In the low-temperature reaction of the perfluorophenyl derivative [NBu(4)](2)[Pt(C(6)F(5))(4)] (3) with Cl(2) or Br(2), the corresponding oxidative-addition products [NBu(4)](2)[trans-Pt(C(6)F(5))(4)X(2)] (X=Cl (14), Br (15)) can also be obtained. In the case in which X=Br and working in CHCl(3) at -55 degrees C, it has been possible to detect the formation of an intermediate species to which we assign the formula [trans-Pt(C(6)F(5))(4)Br(ClCHCl(2))](-) (16). The solvento complex 16 is thermally unstable and prone to undergo reductive elimination of C(6)F(5)--C(6)F(5). In the presence of PhCN, complex [NBu(4)][trans-Pt(C(6)F(5))(4)Br(NCPh)] (17) was isolated and structurally characterized. The reaction of 3 with I(2) gave no organoplatinum(IV) compound. Our comparative study reveals that

  5. Complex Ion Dynamics in Carbonate Lithium-Ion Battery Electrolytes

    Energy Technology Data Exchange (ETDEWEB)

    Ong, Mitchell T.; Bhatia, Harsh; Gyulassy, Attila G.; Draeger, Erik W.; Pascucci, Valerio; Bremer, Peer-Timo; Lordi, Vincenzo; Pask, John E.

    2017-03-16

    Li-ion battery performance is strongly influenced by ionic conductivity, which depends on the mobility of the Li ions in solution, and is related to their solvation structure. In this work, we have performed first-principles molecular dynamics (FPMD) simulations of a LiPF6 salt solvated in different Li-ion battery organic electrolytes. We employ an analytical method using relative angles from successive time intervals to characterize complex ionic motion in multiple dimensions from our FPMD simulations. We find different characteristics of ionic motion on different time scales. We find that the Li ion exhibits a strong caging effect due to its strong solvation structure, while the counterion, PF6– undergoes more Brownian-like motion. Our results show that ionic motion can be far from purely diffusive and provide a quantitative characterization of the microscopic motion of ions over different time scales.

  6. Anoxic carbon degradation in Arctic sediments: Microbial transformations of complex substrates

    Science.gov (United States)

    Arnosti, C.; Finke, N.; Larsen, O.; Ghobrial, S.

    2005-05-01

    Complex substrates are degraded in anoxic sediments by the concerted activities of diverse microbial communities. To explore the effects of substrate complexity on carbon transformations in permanently cold anoxic sediments, four substrates— Spirulina cells, Isochrysis cells, and soluble high molecular weight carbohydrate-rich extracts of these cells (Spir-Ex and Iso-Ex)—were added to sediments collected from Svalbard. The sediments were homogenized, incubated anaerobically in gas-tight bags at 0°C, and enzyme activities, fermentation, and terminal respiration were monitored over a 1134 h time course. All substrate additions yielded a fraction (8%-13%) of carbon that was metabolized to CO 2 over the first 384 h of incubation. The timecourse of VFA (volatile fatty acid) production and consumption, as well as the suite of VFAs produced, was similar for all substrates. After this phase, pathways of carbon degradation diverged, with an additional 43%, 32%, 33%, and 8% of Isochrysis, Iso-Ex, Spirulina, and Spir-Ex carbon respired to CO 2 over the next 750 h of incubation. Somewhat surprisingly, the soluble, carbohydrate-rich extracts did not prove to be more labile substrates than the whole cells from which they were derived. Although Spirulina and Iso-Ex differed in physical and chemical characteristics (solid/soluble, C/N ratio, lipid and carbohydrate content), nearly identical quantities of carbon were respired to CO 2. In contrast, only 15% of Spir-Ex carbon was respired, despite the initial burst of activity that it fueled, its soluble nature, and its relatively high (50%) carbohydrate content. The microbial community in these cold anoxic sediments clearly has the capacity to react rapidly to carbon input; extent and timecourse of remineralization of added carbon is similar to observations made at much higher temperatures in temperate sediments. The extent of carbon remineralization from these specific substrates, however, would not likely have been predicted

  7. Complexes of carbon nanotubes with oligonucleotides in thin Langmuir-Blodgett films to detect electrochemically hybridization

    Science.gov (United States)

    Egorov, A. S.; Egorova, V. P.; Krylova, H. V.; Lipnevich, I. V.; Orekhovskaya, T. I.; Veligura, A. A.; Govorov, M. I.; Shulitsky, B. G.

    2014-10-01

    Self-assembled complexes consisting of thin multi-walled carbon nanotubes (MWCNTs) and DNA-oligonucleotides which are able to a cooperative binding to complementary oligonucleotides have been investigated. It was establised a high-performance charge transport in nanostructured Langmuir-Blodgett complexes thin MWCNTs/DNA. A method to electrochemically detect DNA hybridization on the self-organized structures has been proposed.

  8. Formation of oxygen complexes in controlled atmosphere at surface of doped glassy carbon

    Indian Academy of Sciences (India)

    Aleksandra A Perić-Grujić; Tatjana M Vasiljević; Olivera M Nešković; Miomir V Veljković; Zoran V Laušević; Mila D Laušević

    2006-10-01

    The effects of boron and phosphorus incorporation in phenolic resin precursor to the oxidation resistance of glassy carbon have been studied. In order to reveal the nature and composition of the oxygen complexes formed at the surface of doped glassy carbon, under controlled atmosphere, the surface of the samples was cleaned under vacuum up to 1273 K. Specific functional groups, subsequently formed under dry CO2 or O2 atmosphere on the surface of boron-doped and phosphorus-doped glassy carbon samples, were examined using the temperature-programmed desorption method combined with mass spectrometric analysis. Characterization of surface properties of undoped and doped samples has shown that in the presence of either boron or phosphorus heteroatoms, a lower amount of oxygen complexes formed after CO2 exposure, while, typically, higher amount of oxygen complexes formed after O2 exposure. It has been concluded that the surface of undoped glassy carbon has a greater affinity towards CO2, while in the presence of either boron or phosphorus heteroatoms, the glassy carbon surface affinity becomes greater towards O2, under experimental conditions.

  9. PALADYN, a comprehensive land surface-vegetation-carbon cycle model of intermediate complexity

    Science.gov (United States)

    Willeit, Matteo; Ganopolski, Andrey

    2016-04-01

    PALADYN is presented, a new comprehensive and computationally efficient land surface-vegetation-carbon cycle model designed to be used in Earth system models of intermediate complexity for long-term simulations and paleoclimate studies. The model treats in a consistent manner the interaction between atmosphere, terrestrial vegetation and soil through the fluxes of energy, water and carbon. Energy, water and carbon are conserved. The model explicitly treats permafrost, both in physical processes and as important carbon pool. The model distinguishes 9 surface types of which 5 are different vegetation types, bare soil, land ice, lake and ocean shelf. Including the ocean shelf allows to treat continuous changes in sea level and shelf area associated with glacial cycles. Over each surface type the model solves the surface energy balance and computes the fluxes of sensible, latent and ground heat and upward shortwave and longwave radiation. It includes a single snow layer. The soil model distinguishes between three different macro surface types which have their own soil column: vegetation and bare soil, ice sheet and ocean shelf. The soil is vertically discretized into 5 layers where prognostic equations for temperature, water and carbon are consistently solved. Phase changes of water in the soil are explicitly considered. A surface hydrology module computes precipitation interception by vegetation, surface runoff and soil infiltration. The soil water equation is based on Darcy's law. Given soil water content, the wetland fraction is computed based on a topographic index. Photosynthesis is computed using a light use efficiency model. Carbon assimilation by vegetation is coupled to the transpiration of water through stomatal conductance. The model includes a dynamic vegetation module with 5 plant functional types competing for the gridcell share with their respective net primary productivity. Each macro surface type has its own carbon pools represented by a litter, a fast

  10. Platinum Complexes with Edda (Ethylenediamine -N, N - Diacetate Ligands as Potential Anticancer Agents

    Directory of Open Access Journals (Sweden)

    Jurisevic Milena

    2016-12-01

    Full Text Available The design of platinum based drugs is not a new field of interest. Platinum complexes are widely used as anticancer agents and currently, approximately 30 platinum(II and platinum(IV entered into some of the phases of clinical trials. A special place in today’s research belongs to platinum complexes with diammine ligands. A large number of edda (ethylenediamine- N, N’-diacetate-type ligands and their corresponding metal complexes has been successfully synthesized. This article summarizes recent progress in research on edda-type-platinum complexes. Some of these agents achieves better effect compared to the gold standard (cisplatin. It has been shown that there is a possible relationship between the length of the ligand ester group carbon chain and its cytotoxic effect. In most cases the longer the ester chain is the greater is the antitumor activity. Of particular interest are the noticeable effects of some new platinum compound with edda-type ligand on cell lines that are known to have a high level of cisplatin-resistance. Exanimate complexes appear to have a different mode of mechanism of action compared with cisplatin which includes apoptotic and necrotic cell death. There are indications that further investigations of these compounds may be very useful in overcoming the problems associated global cancer statistic.

  11. PARACEST properties of a dinuclear neodymium(III) complex bound to DNA or carbonate.

    Science.gov (United States)

    Nwe, Kido; Andolina, Christopher M; Huang, Ching-Hui; Morrow, Janet R

    2009-07-01

    A dinuclear Nd(III) macrocyclic complex of 1 (1,4-bis[1-(4,7,10-tris(carbamoylmethyl)-1,4,7,10-tetraazacyclododecane]-p-xylene) and mononuclear complexes of 1,4,7-tris-1,4,7,10-tetraazacyclododecane, 2, and 1,4,7-tris[(N-N-diethyl)carbamoylmethyl]-1,4,7,10-tetraazacyclododecane, 3, are prepared. Complexes of 1 and 2 give rise to a PARACEST (paramagnetic chemical exchange saturation transfer) peak from exchangeable amide protons that resonate approximately 12 ppm downfield from the bulk water proton resonance. The dinuclear Nd(III) complex is promising as a PARACEST contrast agent for MRI applications, because it has an optimal pH of 7.5 and the rate constant for amide proton exchange (2700 s(-1)) is nearly as large as it can be within slow exchange conditions with bulk water. Dinuclear Ln(2)(1) complexes (Ln(III) = Nd(III), Eu(III)) bind tightly to anionic ligands including carbonate, diethyl phosphate, and DNA. The CEST amide peak of Nd(2)(1) is enhanced by certain DNA sequences that contain hairpin loops, but decreases in the presence of diethyl phosphate or carbonate. Direct excitation luminescence studies of Eu(2)(1) show that double-stranded and hairpin-loop DNA sequences displace one water ligand on each Eu(III) center. DNA displaces carbonate ion despite the low dissociation constant for the Eu(2)(1) carbonate complex (K(d) = 15 microM). Enhancement of the CEST effect of a lanthanide complex by binding to DNA is a promising step toward the preparation of PARACEST agents containing DNA scaffolds.

  12. Catalytic Asymmetric Carbon-Carbon Forming Reactions Catalyzed Chiral Schiff Base-Metal Complexes

    Institute of Scientific and Technical Information of China (English)

    Takanori; Tanaka; Masahiko; Hayashi

    2007-01-01

    1 Results In 1991, we disclosed the novel asymmetric catalysts prepared from chiral Schiff base and titanium alkoxide in the reaction of asymmetric silylcyanation of aldehydes (eq.1)[1]. Since our first report, chiral Schiff base-metal complex was proven to be efficient in a variety of asymmetric reactions. We reported the first example of enantioselective addition of diketene to aldehydes promoted by chiral Schiff base-titanium alkoxide complexes (eq.2)[2]. The products of this reaction have been cove...

  13. New strategy for chemically attachment of Schiff base complexes on Multiwalled Carbon Nanotubes surfaces

    Directory of Open Access Journals (Sweden)

    Leila Moradi

    2014-06-01

    Full Text Available Chemically attachment of Schiff base complexes on multiwalled carbon nanotubes (MWCNTs surfaces through a convenient and simple method was studied. In the first step of this method, we present a new method for preparation of aminated MWCNTs in order to attachment of (new chlorinated salen Schiff bases. Amination of multiwalled carbon nanotubes performed under microwave (MW irradiation through a one pot two step reaction. The chemically attachment of salen Schiff bases on functionalized MWCNTs (salen@MWCNTs performed under a facile simple nucleophilic substitution reaction and complexation of attached salen Schiff bases (salen complex@MWCNTs in last step, have been occurred with reaction of transition metal salts and salen@MWCNTs. The obtained products were characterized in detail, using FTIR, XRD, UV-Vis absorption, SEM and EDX methods.

  14. Complex formation during dissolution of metal oxides in molten alkali carbonates

    DEFF Research Database (Denmark)

    Li, Qingfeng; Borup, Flemming; Petrushina, Irina

    1999-01-01

    Dissolution of metal oxides in molten carbonates relates directly to the stability of materials for electrodes and construction of molten carbonate fuel cells. In the present work the solubilities of PbO, NiO, Fe2O3,and Bi2O3 in molten Li/K carbonates have been measured at 650 degrees C under...... carbon dioxide atmosphere. It is found that the solubilities of NiO and PbO decrease while those of Fe2O3 and Bi2O3 remain approximately constant as the lithium mole fraction increases from 0.43 to 0.62 in the melt. At a fixed composition of the melt, NiO and PbO display both acidic and basic dissolution...... as the partial pressure of carbon dioxide varies. By combination of solubility and electromotive force measurements, a model is constructed assuming the dissolution involves complex formation. The possible species for lead are proposed to be [Pb(CO3)(2)](-2) and/or [Pb(CO3)(3)](-4). A similar complex chemistry...

  15. Functionalization of single-walled carbon nanotubes with N-[3-(trimethoxysilyl)propyl]ethylenediamine and its cobalt complex

    OpenAIRE

    Oki, Aderemi; Adams, Luqman; Luo, Zhipping; Osayamen, Edigin; Biney, Paul; Khabashesku, Valery

    2008-01-01

    The reaction of N-[3-(trimethoxysilyl)propyl]ethylenediamine with fluorinated carbon nanotubes (F-CNT) produced the corresponding aminoalkylalkoxysilane functionalized carbon nanotubes. Cobalt salt is then complexed to this functionalized carbon nanotubes by the addition of cobalt chloride to form cobalt complexed nanocomposite in high yield. This composite and precursors were characterized by using Fourier transform infra-red spectroscopy (FTIR), transmission electron microscopy (TEM), energ...

  16. DFT studies of uranyl acetate, carbonate, and malonate, complexes in solution.

    Science.gov (United States)

    Vázquez, Jordi; Bo, Carles; Poblet, Josep Maria; de Pablo, Joan; Bruno, Jordi

    2003-09-22

    The aim of this work is to demonstrate that theoretical chemistry can be used as a complementary tool in determining geometric parameters of a number of uranyl complexes in solution, which are not observable by experimental methods. In addition, we propose plausible structures with partial geometric data from experimental results. A gradient corrected DFT methodology with relativistic effects is used employing a COSMO solvation model. The theoretical calculations show good agreement with experimental X-ray and EXAFS data for the triacetato-dioxo-uranium(VI) and tricarbonato-dioxo-uranium(VI) complexes and are used to assign possible geometries for dicalcium-tricarbonato-dioxo-uranium(VI) and malonato-dioxo-uranium(VI) complexes. The results of this exercise indicate that carbonate bonding in these complexes is mainly bidentate and that hydroxo bridging plays a critical role in the stabilization of the polynuclear uranyl complexes.

  17. Capture of unstable protein complex on the streptavidin-coated single-walled carbon nanotubes

    Energy Technology Data Exchange (ETDEWEB)

    Liu Zunfeng, E-mail: liuz2@chem.leidenuniv.nl; Voskamp, Patrick [Cell Observatory, Biophysical Structural Chemistry, Leiden Institute of Chemistry (Netherlands); Zhang Yue; Chu Fuqiang [Changzhou University, School of Pharmaceutical Engineering and Life Science (China); Abrahams, Jan Pieter, E-mail: abrahams@chem.leidenuniv.nl [Cell Observatory, Biophysical Structural Chemistry, Leiden Institute of Chemistry (Netherlands)

    2013-04-15

    Purification of unstable protein complexes is a bottleneck for investigation of their 3D structure and in protein-protein interaction studies. In this paper, we demonstrate that streptavidin-coated single-walled carbon nanotubes (Strep Bullet SWNT) can be used to capture the biotinylated DNA-EcoRI complexes on a 2D surface and in solution using atomic force microscopy and electrophoresis analysis, respectively. The restriction enzyme EcoRI forms unstable complexes with DNA in the absence of Mg{sup 2+}. Capturing the EcoRI-DNA complexes on the Strep Bullet SWNT succeeded in the absence of Mg{sup 2+}, demonstrating that the Strep Bullet SWNT can be used for purifying unstable protein complexes.

  18. Transformation of Graphitic and Amorphous Carbon Dust to Complex Organic Molecules in a Massive Carbon Cycle in Protostellar Nebulae

    Science.gov (United States)

    Nuth, Joseph A., III; Johnson, Natasha M.

    2012-01-01

    relatively inert carbonaceous dust from the ISM into the vital organic precursors to life such as amino acids and sugars intimately mixed with dust and ice in primitive planetesimals. Since the number of carbon atoms entering the Solar Nebula as dust exceeds the number of atoms entering the nebula as oxide grains. the formation of large quantities of complex organic molecules may represent the largest single chemical cycle in the nebula.

  19. Organo-mineral complexation alters carbon and nitrogen cycling in stream microbial assemblages

    OpenAIRE

    Hunter, William Ross; Wanek, Wolfgang; Prommer, Judith; Mooshammer, Maria; Battin, Tom

    2014-01-01

    Inland waters are of global biogeochemical importance receiving carbon inputs of ~ 4.8 Pg C y-1. Of this 12 % is buried, 18 % transported to the oceans, and 70 % supports aquatic secondary production. However, the mechanisms that determine the fate of organic matter (OM) in these systems are poorly defined. One important aspect is the formation of organo-mineral complexes in aquatic systems and their potential as a route for OM transport and burial vs. their use potential as organic carbon (C...

  20. Joint Optimal Production Planning for Complex Supply Chains Constrained by Carbon Emission Abatement Policies

    Directory of Open Access Journals (Sweden)

    Longfei He

    2014-01-01

    Full Text Available We focus on the joint production planning of complex supply chains facing stochastic demands and being constrained by carbon emission reduction policies. We pick two typical carbon emission reduction policies to research how emission regulation influences the profit and carbon footprint of a typical supply chain. We use the input-output model to capture the interrelated demand link between an arbitrary pair of two nodes in scenarios without or with carbon emission constraints. We design optimization algorithm to obtain joint optimal production quantities combination for maximizing overall profit under regulatory policies, respectively. Furthermore, numerical studies by featuring exponentially distributed demand compare systemwide performances in various scenarios. We build the “carbon emission elasticity of profit (CEEP” index as a metric to evaluate the impact of regulatory policies on both chainwide emissions and profit. Our results manifest that by facilitating the mandatory emission cap in proper installation within the network one can balance well effective emission reduction and associated acceptable profit loss. The outcome that CEEP index when implementing Carbon emission tax is elastic implies that the scale of profit loss is greater than that of emission reduction, which shows that this policy is less effective than mandatory cap from industry standpoint at least.

  1. Platinum(iv) N-heterocyclic carbene complexes: their synthesis, characterisation and cytotoxic activity.

    Science.gov (United States)

    Bouché, M; Dahm, G; Wantz, M; Fournel, S; Achard, T; Bellemin-Laponnaz, S

    2016-07-28

    Platinum(ii) N-heterocyclic carbene complexes have been oxidized by bromine or iodobenzene dichloride to provide the fully characterised corresponding platinum(iv) NHC complexes. Antiproliferative activities of Pt(iv) NHC complexes were assayed against several cancer cell lines and the results were correlated with respect to their stability. Mechanistic investigations revealed that mitochondrial dysfunction and ROS production were associated with the cytotoxic process induced by these compounds.

  2. Quantum mechanical calculation of aqueuous uranium complexes: carbonate, phosphate, organic and biomolecular species

    Directory of Open Access Journals (Sweden)

    Jha Prashant

    2009-08-01

    Full Text Available Abstract Background Quantum mechanical calculations were performed on a variety of uranium species representing U(VI, U(V, U(IV, U-carbonates, U-phosphates, U-oxalates, U-catecholates, U-phosphodiesters, U-phosphorylated N-acetyl-glucosamine (NAG, and U-2-Keto-3-doxyoctanoate (KDO with explicit solvation by H2O molecules. These models represent major U species in natural waters and complexes on bacterial surfaces. The model results are compared to observed EXAFS, IR, Raman and NMR spectra. Results Agreement between experiment and theory is acceptable in most cases, and the reasons for discrepancies are discussed. Calculated Gibbs free energies are used to constrain which configurations are most likely to be stable under circumneutral pH conditions. Reduction of U(VI to U(IV is examined for the U-carbonate and U-catechol complexes. Conclusion Results on the potential energy differences between U(V- and U(IV-carbonate complexes suggest that the cause of slower disproportionation in this system is electrostatic repulsion between UO2 [CO3]35- ions that must approach one another to form U(VI and U(IV rather than a change in thermodynamic stability. Calculations on U-catechol species are consistent with the observation that UO22+ can oxidize catechol and form quinone-like species. In addition, outer-sphere complexation is predicted to be the most stable for U-catechol interactions based on calculated energies and comparison to 13C NMR spectra. Outer-sphere complexes (i.e., ion pairs bridged by water molecules are predicted to be comparable in Gibbs free energy to inner-sphere complexes for a model carboxylic acid. Complexation of uranyl to phosphorus-containing groups in extracellular polymeric substances is predicted to favor phosphonate groups, such as that found in phosphorylated NAG, rather than phosphodiesters, such as those in nucleic acids.

  3. Reactivity and Biological Properties of a Series of Cytotoxic PtI2(amine)(2) Complexes, Either cis or trans Configured

    NARCIS (Netherlands)

    Messori, Luigi; Cubo, Leticia; Gabbiani, Chiara; Alvarez-Valdes, Amparo; Michelucci, Elena; Pieraccini, Giuseppe; Rios-Luci, Carla; Leon, Leticia G.; Padron, Jose M.; Navarro-Ranninger, Carmen; Casini, Angela; Quiroga, Adoracion G.

    2012-01-01

    Six diiodido-diamine platinum(II) complexes, either cis or trans configured, were prepared, differing only in the nature of the amine ligand (isopropylamine, dimethylamine, or methylamine), and their antiproliferative properties were evaluated against a panel of human tumor cell lines. Both series o

  4. Carbon nanotubes dispersed in aqueous solution by ruthenium(ii) polypyridyl complexes

    Science.gov (United States)

    Huang, Kewei; Saha, Avishek; Dirian, Konstantin; Jiang, Chengmin; Chu, Pin-Lei E.; Tour, James M.; Guldi, Dirk M.; Martí, Angel A.

    2016-07-01

    Cationic ruthenium(ii) polypyridyl complexes with appended pyrene groups have been synthesized and used to disperse single-walled carbon nanotubes (SWCNT) in aqueous solutions. To this end, planar pyrene groups enable association by means of π-stacking onto carbon nanotubes and, in turn, the attachment of the cationic ruthenium complexes. Importantly, the ionic nature of the ruthenium complexes allows the formation of stable dispersions featuring individualized SWCNTs in water as confirmed in a number of spectroscopic and microscopic assays. In addition, steady-state photoluminescence spectroscopy was used to probe the excited state interactions between the ruthenium complexes and SWCNTs. These studies show that the photoluminescence of both, that is, of the ruthenium complexes and of SWCNTs, are quenched when they interact with each other. Pump-probe transient absorption experiments were performed to shed light onto the nature of the photoluminescence quenching, showing carbon nanotube-based bands with picosecond lifetimes, but no new bands which could be unambigously assigned to photoinduced charge transfer process. Thus, from the spectroscopic data, we conclude that quenching of the photoluminescence of the ruthenium complexes is due to energy transfer to proximal SWCNTs.Cationic ruthenium(ii) polypyridyl complexes with appended pyrene groups have been synthesized and used to disperse single-walled carbon nanotubes (SWCNT) in aqueous solutions. To this end, planar pyrene groups enable association by means of π-stacking onto carbon nanotubes and, in turn, the attachment of the cationic ruthenium complexes. Importantly, the ionic nature of the ruthenium complexes allows the formation of stable dispersions featuring individualized SWCNTs in water as confirmed in a number of spectroscopic and microscopic assays. In addition, steady-state photoluminescence spectroscopy was used to probe the excited state interactions between the ruthenium complexes and SWCNTs

  5. Quantitative carbon detector (QCD) for calibration-free, high-resolution characterization of complex mixtures.

    Science.gov (United States)

    Maduskar, Saurabh; Teixeira, Andrew R; Paulsen, Alex D; Krumm, Christoph; Mountziaris, T J; Fan, Wei; Dauenhauer, Paul J

    2015-01-21

    Current research of complex chemical systems, including biomass pyrolysis, petroleum refining, and wastewater remediation requires analysis of large analyte mixtures (>100 compounds). Quantification of each carbon-containing analyte by existing methods (flame ionization detection) requires extensive identification and calibration. In this work, we describe an integrated microreactor system called the Quantitative Carbon Detector (QCD) for use with current gas chromatography techniques for calibration-free quantitation of analyte mixtures. Combined heating, catalytic combustion, methanation and gas co-reactant mixing within a single modular reactor fully converts all analytes to methane (>99.9%) within a thermodynamic operable regime. Residence time distribution of the QCD reveals negligible loss in chromatographic resolution consistent with fine separation of complex mixtures including cellulose pyrolysis products.

  6. Synthesis of acetyl coenzyme A by carbon monoxide dehydrogenase complex from acetate-grown Methanosarcina thermophila.

    OpenAIRE

    Abbanat, D R; Ferry, J G

    1990-01-01

    The carbon monoxide dehydrogenase (CODH) complex from Methanosarcina thermophila catalyzed the synthesis of acetyl coenzyme A (acetyl-CoA) from CH3I, CO, and coenzyme A (CoA) at a rate of 65 nmol/min/mg at 55 degrees C. The reaction ended after 5 min with the synthesis of 52 nmol of acetyl-CoA per nmol of CODH complex. The optimum temperature for acetyl-CoA synthesis in the assay was between 55 and 60 degrees C; the rate of synthesis at 55 degrees C was not significantly different between pHs...

  7. Hydroxyl, water, ammonia, carbon monoxide and neutral carbon towards the Sgr A complex

    CERN Document Server

    Karlsson, Roland; Hjalmarson, Åke; Winnberg, Anders; Fathi, Kambiz; Frisk, Urban; Olberg, Michael

    2013-01-01

    We observed OH, H$_2$O, HN$_3$, C$^{18}$O, and C$_I$ towards the +50 km/s cloud (M-0.02-0.07), the CND and the +20 km/s (M-0.13-0.08) cloud in the Sgr A complex with the VLA, Odin and SEST. Strong OH absorption, H$_2$O emission and absorption lines were seen at all three positions. Strong C$^{18}$O emissions were seen towards the +50 and +20 km/s clouds. The CND is rich in H$_2$O and OH, and these abundances are considerably higher than in the surrounding clouds, indicating that shocks, star formation and clump collisions prevail in those objects. A comparison with the literature reveals that it is likely that PDR chemistry including grain surface reactions, and perhaps also the influences of shocks has led to the observed abundances of the observed molecular species studied here. In the redward high-velocity line wings of both the +50 and +20 km/s clouds and the CND, the very high H$_2$O abundances are suggested to be caused by the combined action of shock desorption from icy grain mantles and high-temperatu...

  8. New surfactant phosphine ligands and platinum(II) metallosurfactants. Influence of metal coordination on the critical micelle concentration and aggregation properties.

    Science.gov (United States)

    Parera, Elisabet; Comelles, Francesc; Barnadas, Ramon; Suades, Joan

    2010-01-19

    We have prepared the first platinum(II) metallosurfactants from a new family of linear surfactant phosphines Ph(2)P(CH(2))(n)SO(3)Na {1 (n = 2), 2 (n = 6), and 3 (n = 10)}, which were synthesized by reaction between the halosulfonates X(CH(2))(n)SO(3)Na and sodium diphenylphosphide. The metallosurfactants cis-[PtCl(2)L(2)] (L = 1-3) were obtained after reaction between the phosphines and PtCl(2) in dimethylsulfoxide. All compounds were fully characterized by the usual methods {NMR ((1)H, (13)C, (31)P, (195)Pt), IR, MS-ESI and HRMS}. By exploring the surfactant properties of phosphines 1-3 and their respective platinum metallosurfactants cis-[PtCl(2)L(2)] (L = 1-3) through surface tension measurements, dynamic light scattering spectroscopy, and cryo-TEM microscopy, we were able to analyze the influence of the metal coordination on the critical micelle concentration (cmc) and the aggregation properties. The cmc values of platinum metallosurfactants were considerably lower than those obtained for the free phosphines 1-3. This behavior could be understood by an analogy between the structure of cis-[PtCl(2)L(2)] complexes and bolaform surfactants. The calculated values of area per molecule also showed different tendencies between 1-3 and cis-[PtCl(2)L(2)] complexes, which could be explained on the basis of the possible conformations of these compounds in the air-water interface. The study of aggregates by dynamic light scattering spectroscopy and cryo-TEM microscopy showed the formation of spherical disperse medium size vesicles in all cases. However, substantial differences were observed between the three free phosphines (the population of micellar aggregates increased with long chain length) and also between phosphines and their respective metallosurfactants.

  9. Age, extent and carbon storage of the central Congo Basin peatland complex.

    Science.gov (United States)

    Dargie, Greta C; Lewis, Simon L; Lawson, Ian T; Mitchard, Edward T A; Page, Susan E; Bocko, Yannick E; Ifo, Suspense A

    2017-02-02

    Peatlands are carbon-rich ecosystems that cover just three per cent of Earth's land surface, but store one-third of soil carbon. Peat soils are formed by the build-up of partially decomposed organic matter under waterlogged anoxic conditions. Most peat is found in cool climatic regions where unimpeded decomposition is slower, but deposits are also found under some tropical swamp forests. Here we present field measurements from one of the world's most extensive regions of swamp forest, the Cuvette Centrale depression in the central Congo Basin. We find extensive peat deposits beneath the swamp forest vegetation (peat defined as material with an organic matter content of at least 65 per cent to a depth of at least 0.3 metres). Radiocarbon dates indicate that peat began accumulating from about 10,600 years ago, coincident with the onset of more humid conditions in central Africa at the beginning of the Holocene. The peatlands occupy large interfluvial basins, and seem to be largely rain-fed and ombrotrophic-like (of low nutrient status) systems. Although the peat layer is relatively shallow (with a maximum depth of 5.9 metres and a median depth of 2.0 metres), by combining in situ and remotely sensed data, we estimate the area of peat to be approximately 145,500 square kilometres (95 per cent confidence interval of 131,900-156,400 square kilometres), making the Cuvette Centrale the most extensive peatland complex in the tropics. This area is more than five times the maximum possible area reported for the Congo Basin in a recent synthesis of pantropical peat extent. We estimate that the peatlands store approximately 30.6 petagrams (30.6 × 10(15) grams) of carbon belowground (95 per cent confidence interval of 6.3-46.8 petagrams of carbon)-a quantity that is similar to the above-ground carbon stocks of the tropical forests of the entire Congo Basin. Our result for the Cuvette Centrale increases the best estimate of global tropical peatland carbon stocks by

  10. Age, extent and carbon storage of the central Congo Basin peatland complex

    Science.gov (United States)

    Dargie, Greta C.; Lewis, Simon L.; Lawson, Ian T.; Mitchard, Edward T. A.; Page, Susan E.; Bocko, Yannick E.; Ifo, Suspense A.

    2017-01-01

    Peatlands are carbon-rich ecosystems that cover just three per cent of Earth’s land surface, but store one-third of soil carbon. Peat soils are formed by the build-up of partially decomposed organic matter under waterlogged anoxic conditions. Most peat is found in cool climatic regions where unimpeded decomposition is slower, but deposits are also found under some tropical swamp forests. Here we present field measurements from one of the world’s most extensive regions of swamp forest, the Cuvette Centrale depression in the central Congo Basin. We find extensive peat deposits beneath the swamp forest vegetation (peat defined as material with an organic matter content of at least 65 per cent to a depth of at least 0.3 metres). Radiocarbon dates indicate that peat began accumulating from about 10,600 years ago, coincident with the onset of more humid conditions in central Africa at the beginning of the Holocene. The peatlands occupy large interfluvial basins, and seem to be largely rain-fed and ombrotrophic-like (of low nutrient status) systems. Although the peat layer is relatively shallow (with a maximum depth of 5.9 metres and a median depth of 2.0 metres), by combining in situ and remotely sensed data, we estimate the area of peat to be approximately 145,500 square kilometres (95 per cent confidence interval of 131,900–156,400 square kilometres), making the Cuvette Centrale the most extensive peatland complex in the tropics. This area is more than five times the maximum possible area reported for the Congo Basin in a recent synthesis of pantropical peat extent. We estimate that the peatlands store approximately 30.6 petagrams (30.6 × 1015 grams) of carbon belowground (95 per cent confidence interval of 6.3–46.8 petagrams of carbon)—a quantity that is similar to the above-ground carbon stocks of the tropical forests of the entire Congo Basin. Our result for the Cuvette Centrale increases the best estimate of global tropical peatland carbon

  11. Synthesis of PCP-supported nickel complexes and their reactivity with carbon dioxide.

    Science.gov (United States)

    Schmeier, Timothy J; Nova, Ainara; Hazari, Nilay; Maseras, Feliu

    2012-05-29

    The Ni amide and hydroxide complexes [(PCP)Ni(NH(2))] (2; PCP=bis-2,6-di-tert-butylphosphinomethylbenzene) and [(PCP)Ni(OH)] (3) were prepared by treatment of [(PCP)NiCl] (1) with NaNH(2) or NaOH, respectively. The conditions for the formation of 3 from 1 and NaOH were harsh (2 weeks in THF at reflux) and a more facile synthetic route involved protonation of 2 with H(2)O, to generate 3 and ammonia. Similarly the basic amide in 2 was protonated with a variety of other weak acids to form the complexes [(PCP)Ni(2-Me-imidazole)] (4), [(PCP)Ni(dimethylmalonate)] (5), [(PCP)Ni(oxazole)] (6), and [(PCP)Ni(CCPh)] (7), respectively. The hydroxide compound 3, could also be used as a Ni precursor and treatment of 3 with TMSCN (TMS=trimethylsilyl) or TMSN(3) generated [(PCP)Ni(CN)] (8) or [(PCP)Ni(N(3))] (9), respectively. Compounds 3-7, and 9 were characterized by X-ray crystallography. Although 3, 4, 6, 7, and 9 are all four-coordinate complexes with a square-planar geometry around Ni, 5 is a pseudo-five-coordinate complex, with the dimethylmalonate ligand coordinated in an X-type fashion through one oxygen atom, and weakly as an L-type ligand through another oxygen atom. Complexes 2-9 were all reacted with carbon dioxide. Compounds 2-4 underwent facile reaction at low temperature to form the κ(1)-O carboxylate products [(PCP)Ni{OC(O)NH(2)}] (10), [(PCP)Ni{OC(O)OH}] (11), and [(PCP)Ni{OC(O)-2-Me-imidazole}] (12), respectively. Compounds 10 and 11 were characterized by X-ray crystallography. No reaction was observed between 5-9 and carbon dioxide, even at elevated temperatures. DFT calculations were performed to model the thermodynamics for the insertion of carbon dioxide into 2-9 to form a κ(1)-O carboxylate product and understand the pathways for carbon dioxide insertion into 2, 3, 6, and 7. The computed free energies indicate that carbon dioxide insertion into 2 and 3 is thermodynamically favorable, insertion into 8 and 9 is significantly uphill, insertion into 5 and 7

  12. Can uranyl complexes encapsulate to carbon nanotubes? A periodic DFT study

    Indian Academy of Sciences (India)

    K SRINIVASU; MAHESH SUNDARARAJAN

    2017-06-01

    Periodic density functional theory (DFT)-based calculations were carried out on a series of uranyl complexes encapsulated within single walled (SW)-CNT to understand their encapsulation affinities. We find that uranyl-aqua complex ([UO₂(H₂O)₅]²⁺) binds stronger as compared to uranyl-hydroxo-complex ([UO₂(OH)₄]²⁻) due to the variable overall charge of the complex. Further, binding affinities of uranyl formate complexes with different formate stoichiometries (1:1, 1:2 and 1:3) with SW-CNT are considered. Here again, due to variable charges, cationic mono-‘formate-uranyl ([UO2(FM)(H₂O)₃]¹⁺) complex binds stronger as compared to anionic tri-formate uranyl ([UO2(FM)₃]¹⁻). Further, due to the very weak binding commonly found in [UO₂(FM)₃]¹⁻ to CNT, the tubular ends of SW-CNT are sealed with functionalized C₃₆ fullerene. The binding affinity of uranyl complex is not improved when C₃₆ fullerene is used to seal to the SW-CNT as compared to its unsealed counterpart. However, upon functionalizing (at the hub carbon) the C36 cork, the binding affinity of [UO₂(FM)3]¹⁻ is larger inside the CNT due to favorable hydrogen bonding interactions with the uranyl oxygens. Our findings are consistent with the experimental observations which will help to design novel nanomaterials for nuclear waste management processes.

  13. Synthesis and Characterization of Hexahapto-Chromium Complexes of Single-Walled Carbon Nanotubes

    KAUST Repository

    Kalinina, Irina

    2016-12-17

    This chapter employs purified pristine single-walled carbon nanotubes (SWNTs) and octadecylaminefunctionalized-SWNTs. These SWNTs are employed for investigate the potential of the SWNT sidewall to function as a hexahapto ligand for chromium (Cr), with in-depth characterization of the products using some of the techniques, such as thermogravimetric analysis (TGA), transmission electron microscopy (TEM), x-ray photoelectron spectroscopy (XPS). Purified electric arc (EA)-produced SWNTs (P2-SWNT) and octadecylaminefunctionalized SWNTs were obtained from Carbon Solutions, Inc. The TEM images show the removal of the Cr particles from the outer surface of the SWNT bundles in the SWNT-Cr complexes after decomplexation; Cr attachment to the surface of the as-prepared complexes (η6-SWNT)Cr(CO)3 and (η6-SWNT-CONH(CH2)17CH3)Cr(CO)3 is clearly evident. The positions of the bands in the Raman spectra of SWNTs are sensitive to doping and thus the chapter examines the effect of complexation of the Cr(CO)3 and Cr(η6-benzene) units on the position of the G and 2D bands in the (η6-SWNT)Cr(CO)3 and (η6-SWNT)Cr(η6-benzene) complexes.

  14. Heterologous Production of an Energy-Conserving Carbon Monoxide Dehydrogenase Complex in the Hyperthermophile Pyrococcus furiosus

    Directory of Open Access Journals (Sweden)

    Gerrit Jan Schut

    2016-01-01

    Full Text Available Carbon monoxide (CO is an important intermediate in anaerobic carbon fixation pathways in acetogenesis and methanogenesis. In addition, some anaerobes can utilize CO as an energy source. In the hyperthermophilic archaeon Thermococcus onnurineus, which grows optimally at 80°C, CO oxidation and energy conservation is accomplished by a respiratory complex encoded by a 16-gene cluster containing a carbon monoxide dehydrogenase, a membrane-bound [NiFe]-hydrogenase and a Na+/H+ antiporter module. This complex oxidizes CO, evolves CO2 and H2, and generates a Na+ motive force that is used to conserve energy by a Na+-dependent ATP synthase. Herein we used a bacterial artificial chromosome to insert the 13.2 kb gene cluster encoding the CO-oxidizing respiratory complex of T. onnurineus into the genome of the heterotrophic archaeon, Pyrococcus furiosus, which grows optimally at 100°C. P. furiosus is normally unable to utilize CO, however, the recombinant strain readily oxidized CO and generated H2 at 80°C. Moreover, CO also served as an energy source and allowed the P. furiosus strain to grow with a limiting concentration of sugar or with peptides as the carbon source. Moreover, CO oxidation by P. furiosus was also coupled to the re-utilization, presumably for biosynthesis, of acetate generated by fermentation. The functional transfer of CO utilization between Thermococcus and Pyrococcus species demonstrated herein is representative of the horizontal gene transfer of an environmentally-relevant metabolic capability. The transfer of CO utilizing, hydrogen-producing genetic modules also has applications for biohydrogen production and a CO-based industrial platform for various thermophilic organisms.

  15. The abundances of atomic carbon and carbon monoxide compared with visual extinction in the Ophiuchus molecular cloud complex

    Science.gov (United States)

    Frerking, Margaret A.; Keene, Jocelyn; Blake, Geoffrey A.; Phillips, T. G.

    1989-01-01

    Emission from the 492 GHz lines of C I have been observed toward six positions in the Ophiuchus molecular cloud complex for which accurate visual extinctions are available. The column density of C I increases with A(V) to greater than 2 x 10 to the 17th/sq cm at 100 mag, the column-averaged fractional abundance reaches a peak of about 2.2 x 10 to the -5th for A(V) in the range 4-11 mag and the column-averaged abundance ratio of C I to CO decreases with A(V) from about 1 at 2 mag to greater that about 0.03 at 100 mag. These results imply that, while C I is not the primary reservoir of gaseous carbon even at cloud edges, its fractional abundance remains high for at least 10 mag into the cloud and may be significant at even greater depths.

  16. Quinoxaline-2-carboxamide as a carrier ligand in two new platinum(ii) compounds: Synthesis, crystal structure, cytotoxic activity and DNA interaction

    NARCIS (Netherlands)

    Marques Gallego, P.; Amparo Gamiz-Gonzalez, M.; Fortea-Pérez, F. R.; Lutz, M.; Spek, A.L.; Pevec, A.; Kozlevar, B.; Reedijk, J.

    2010-01-01

    The search for platinum compounds structurally different from cisplatin has led to two new platinum(II) compounds containing quinoxaline-2-carboxamide as a carrier ligand, i.e. cis-[Pt(qnxca)(MeCN)Cl2] (1) and the [Pt(qnxca−H)(dmso)Cl] (2). Both compounds have been synthesized and characterized usin

  17. On the thermal stability of vacancy-carbon complexes in alpha iron.

    Science.gov (United States)

    Terentyev, D; Bonny, G; Bakaev, A; Van Neck, D

    2012-09-26

    In this work we have summarized the available ab initio data addressing the interaction of carbon with vacancy defects in bcc Fe and performed additional calculations to extend the available dataset. Using an ab initio based parameterization, we apply object kinetic Monte Carlo (OKMC) simulations to model the process of isochronal annealing in bcc Fe doped with carbon to compare with experimental data. As a result of this work, we clarify that a binding energy of ~0.65 eV for a vacancy-carbon (V-C) pair fits the available experimental data best. It is found that the V (2)-C complex is less stable than the V-C pair and its dissociation with activation energy of 0.55 + 0.49 eV also rationalizes a number of experimental data where the breakup of V-C complexes was assumed instead. From the summarized ab initio data, the subsequently obtained OKMC results and critical discussion, provided here, we suggest that the twofold interpretation of the V-C binding energy, which is believed to vary between 0.47 and 0.65 eV, depending on the ab initio approximation, should be removed. The stability and mobility of small and presumably immobile SIA clusters formed at stage II is also discussed in the view of experimental data.

  18. CARBON DIOXIDE INFLUENCE ON THE THERMAL FORMATION OF COMPLEX ORGANIC MOLECULES IN INTERSTELLAR ICE ANALOGS

    Energy Technology Data Exchange (ETDEWEB)

    Vinogradoff, V.; Fray, N.; Bouilloud, M.; Cottin, H. [LISA Laboratoire Interuniversitaire des Systèmes Atmosphériques, UMR CNRS 7583, Université Paris Est Créteil (UPEC), Université Paris Diderot (UPD), Institut Pierre Simon Laplace, Labex ESEP, Paris (France); Duvernay, F.; Chiavassa, T., E-mail: vvinogradoff@mnhn.fr [PIIM, Laboratoire de Physique des Interactions Ioniques et Moléculaires, Université Aix-Marseille, UMR CNRS 7345, Marseille (France)

    2015-08-20

    Interstellar ices are submitted to energetic processes (thermal, UV, and cosmic-ray radiations) producing complex organic molecules. Laboratory experiments aim to reproduce the evolution of interstellar ices to better understand the chemical changes leading to the reaction, formation, and desorption of molecules. In this context, the thermal evolution of an interstellar ice analogue composed of water, carbon dioxide, ammonia, and formaldehyde is investigated. The ice evolution during the warming has been monitored by IR spectroscopy. The formation of hexamethylenetetramine (HMT) and polymethylenimine (PMI) are observed in the organic refractory residue left after ice sublimation. A better understanding of this result is realized with the study of another ice mixture containing methylenimine (a precursor of HMT) with carbon dioxide and ammonia. It appears that carbamic acid, a reaction product of carbon dioxide and ammonia, plays the role of catalyst, allowing the reactions toward HMT and PMI formation. This is the first time that such complex organic molecules (HMT, PMI) are produced from the warming (without VUV photolysis or irradiation with energetic particles) of abundant molecules observed in interstellar ices (H{sub 2}O, NH{sub 3}, CO{sub 2}, H{sub 2}CO). This result strengthens the importance of thermal reactions in the ices’ evolution. HMT and PMI, likely components of interstellar ices, should be searched for in the pristine objects of our solar system, such as comets and carbonaceous chondrites.

  19. Characterization of a Carbon Dioxide-Hexaflourobenzene Complex Using Matrix Isolation Infrared Spectroscopy

    Science.gov (United States)

    Amicangelo, Jay C.; Gall, Bradley K.; Horn, Maryn N.

    2017-06-01

    Matrix isolation infrared spectroscopy was used to characterize a 1:1 complex of carbon dioxide (CO_2) with hexaflourobenzene (C_6F_6). Co-deposition experiments with CO_2 and {_6F_6} were performed at 20 K using argon as the matrix gas. New infrared peaks attributable to the CO_2-C_6F_6 complex were observed near the O-C-O antisymmetric stretching vibration of the CO_2 monomer and near the C-F stretching vibration of the C_6F_6 monomer. The initial identification of the newly observed infrared peaks to those of a CO_2-C_6F_6 complex was established by performing several concentration studies in which the sample-to-matrix ratios of the monomers were varied between 1:100 to 1:1600, by comparing the resulting co-deposition spectra with the spectra of the individual monomers, and by matrix annealing experiments (30 - 35 K). Co-deposition experiments were also performed using isotopically labeled carbon dioxide (^{13}CO_2) and the analogous peaks for the ^{13}CO_2-C_6F_6 complex were observed. Quantum chemical calculations were performed for the CO_2-C_6F_6 complex at the MP2/aug-cc-pVDZ level of theory in order to explore the intermolecular potential energy surface of the complex and to obtain optimized complex geometries and predicted vibrational frequencies of the complex. The calculations for the exploration of the potential energy surface involved rigid scans along the intermolecular distance and various angle coordinates for several general orientations of the two monomers. Based on these calculations, full geometry optimizations were then performed and two stable complex minima were found: one in which the CO_2 is perpendicular and centered to the C_6F_6 ring (ΔE_{int} = -7.9 kJ/mol) and one in which the CO_2 is parallel to the C_6F_6 ring but displaced from the center (ΔE_{int} = -6.0 kJ/mol). Comparing the predicted vibrational spectra for both complexes to the observed experimental spectra, particularly for the O-C-O antisymmetric stretching region, it is

  20. A Ni-Fe Layered Double Hydroxide-Carbon Nanotube Complex for Water Oxidation

    CERN Document Server

    Gong, Ming; Wang, Hailiang; Liang, Yongye; Wu, Justin Zachary; Zhou, Jigang; Wang, Jian; Regier, Tom; Wei, Fei; Dai, Hongjie

    2013-01-01

    Highly active, durable and cost-effective electrocatalysts for water oxidation to evolve oxygen gas hold a key to a range of renewable energy solutions including water splitting and rechargeable metal-air batteries. Here, we report the synthesis of ultrathin nickel iron layered double hydroxide nanoplates on mildly oxidized multi-walled carbon nanotubes. Incorporation of Fe into the nickel hydroxide induced the formation of NiFe-layered double hydroxide. The nanoplates were covalently attached to a network of nanotubes, affording excellent electrical wiring to the nanoplates. The ultra-thin Ni-Fe layered double hydroxide nanoplates/carbon nanotube complex was found to exhibit unusually high electro-catalytic activity and stability for oxygen evolution and outperformed commercial precious metal Ir catalysts.

  1. Complex and new modification techniques of thiocholine detection electrodes with carbon nanotubes

    Science.gov (United States)

    Zhang, Shu-Ping; Zheng, Yi; Shan, Lian-Gang; Shi, Li-yi; Leng, Kai-liang

    2008-11-01

    A new and complex modification technique of glassy carbon electrode (GCE) with multi-walled carbon nanotubes (MWNTs) was developed. Firstly, MWNTs were electro-deposited on GCE at 1.70 V for 2 h. Secondly, by layer-by-layer (LBL) self-assembly technique, a functional membrane of {PDDA/MWNTs} n were fabricated by alternative immersion in 1% PDDA solution and 1 mg L -1 MWNTs dispersion either. As a result, the modified membrane with five {PDDA/MWNTs} bilayers have good sensitivity, stability, anti-fouling ability and catalytic activity for thiocholine (TCh) detection, the oxidation potential on the modified GCE was decreased almost by 50% while the peak current was increased almost by 100% compared with that on bare GCE. Meanwhile, it showed a low detection limit of less than 7.500 × 10 -7 mol L -1 TCh.

  2. Preparation of Carbon Nanotubes by the Catalysis of Polymer Metal Complex on Porous Al203 Matrix

    Institute of Scientific and Technical Information of China (English)

    SHI YanLi; ZHANG XiaoGang; LI HuLin

    2001-01-01

    @@ At present, synthesis of carbon nanotubes (CNTs) is normally conducted on a vapor-to-solid interface at ca. 500-3500℃ via various vapor phase methods, such as are discharge, laser ablation, catalytic pyrolysis and chemical vapor deposition, etc.1-2 Recently, channel materials (such as channels of alumina and of AlPO4-5 zeolite) 3 have been utilized as solid-state templates to grow CNTs inside the channel. Here we described a novel method to prepare the carbon nanotubes based on the decomposition of C2H2 gas on the Co-Ni catalyst anchored by polymer complex on the porous A12O3 matrix. The degree of graphitization of synthesized CNTs and catalysts are of great interest.

  3. Preparation of Carbon Nanotubes by the Catalysis of Polymer Metal Complex on Porous Al203 Matrix

    Institute of Scientific and Technical Information of China (English)

    SHI; YanLi

    2001-01-01

    At present, synthesis of carbon nanotubes (CNTs) is normally conducted on a vapor-to-solid interface at ca. 500-3500℃ via various vapor phase methods, such as are discharge, laser ablation, catalytic pyrolysis and chemical vapor deposition, etc.1-2 Recently, channel materials (such as channels of alumina and of AlPO4-5 zeolite) 3 have been utilized as solid-state templates to grow CNTs inside the channel. Here we described a novel method to prepare the carbon nanotubes based on the decomposition of C2H2 gas on the Co-Ni catalyst anchored by polymer complex on the porous A12O3 matrix. The degree of graphitization of synthesized CNTs and catalysts are of great interest.  ……

  4. Adsorption of some metal complexes derived from acetyl acetone on activated carbon and purolite S-930

    Directory of Open Access Journals (Sweden)

    Salam A.H. Al-Ameri

    2014-12-01

    Full Text Available A new Schiff base (HL derived from condensation of p-anisidine and acetyl acetone has been prepared and used as a chelating ligand to prepare Cr(III, Mn(II, Co(II, Ni(II and Cu(II complexes. The study of the nature of these complexes formed in ethanol solution following the mole ratio method (2:1, L:M gave results which were compared successfully with these obtained from isolated solid state studies. These studies revealed that the complexes having square planner geometry of the type (ML2, M = Co(II, Ni(II and Cu(II, and octahedral geometry of the type [CrIIIL2(H2O2]Cl and [MNIIL2(H2O2]. The adsorption studies of three complexes Cr(III, Mn(II, and Co(II on activated carbon, H and Na-forms of purolite S-930 resin show high adsorption percentage for Cr(III on purolite S-930 due to ion exchange interaction compared with high adsorption of neutral Mn(II, Co(II complexes on activated charcoal. Linear plot of log Qe versus log Ce showed that the adsorption isotherm of these three complexes on activated carbon, H and Na-forms of purolite S-930 surface obeys Freundlich isotherm and was similar to S-curve type according to Giles classification which investigates heterogeneous adsorption. The regression values indicate that the adsorption data for these complexes fitted well within the Freundlich isothermal plots for the concentration studied. The accuracy and precision of the concentration measurements of these complexes were determined by preparing standard laboratory samples, the results show relative error ranging from ±1.08 to 5.31, ±1.04 to 4.82 and ±0.28 to 3.09 and the relative standard deviation did not exceed ±6.23, ±2.77 and ±4.38% for A1, A2 and A3 complexes, respectively.

  5. Charge transport and optical properties of the complexes of indigo wrapped over carbon nanotubes.

    Science.gov (United States)

    Joshi, Ankita; Ramachandran, C N

    2016-05-18

    A new molecular system comprising the non-covalently functionalized complexes of single walled (6,6) carbon nanotubes (SWCNTs) of finite length with indigo is proposed based on the dispersion-corrected density functional theory calculations. In the complexes viz. the dyad and triad, indigo is wrapped over carbon nanotubes in the ratio of 1 : 1 and 2 : 1, respectively. A comprehensive study of stabilization energy, ionization energy, electron affinity, the energy gap between the highest occupied and lowest unoccupied molecular orbitals (ΔELUMO-HOMO), and absorption spectra unravels the structure-property relationship of the complexes. The energy gap of ∼1 eV between the HOMO and the LUMO of the complexes suggests that they can be semiconductive. The energy levels of the frontier molecular orbitals of indigo and CNT suggest the possibility of the photoinduced charge transfer between them. Using the charge hopping rate based on Marcus theory, a hole mobility as high as 8.77 cm(2) V(-1) s(-1) is obtained for the dyad. For both the dyad and triad, a higher value of hole mobility than electron mobility is observed, thereby suggesting them to be useful for p-type semiconductor devices. The time-dependent density functional theory (TD-DFT) calculations predict that the absorption of indigo-CNT complexes occurs in the visible and the near-infrared regions finding applications in organic light emitting diodes (OLEDs). Furthermore, the effects of the length and the capping of CNTs as well as the orientation of indigo over the CNTs on the charge transport properties are also discussed.

  6. Heterologous Production of an Energy-Conserving Carbon Monoxide Dehydrogenase Complex in the Hyperthermophile Pyrococcus furiosus

    Science.gov (United States)

    Schut, Gerrit J.; Lipscomb, Gina L.; Nguyen, Diep M. N.; Kelly, Robert M.; Adams, Michael W. W.

    2016-01-01

    Carbon monoxide (CO) is an important intermediate in anaerobic carbon fixation pathways in acetogenesis and methanogenesis. In addition, some anaerobes can utilize CO as an energy source. In the hyperthermophilic archaeon Thermococcus onnurineus, which grows optimally at 80°C, CO oxidation and energy conservation is accomplished by a respiratory complex encoded by a 16-gene cluster containing a CO dehydrogenase, a membrane-bound [NiFe]-hydrogenase and a Na+/H+ antiporter module. This complex oxidizes CO, evolves CO2 and H2, and generates a Na+ motive force that is used to conserve energy by a Na+-dependent ATP synthase. Herein we used a bacterial artificial chromosome to insert the 13.2 kb gene cluster encoding the CO-oxidizing respiratory complex of T. onnurineus into the genome of the heterotrophic archaeon, Pyrococcus furiosus, which grows optimally at 100°C. P. furiosus is normally unable to utilize CO, however, the recombinant strain readily oxidized CO and generated H2 at 80°C. Moreover, CO also served as an energy source and allowed the P. furiosus strain to grow with a limiting concentration of sugar or with peptides as the carbon source. Moreover, CO oxidation by P. furiosus was also coupled to the re-utilization, presumably for biosynthesis, of acetate generated by fermentation. The functional transfer of CO utilization between Thermococcus and Pyrococcus species demonstrated herein is representative of the horizontal gene transfer of an environmentally relevant metabolic capability. The transfer of CO utilizing, hydrogen-producing genetic modules also has applications for biohydrogen production and a CO-based industrial platform for various thermophilic organisms. PMID:26858706

  7. Laser-induced synthesis of a nanostructured polymer-like metal-carbon complexes

    Science.gov (United States)

    Arakelian, S.; Kutrovskaya, S.; Kucherik, A.; Osipov, A.; Povolotckaia, A.; Povolotskiy, A.; Manshina, A.

    2016-04-01

    Synthesis of nanotructured metal-carbon materials by laser irradiation is an actual branch of laser physics and nanotechnology. Laser sources with different pulse duration allow changing the heating rate with realization of different transition scenarios and synthesis materials with various physical properties. We study the process of the formation of nanostructured metal-clusters and complexes using laser irradiation of colloidal systems which were consisted of carbon micro- nanoparticles and nanoparticles of noble metals. For carbon nanoparticles synthesis we use the method of laser ablation in liquid. For the realization of different regimes of laser surface modification of the target (glassycarbon and shungite) and the formation of micro- nanoparticles in a liquid the YAG:Nd laser with a pulse duration from 0.5 ms up to 20 ms (pulse energy up to 50J) was applied. We have used the CW-laser with moderate intensity in liquid (water or ethanol) for nanoparticle of noble metals synthesis. Thus, colloidal systems were obtained by using CW-laser with λ = 1.06 μm, I ~ 105-6 W/cm2, and t = 10 min. The average size of resulting particles was approximately about 10 to 100 nm. The nanoparticle obtaining was provided in the colloidal solution with different laser parameters. In this work we have investigated the mechanism of the metal-carbon cluster formation during the process of irradiation of colloidal system which were consisted of separate carbon, silver and gold nanoparticles. This system was irradiated by nanosecond laser (100 ns) with average power up to 50W.

  8. Supercritical carbon dioxide interpolymer complexes improve survival of B. longum Bb-46 in simulated gastrointestinal fluids.

    Science.gov (United States)

    Thantsha, Mapitsi S; Cloete, Thomas E; Moolman, Francis S; Labuschagne, Philip W

    2009-01-31

    Gastric acidity is the main factor affecting viability of probiotics in the gastrointestinal tract (GIT). This study investigated the survival in simulated gastrointestinal fluids of Bifidobacterium longum Bb-46 encapsulated in interpolymer complexes formed in supercritical carbon dioxide (scCO(2)). Bacteria were exposed sequentially to simulated gastric fluid (SGF, pH 2) for 2 h and simulated intestinal fluid (SIF, pH 6.8) for 6 or 24 h. Total encapsulated bacteria were determined by suspending 1 g of product in SIF for 6 h at 37 degrees C prior to plating out. Plates were incubated anaerobically at 37 degrees C for 72 h. The interpolymer complex displayed pH-responsive release properties, with little to no release in SGF and substantial release in SIF. There was a limited reduction in viable counts at the end of exposure period due to encapsulation. Protection efficiency of the interpolymer complex was improved by addition of glyceryl monostearate (GMS). Gelatine capsules delayed release of bacteria from the interpolymer complex thus minimizing time of exposure to the detrimental conditions. Use of poly(caprolactone) (PCL), ethylene oxide-propylene oxide triblock copolymer (PEO-PPO-PEO) decreased the protection efficiency of the matrix. Interpolymer complex encapsulation showed potential for protection of probiotics and therefore for application in food and pharmaceuticals.

  9. Synthesis of the Multinuclear Cobaloxime Complexes via Click Chemistry as Catalysts for the Formation of Cyclic Carbonates from Carbon Dioxide and Epoxides

    Indian Academy of Sciences (India)

    Ahmet Kilic; Armagan Keles; Emine Aytar; Mustafa Durgun; Mahmut Ulusoy

    2015-09-01

    In this study, the structurally similar multinuclear cobaloxime complexes based on dioxime ligands were synthesized and characterized as trinuclear complexes with respect to varied axial groups. The multinuclear cobaloxime complexes were characterized by 1H, 13C-NMR, FT-IR, UV-Vis, LC-MS spectra, melting point and magnetic susceptibility measurements. These multinuclear cobaloxime complexes have been successfully applied to the synthesis of cyclic carbonates from CO2 and epoxides under optimized conditions and with-out using any solvent. All multinuclear cobaloxime complexes obtained by click chemistry are good catalysts for the cycloaddition of CO2 to different epoxides in the presence of pyridine as a co-catalyst. Additionally, the effects of epoxides, bases, temperature, pressure, and time on the yield of cyclic carbonates were investigated.

  10. Comparison of complex permittivities of isotonic colloids containing single-wall carbon nanotubes of varying chirality.

    Science.gov (United States)

    Nair, Tejas; Symanowski, James T; Gach, H Michael

    2012-02-01

    The application of bio-compatible, conductive nanoparticles in combination with radiofrequency (RF) irradiation to raise tissue temperatures between 40 and 60 °C for hyperthermia and ablation spurred interest in the complex permittivities of isotonic nanoparticle-based colloids. Nanoparticles with large aspect ratios and high permittivities increase the bulk permittivity of the colloid and RF losses at the macroscopic scale. The complex permittivities of isotonic colloids with and without single-wall carbon nanotubes (SWCNTs) containing either metallic, semiconducting, or mixed chiralities were measured from 20 MHz to 1 GHz at room temperature. The colloids were made with one of three different isotonic solvents: phosphate buffered saline (PBS), and Dulbecco's modified eagle medium (DMEM) with and without 0.5% weight/volume bovine serum albumin to simulate cytosol and blood, respectively. The concentration of elemental carbon from the SWCNTs in the colloids ranged from 16 to 17 mM. The permittivities were corrected for electrode polarization effects by fitting the data to the Cole-Cole relaxation model with a constant phase angle element. The presence of SWCNTs increased both the real and imaginary components of the permittivities of the colloids. For all three solvents, the direct current (DC) components of the real and imaginary permittivities were greatest for the colloids containing the mixed chirality SWCNTs, followed by the colloids with semiconducting SWCNTs, and then metallic SWCNTs. Copyright © 2011 Wiley Periodicals, Inc.

  11. Molecular recognition using corona phase complexes made of synthetic polymers adsorbed on carbon nanotubes.

    Science.gov (United States)

    Zhang, Jingqing; Landry, Markita P; Barone, Paul W; Kim, Jong-Ho; Lin, Shangchao; Ulissi, Zachary W; Lin, Dahua; Mu, Bin; Boghossian, Ardemis A; Hilmer, Andrew J; Rwei, Alina; Hinckley, Allison C; Kruss, Sebastian; Shandell, Mia A; Nair, Nitish; Blake, Steven; Şen, Fatih; Şen, Selda; Croy, Robert G; Li, Deyu; Yum, Kyungsuk; Ahn, Jin-Ho; Jin, Hong; Heller, Daniel A; Essigmann, John M; Blankschtein, Daniel; Strano, Michael S

    2013-12-01

    Understanding molecular recognition is of fundamental importance in applications such as therapeutics, chemical catalysis and sensor design. The most common recognition motifs involve biological macromolecules such as antibodies and aptamers. The key to biorecognition consists of a unique three-dimensional structure formed by a folded and constrained bioheteropolymer that creates a binding pocket, or an interface, able to recognize a specific molecule. Here, we show that synthetic heteropolymers, once constrained onto a single-walled carbon nanotube by chemical adsorption, also form a new corona phase that exhibits highly selective recognition for specific molecules. To prove the generality of this phenomenon, we report three examples of heteropolymer-nanotube recognition complexes for riboflavin, L-thyroxine and oestradiol. In each case, the recognition was predicted using a two-dimensional thermodynamic model of surface interactions in which the dissociation constants can be tuned by perturbing the chemical structure of the heteropolymer. Moreover, these complexes can be used as new types of spatiotemporal sensors based on modulation of the carbon nanotube photoemission in the near-infrared, as we show by tracking riboflavin diffusion in murine macrophages.

  12. The complex ion structure of warm dense carbon measured by spectrally resolved x-ray scattering

    Energy Technology Data Exchange (ETDEWEB)

    Kraus, D.; Barbrel, B.; Falcone, R. W. [Department of Physics, University of California, Berkeley, California 94720 (United States); Vorberger, J. [Max-Planck-Institut für Physik komplexer Systeme, Nöthnitzer Straße 38, 01187 Dresden (Germany); Helfrich, J.; Frydrych, S.; Ortner, A.; Otten, A.; Roth, F.; Schaumann, G.; Schumacher, D.; Siegenthaler, K.; Wagner, F.; Roth, M. [Institut für Kernphysik, Technische Universität Darmstadt, Schlossgartenstraße 9, 64289 Darmstadt (Germany); Gericke, D. O.; Wünsch, K. [Centre for Fusion, Space and Astrophysics, Department of Physics, University of Warwick, Coventry CV4 7AL (United Kingdom); Bachmann, B.; Döppner, T. [Lawrence Livermore National Laboratory, Livermore, California 94550 (United States); Bagnoud, V.; Blažević, A. [GSI Helmholtzzentrum für Schwerionenforschung GmbH, Planckstraße 1, 64291 Darmstadt (Germany); and others

    2015-05-15

    We present measurements of the complex ion structure of warm dense carbon close to the melting line at pressures around 100 GPa. High-pressure samples were created by laser-driven shock compression of graphite and probed by intense laser-generated x-ray sources with photon energies of 4.75 keV and 4.95 keV. High-efficiency crystal spectrometers allow for spectrally resolving the scattered radiation. Comparing the ratio of elastically and inelastically scattered radiation, we find evidence for a complex bonded liquid that is predicted by ab-initio quantum simulations showing the influence of chemical bonds under these conditions. Using graphite samples of different initial densities we demonstrate the capability of spectrally resolved x-ray scattering to monitor the carbon solid-liquid transition at relatively constant pressure of 150 GPa. Showing first single-pulse scattering spectra from cold graphite of unprecedented quality recorded at the Linac Coherent Light Source, we demonstrate the outstanding possibilities for future high-precision measurements at 4th Generation Light Sources.

  13. Asynchronous Reductive Release of Iron and Organic Carbon from Hematite-Humic Acid Complexes

    Science.gov (United States)

    Adhikari, D.; Poulson, S.; Sumaila, S.; Dynes, J.; McBeth, J. M.; Yang, Y.

    2015-12-01

    Association with solid-phase iron plays an important role in the accumulation and stabilization of soil organic matter (SOM). Ferric minerals are subject to redox reactions, which can compromise the stability of iron-bound SOM. To date, there is limited information available concerning the fate of iron-bound SOM during redox reactions. In this study, we investigated the release kinetics of hematite-bound organic carbon (OC) during the abiotic reduction of hematite-humic acid (HA) complexes by dithionite, as an analog for the fate of iron-bound SOM in natural redox reactions. Carbon 1s near edge X-ray absorption fine structure (NEXAFS) spectroscopy was used to examine the ratio of the aromatic, phenolic and carboxylic/imide functional groups of the adsorbed OC before and after reduction. Our results indicate that the reductive release of iron obeyed first-order kinetics with release rate constants of 6.67×10-3 to 13.0×10-3 min-1. The iron-bound OC was released rapidly during the initial stage with release rate constants of 0.011 to 1.49 min-1, and then became stable with residual fractions of 4.6% to 58.2% between 120 and 240 min. The release rate of aromatic OC was much faster than for the non-aromatic fraction of HA, and 90% of aromatic OC was released within the first hour for most samples. The more rapid release of aromatic OC was attributed to its potential distribution on the outer layer because of steric effects and the possible reduction of quinoids. Our findings show that in the reductive reaction the mobilization of iron-bound organic carbon was asynchronous with the reduction of iron, and aromatic carbon was released more readily than other organic components. This study illustrates the importance of evaluating the stability of iron-bound SOM, especially under aerobic-anaerobic transition conditions.

  14. Heterogeneous platinum-catalyzed hydrogenation of dialkyl(diolefin)platinum(II) complexes: A new route to platinum surface alkyls

    OpenAIRE

    McCarthy, Thomas J.; Shih, Yen-Shiang; Whitesides, George M.

    1981-01-01

    Platinum metal catalyzes the reduction of dialkyl(diolefin)platinum(II) complexes by dihydrogen to alkanes and platinum(0). The reaction involves adsorption of the platinum(II) complex on the platinum(0) catalyst surface with conversion of the alkyl moieties to platinum surface alkyls; these appear as alkane products. The platinum atom originally present in the soluble organoplatinum species becomes part of the platinum(0) surface.

  15. Evidence of Different Stoichiometries for the Limiting Carbonate Complexes across the Lanthanide(III) Series

    Energy Technology Data Exchange (ETDEWEB)

    Philippini, V.; Vercouter, T.; Vitorge, P. [CEA Saclay, DEN DPC SECR Lab Speciat Radionucleides and Mol, F-91191 Gif Sur Yvette (France); Vitorge, P. [Univ Evry Val Essonne, CNRS, Lab Anal and Modelisat Biol and Environm, UMR 8587, F-91025 Evry (France)

    2010-07-01

    The stoichiometries of limiting carbonate complexes of lanthanide(III) ions were investigated by solubility measurements of hydrated NaLn(CO{sub 3}){sub 2} solid compounds (Ln = La, Nd, Eu and Dy) at room temperature in aqueous solutions of high ionic strength (3. 5 mol. kg{sup -1}) NaClO{sub 4}) and high CO{sub 3}{sup 2-} concentrations (0. 1 to 1. 5 mol. kg{sup -1}). The results were interpreted by considering the stability of carbonate complexes, with limiting species found to be La(CO{sub 3}){sub 4}{sup 5-}, Nd(CO{sub 3}){sub 4}{sup 5-}, Eu(CO{sub 3}){sub 3}{sup 3-} and Dy(CO{sub 3}){sub 3}{sup 3-}. TRLFS measurements on the Eu and Dy solutions confirmed the predominance of a single aqueous complex in all the samples. Equilibrium constants were determined for the reaction Ln(CO{sub 3}){sub 3}{sup 3-} + CO{sub 3}{sup 2-} reversible arrow Ln(CO{sub 3}){sub 4}{sup 5-}: log(10) K{sub 4,} {sub L}a{sup 3}. 5{sup m} {sup N}a{sup C}l{sup O}{sub 4} = 0. 7 {+-} 0. 3, log(10) K{sub 4,} {sub N}d{sup 3}. 5{sup m} {sup N}a{sup C}l{sup O}{sub 4} = 1. 3 {+-} 0. 3, and for Ln = Eu and Dy, log(10) K{sub 4,} {sub L}n{sup 3}. 5{sup m} {sup N}a{sup C}l{sup O}{sub 4}) {<=} -0. 4. These results suggest that tetra-carbonato complexes are stable only for the light lanthanide ions in up to 1. 5 molal CO{sub 3}{sup 2-} aqueous solutions, in agreement with our recent capillary electrophoresis study. Comparison with literature results indicates that analogies between actinide(III) and lanthanide(III) ions of similar ionic radii do not hold in concentrated carbonate solutions. Am(CO{sub 3}){sub 3}{sup 3-} was previously evidenced by solubility measurements, whereas we have observed that Nd(CO{sub 3}){sub 4}{sup 5-} predominates in similar conditions. We may speculate that small chemical differences between Ln(III) and An(III) could result in macroscopic differences when their coordination sphere is complete. (authors)

  16. Ultrasound detection of damage in complex carbon fibre/metal structures

    Science.gov (United States)

    Thursby, G. J.; MacLean, A.; Hogg, H.; Culshaw, B.

    2006-03-01

    We describe work carried out to monitor the structural health of a complex structure comprising both carbon fibre and metal components using ultrasound techniques. The work is designed to be used in a high performance car, but could find applications in other areas such as the aerospace industry. There are two different types of potential problem that need to be examined; the first is damage (e.g. holes, delaminations) to carbon fibre structure, and the second is damage to joints either between two carbon fibre components or between a carbon fibre component and a metallic one. The techniques used are based around the use of PZT transducers for both the generation and detection of ultrasonic Lamb waves. To date we have been carrying out experiments on mock-up samples, but are due to conduct tests on an actual vehicle. Lamb waves propagate in modes whose order is determined by the frequency thickness product. Their properties, such as phase and amplitude can be modified by the presence of damage, such as holes and delaminations. If we record the response of a healthy structure, we can then compare it with signals obtained on subsequent occasions to determine if any significant change has taken place. It is essential, however, to be able to differentiate between the effects of damage and those of environmental changes such as temperature. For this reason we have monitored the response of a sample at different temperatures both before and after drilling a hole in it to simulate damage. Depending on the positions of the transducers with respect to the damaged area, it is possible to detect either attenuation of the entire signal or changes in a specific portion of the signal produced by reflections. Results from these experiments will be presented at the conference. Signal processing techniques for separating damage from the effects of temperature will also be discussed. We also look at the deterioration of joints, which can either be epoxy bonded (carbon fibre to

  17. UV/TiO2 photocatalytic disinfection of carbon-bacteria complexes in activated carbon-filtered water: Laboratory and pilot-scale investigation.

    Science.gov (United States)

    Zhao, Jin Hui; Chen, Wei; Zhao, Yaqian; Liu, Cuiyun; Liu, Ranbin

    2015-01-01

    The occurrence of carbon-bacteria complexes in activated carbon filtered water has posed a public health problem regarding the biological safety of drinking water. The application of combined process of ultraviolet radiation and nanostructure titanium dioxide (UV/TiO2) photocatalysis for the disinfection of carbon-bacteria complexes were assessed in this study. Results showed that a 1.07 Lg disinfection rate can be achieved using a UV dose of 20 mJ cm(-2), while the optimal UV intensity was 0.01 mW cm(-2). Particle sizes ≥8 μm decreased the disinfection efficiency, whereas variation in particle number in activated carbon-filtered water did not significantly affect the disinfection efficiency. Photoreactivation ratio was reduced from 12.07% to 1.69% when the UV dose was increased from 5 mJ cm(-2) to 20 mJ cm(-2). Laboratory and on-site pilot-scale experiments have demonstrated that UV/TiO2 photocatalytic disinfection technology is capable of controlling the risk posed by carbon-bacteria complexes and securing drinking water safety.

  18. Theoretical study of the binding nature of glassy carbon with nickel(II) phthalocyanine complexes

    Energy Technology Data Exchange (ETDEWEB)

    Cortez, Luis [Laboratorio de Quimica Teorica, Facultad de Quimica y Biologia, Universidad de Santiago de Chile (USACH), Casilla 40, Correo 33, Santiago (Chile); Berrios, Cristhian [Laboratorio de Electrocatalisis, Facultad de Quimica y Biologia, Universidad de Santiago de Chile (USACH), Casilla 40, Correo 33, Santiago (Chile); Yanez, Mauricio [Laboratorio de Recursos Renovables, Centro de Biotecnologia, Universidad de Concepcion, Casilla-160 C, Concepcion (Chile); Cardenas-Jiron, Gloria I., E-mail: gloria.cardenas@usach.cl [Laboratorio de Quimica Teorica, Facultad de Quimica y Biologia, Universidad de Santiago de Chile (USACH), Casilla 40, Correo 33, Santiago (Chile)

    2009-11-26

    A theoretical study at the semiempirical RHF/PM3(tm) level (tm: transition metal) of the binding nature between a glassy carbon (GC) cluster and a nickel(II) complex (nickel(II) phthalocyanine NiPc, nickel(II) tetrasulphophthalocyanine NiTSPc) was performed. Three types of interactions for GC...NiPc (NiTSPc) were studied: (a) through an oxo (O) bridge, (b) through an hydroxo (OH) bridge, and (c) non-bridge. One layer (NiPc, NiTSPc) and two layers (NiPc...NiPc) of complex were considered. The binding energy calculated showed that in both cases NiPc and NiTSPc, the oxo structures are more stable than the hydroxo ones, and than the non-bridge systems. Charge analysis (NAO) predicted that GC gained more electrons in an oxo structure than in the analogues hydroxo. The theoretical results showed an agreement with the experimental data available, an oxo binding between GC and a nickel complex (NiPc, NiTSPc) in aqueous alkaline solutions is formed.

  19. Endohedral and exohedral complexes of substituted benzenes with carbon nanotubes and graphene

    Science.gov (United States)

    Munusamy, Elango; Wheeler, Steven E.

    2013-09-01

    Non-covalent complexes of cyclohexane and a series of substituted benzenes with short carbon nanotube (CNT) models are investigated primarily at the B97-D3/TZV(2d,2p) level of theory. Understanding non-covalent interactions of arenes with CNTs is vital for the development of next-generation organic electronic materials and for harnessing CNTs as nano-reactors and vehicles for drug delivery. The interaction of benzene and cyclohexane with the interior and exterior of CNTs depends on the nanotube diameter, particularly for endohedral complexes. Both benzene and cyclohexane interact more strongly with the interior of CNTs than the outside, with benzene exhibiting stronger interactions than cyclohexane for CNTs larger than (8,8). Studies of two benzenes inside of CNTs predict the formation of one-dimensional sandwich and parallel-displaced stacks of benzenes within certain sized CNTs, which could have interesting optoelectronic properties. Concerning the impact of substituents on the interaction of benzene with CNTs, we find that electrostatic interactions do not control substituent effects. That is, the electron-donating or -withdrawing character of the substituents is not correlated with the predicted interaction energies. Moreover, substituent effects are the same for both endohedral and exohedral complexes, despite the different electronic character of the interior and exterior CNT walls. Ultimately, substituent effects in π-stacking interactions with CNTs and graphene are explained by differences in dispersion interactions between the substituents and CNT walls or graphene surface.

  20. Supramolecular complexes of multivalent cholesterol-containing polymers to solubilize carbon nanotubes in apolar organic solvents.

    Science.gov (United States)

    Nguendia, Jules Zeuna; Zhong, Weiheng; Fleury, Alexandre; De Grandpré, Guillaume; Soldera, Armand; Sabat, Ribal Georges; Claverie, Jerome P

    2014-05-01

    Copolymers of 2-ethylhexyl acrylate (EHA) and cholesteryloxycarbonyl-2-hydroxymethacrylate (CEM) were prepared by reversible addition-fragmentation chain-transfer (RAFT) polymerization. Supramolecular complexes of these copolymers with carbon nanotubes (CNTs) were soluble in THF, toluene, and isooctane. The colloidal solutions remained stable for months without aggregation. The rationale for the choice of CEM was based on the high adsorption energy of cholesterol on the CNT surface, as computed by DFT calculations. Adsorption isotherms were experimentally measured for copolymers of various architectures (statistical, diblock, and star copolymers), thereby demonstrating that 2-5 cholesterol groups were adsorbed per polymer chain. Once the supramolecular complex had dried, the CNTs could be easily resolubilized in isooctane without the need for high-power sonication and in the absence of added polymer. Analysis by atomic force microscopy (AFM), scanning electron microscopy (SEM), and transmission electron microscopy (TEM) indicated that the CNTs were devoid of bundles. The supramolecular complexes could also be employed in an inverse emulsion polymerization of 2-hydroxyethylmethacrylate (HEMA) in isooctane and dodecane, thereby leading to the formation of a continuous polymeric sheath around the CNTs. Thus, this technique leads to the formation of very stable dispersions in non-polar organic solvents, without altering the fundamental properties of the CNTs. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  1. Architecture and evolution of an Early Permian carbonate complex on a tectonically active island in east-central California

    Science.gov (United States)

    Stevens, Calvin H.; Magginetti, Robert T.; Stone, Paul

    2015-01-01

    The newly named Upland Valley Limestone represents a carbonate complex that developed on and adjacent to a tectonically active island in east-central California during a brief interval of Early Permian (late Artinskian) time. This lithologically unique, relatively thin limestone unit lies within a thick sequence of predominantly siliciclastic rocks and is characterized by its high concentration of crinoidal debris, pronounced lateral changes in thickness and lithofacies, and a largely endemic fusulinid fauna. Most outcrops represent a carbonate platform and debris derived from it and shed downslope, but another group of outcrops represents one or possibly more isolated carbonate buildups that developed offshore from the platform. Tectonic activity in the area occurred before, probably during, and after deposition of this short-lived carbonate complex.

  2. A modular framework for management of complexity in international forest-carbon policy

    Science.gov (United States)

    Law, Elizabeth A.; Thomas, Sebastian; Meijaard, Erik; Dargusch, Paul J.; Wilson, Kerrie A.

    2012-03-01

    Complex and variable ecological and social settings make the programme on reducing emissions through avoided deforestation, forest degradation and other forestry activities in developing countries (REDD+) a challenging policy to design. The total value to society of each type of REDD+ outcome is dependent on the fundamentally different risk profiles of alternative forest-management approaches and their scope and potential for co-benefits. We suggest a modular policy framework for REDD+ that distinguishes and differentially compensates the distinct outcomes. This could represent an improved framework to promote and manage incentives for effective forest-carbon initiatives, offer better scope to find common ground in policy negotiations and allow faster adaptation of policy to an uncertain future.

  3. Organometallic Complexes Anchored to Conductive Carbon for Electrocatalytic Oxidation of Methane at Low Temperature.

    Science.gov (United States)

    Joglekar, Madhura; Nguyen, Vinh; Pylypenko, Svitlana; Ngo, Chilan; Li, Quanning; O'Reilly, Matthew E; Gray, Tristan S; Hubbard, William A; Gunnoe, T Brent; Herring, Andrew M; Trewyn, Brian G

    2016-01-13

    Low-temperature direct methane fuel cells (DMEFCs) offer the opportunity to substantially improve the efficiency of energy production from natural gas. This study focuses on the development of well-defined platinum organometallic complexes covalently anchored to ordered mesoporous carbon (OMC) for electrochemical oxidation of methane in a proton exchange membrane fuel cell at 80 °C. A maximum normalized power of 403 μW/mg Pt was obtained, which was 5 times higher than the power obtained from a modern commercial catalyst and 2 orders of magnitude greater than that from a Pt black catalyst. The observed differences in catalytic activities for oxidation of methane are linked to the chemistry of the tethered catalysts, determined by X-ray photoelectron spectroscopy. The chemistry/activity relationships demonstrate a tangible path for the design of electrocatalytic systems for C-H bond activation that afford superior performance in DMEFC for potential commercial applications.

  4. Polymeric Framboidal Nanoparticles Loaded with a Carbon Monoxide Donor via Phenylboronic Acid-Catechol Complexation.

    Science.gov (United States)

    van der Vlies, André J; Inubushi, Ryosuke; Uyama, Hiroshi; Hasegawa, Urara

    2016-06-15

    Carbon monoxide (CO) is an essential gaseous signaling molecule in the human body. Toward the controlled delivery of CO to the target tissues or cells, nanomaterial-based CO donors have attracted growing attention. Here, we present CO-releasing polymeric nanoparticles (CONPs) prepared by simple mixing of phenylboronic acid-containing framboidal nanoparticles with the catechol-bearing CO-donor Ru(CO)3Cl(L-DOPA) via phenylboronic acid-catechol complexation. The CONPs release CO in response to cysteine and suppress the production of the pro-inflammatory mediators interleukin 6 (IL-6) and nitric oxide (NO) in lipopolysaccharide (LPS)-stimulated murine macrophages. This CONP platform may show promise in therapeutic applications of CO.

  5. Hydrogen bonded complexes of cyanuric acid with pyridine and guanidinium carbonate

    Indian Academy of Sciences (India)

    K Sivashankar

    2000-12-01

    Hydrogen bonded complexes of cyanuric acid (CA) with pyridine, [C3N3H3O3:C5H5N], 1, and guanidinium carbonate [C3H2N3][C(NH2)3], 2, have been prepared at room temperature and characterized by single-crystal X-ray diffraction. Structure of 1 shows pyridine molecules substituting the inter-tape hydrogen bond in CA by N-H…N and C-H…O hydrogen bonds. The structure reveals CA-pyridine hydrogen-bonded single helices held together by dimeric N-H…O hydrogen bonding between CA molecules. In 2, the CA tapes, resembling a sine wave interact with the guanidinium cations through N-H…O and N-H…N hydrogen bonds forming guanidinium cyanurate sheets.

  6. Carbon-tuned bonding method significantly enhanced the hydrogen storage of BN-Li complexes.

    Science.gov (United States)

    Deng, Qing-ming; Zhao, Lina; Luo, You-hua; Zhang, Meng; Zhao, Li-xia; Zhao, Yuliang

    2011-11-01

    Through first-principles calculations, we found doping carbon atoms onto BN monolayers (BNC) could significantly strengthen the Li bond on this material. Unlike the weak bond strength between Li atoms and the pristine BN layer, it is observed that Li atoms are strongly hybridized and donate their electrons to the doped substrate, which is responsible for the enhanced binding energy. Li adsorbed on the BNC layer can serve as a high-capacity hydrogen storage medium, without forming clusters, which can be recycled at room temperature. Eight polarized H(2) molecules are attached to two Li atoms with an optimal binding energy of 0.16-0.28 eV/H(2), which results from the electrostatic interaction of the polarized charge of hydrogen molecules with the electric field induced by positive Li atoms. This practical carbon-tuned BN-Li complex can work as a very high-capacity hydrogen storage medium with a gravimetric density of hydrogen of 12.2 wt%, which is much higher than the gravimetric goal of 5.5 wt % hydrogen set by the U.S. Department of Energy for 2015.

  7. Treatment of complex Remazol dye effluent using sawdust- and coal-based activated carbons.

    Science.gov (United States)

    Vijayaraghavan, K; Won, Sung Wook; Yun, Yeoung-Sang

    2009-08-15

    A complex Remazol dye effluent, comprised of four reactive dyes and auxiliary chemicals, was decolorized using SPS-200 (sawdust-based) and SPC-100 (coal-based) activated carbons. A detailed characterization revealed that the pore diameter of the activated carbon played an important role in dye adsorption. The solution pH had no significant effect on the adsorption capacity in the pH range of 2-10.7. According to the Langmuir model, the maximum uptakes of SPS-200 were 415.4, 510.3, 368.5 and 453.0 mg g(-1) for Reactive Black 5 (RB5), Reactive Orange 16 (RO16), Remazol Brilliant Blue R (RBBR) and Remazol Brilliant Violet 5R (RBV), respectively. Conversely, those of SPC-100 were slightly lower, at 150.8, 197.4, 178.3 and 201.1 mg g(-1) for RB5, RO16, RBBR and RBV, respectively. In the case of Remazol effluent, SPS-200 exhibited a decolorization efficiency of 100% under unadjusted pH conditions at 10.7, compared to that of 52% for SPC-100.

  8. 28-Homobrassinolide Modulate Antenna Complexes and Carbon Skeleton of Brassica juncea L. under Temperature Stress

    Directory of Open Access Journals (Sweden)

    Harpreet Kaur

    2014-08-01

    Full Text Available The aim of present study was to explore the ameliorative impact of 28-homoBL on morpho-physiological attributes, photosynthetic pigments and sugars of Brassica juncea L. exposed to oxidative stress caused by extreme temperatures (4 and 44 °C. For this, experiments were carried out at the Plant Physiology Laboratory, Department of Botany, Punjabi University, Patiala. Effect of different degrees of temperature (4 and 44 °C taking 24 °C as control was studied. 28-homoBL (10-6, 10-9 and 10-12M primed and unprimed seeds of B. juncea L. in terms of antenna complexes and end products of photosynthesis that is total carbohydrates and total soluble sugars was investigated. All concentrations of 28-homoBL used in present study showed different effects on morphology and light quenching pigments. All concentrations of 28-homoBL showed promoting effect on growth and light quenching pigments. The carbon makeup ameliorated positively in stressed and non-stressed components of photosynthetic machinery and 10-9 M 28-homoBL showed best results. In conclusion 28-homoBL showed great potential in protecting the reaction centre of photosynthetic machinery from oxidative stress caused by extreme low and high temperatures but in very dose dependent manner and thus modulate the carbon skeleton of the plant.

  9. Cationic organobismuth complex as an effective catalyst for conversion of CO2 into cyclic carbonates

    Institute of Scientific and Technical Information of China (English)

    Xiaowen ZHANG; Weili DAI; Shuangfeng YIN; Shenglian LUO; Chak-Tong AU

    2009-01-01

    In order to achieve high-efficiency conversion of CO2 into valuable chemicals, and to exploit new appli-cations of organobismuth compounds, cationic organo-bismuth complex with 5,6,7,12-tetrahydrodibenz[c,f] [ 1,5 ]azabismocine framework was examined for the first time for the coupling of CO2 into cyclic carbonates, using ter-minal epoxides as substrates and tetrabutylammonium halide as co-catalyst in a solvent-free environment under mild conditions. It is shown that the catalyst exhibited high activity and selectivity for the coupling reaction of CO2 with a wide range of terminal epoxide. The selectivity of propylene carbonates could reach 100%, and the max-imum turnover frequency was up to 10740 h-1 at 120℃ and 3 MPa CO2 pressure when tetrabutylammonium iod-ide was used as co-catalyst. Moreover, the catalyst is environment friendly, resistant to air and water, and can be readily reused and recycled without any loss of activity,demonstrating a potential in industrial application.

  10. Nitrogen-doped carbon nanofoam derived from amino acid chelate complex for supercapacitor applications

    Science.gov (United States)

    Ramakrishnan, Prakash; Shanmugam, Sangaraju

    2016-06-01

    We report a novel strategy to fabricate the nitrogen-doped mesoporous carbon nanofoam structures (N-MCNF), derived from magnesium amino acid chelate complex (Mg-acc-complex) for its application towards high performance supercapacitor (SCs) system. A series of N-MCNF with well-connected carbon nanofoam structure have been developed by varying the synthesis temperature. The fabricated N-MCNF material possesses a high surface area (1564 m2 g-1) and pore volume (1.767 cm3 g-1) with nitrogen content of 3.42 wt%. A prototypical coin cell type symmetric N-MCNF SC device has been assembled with 1-ethyl-3-methylimidazolium tetrafluoroborate [EMIMBF4] ionic liquid electrolyte, and evaluated for SCs studies. The N-MCNF with high textural properties delivers unprecedented SC performance, such as high specific capacitance (204 Fg-1 at 0.25 Ag-1, 25 °C), high energy density (63.4 Wh kg-1), high power density (35.9 kW kg-1) and long-term cycle life (32,500 cycles). Significantly, N-MCNF materials exhibited high power rate performance, at 500 mV-1 (115 Fg-1) and 25 Ag-1 (166 Fg-1) owing to the uniform mesopore size distribution (∼4 nm). The N-MCNF SC device delivered maximum energy densities of 83.4 and 93.3 Wh kg-1 at 60 °C and 90 °C, respectively. Such outstanding N-MCNF SC device is successfully demonstrated in solar energy harvester applications.

  11. Introduction to the special section: Recent advancement on integrated carbonate reservoirs prediction with complex secondary storage space

    Institute of Scientific and Technical Information of China (English)

    2011-01-01

    Carbonate reservoirs in Western China show tremendous exploration and development potential.These have become the key area for oil and gas reserves addition and sustainable resource development for China.Compared to conventional carbonate reservoirs,prediction of this kind of reservoir predominated by secondary storage is much more difficult and presents significant challenges.Seismic detection of dissolution pores and fractures always requires a high standard of technology,which puts further serious challenges on exploration and creates many technological issues for field development plans.The key geophysical problems are tackled based on a detailed analysis of exploration issues for such complex carbonate reservoirs.

  12. Hydroxyl, water, ammonia, carbon monoxide, and neutral carbon towards the Sagittarius A complex. VLA, Odin, and SEST observations

    Science.gov (United States)

    Karlsson, R.; Sandqvist, Å.; Hjalmarson, Å.; Winnberg, A.; Fathi, K.; Frisk, U.; Olberg, M.

    2013-06-01

    Aims: The Sagittarius A complex in the Galactic centre comprises an ensemble of molecular clouds of different species with a variety of geometrical and kinematic properties. This work aims to study molecular abundances, morphology, and kinematics by comparing hydroxyl, water, carbon monoxide, ammonia, and atomic carbon and some of their isotopologues, in the +50 km s-1 cloud, the circumnuclear disk (CND), the +20 km s-1 cloud, the expanding molecular ring and the line-of-sight spiral arm features, including the Local/Sgr arm, the -30 km s-1 arm, and the 3-kpc arm. Methods: We observed the +50 km s-1 cloud, the CND and the +20 km s-1 cloud, and other selected positions at the Galactic centre with the VLA, and the Odin satellite. The VLA was used to map the 1665 and 1667 MHz OH lambda doublet main lines of the (2Π3/2) state, and the Odin satellite was used to map the 557 GHz H2O (110 - 101) line as well as to observe the 548 GHz H218O (110-101) line, the 572 GHz NH3 (10 - 00) line, the 576 GHz CO J = 5 - 4 line and the 492 GHz C i (3P1-3P0) line. Furthermore, the SEST was used to map a region of the Sgr A complex in the 220 GHz C18O J = 2-1 line. Results: Strong OH absorption, H2O emission and absorption lines were seen at all observed positions, and the H218O line was detected in absorption towards the +50 km s-1 cloud, the CND, the +20 km s-1cloud, the expanding molecular ring, and the 3-kpc arm. Strong CO J = 5-4, C18O J = 2-1, and neutral carbon C i emissions were seen towards the +50 and +20 km s-1 clouds. NH3 was only detected in weak absorption originating in the line-of-sight spiral arm features. The abundances of OH and H2O in the +50 and +20 km s-1 clouds reflect the different physical environments in the clouds, where shocks and star formation prevail in the +50 km s-1 cloud and giving rise to a higher rate of H2O production there than in the +20 km s-1 cloud. In the CND, cloud collisions and shocks are frequent, and the CND is also subject to intense UV

  13. Organo-mineral complexation alters carbon and nitrogen cycling in stream microbial assemblages

    Science.gov (United States)

    Hunter, William Ross; Wanek, Wolfgang; Prommer, Judith; Mooshammer, Maria; Battin, Tom

    2014-05-01

    Inland waters are of global biogeochemical importance receiving carbon inputs of ~ 4.8 Pg C y-1. Of this 12 % is buried, 18 % transported to the oceans, and 70 % supports aquatic secondary production. However, the mechanisms that determine the fate of organic matter (OM) in these systems are poorly defined. One important aspect is the formation of organo-mineral complexes in aquatic systems and their potential as a route for OM transport and burial vs. microbial utilization as organic carbon (C) and nitrogen (N) sources. Organo-mineral particles form by sorption of dissolved OM to freshly eroded mineral surfaces and may contribute to ecosystem-scale particulate OM fluxes. We tested the availability of mineral-sorbed OM as a C & N source for streamwater microbial assemblages and streambed biofilms. Organo-mineral particles were constructed in vitro by sorption of 13C:15N-labelled amino acids to hydrated kaolin particles, and microbial degradation of these particles compared with equivalent doses of 13C:15N-labelled free amino acids. Experiments were conducted in 120 ml mesocosms over 7 days using biofilms and streamwater sampled from the Oberer Seebach stream (Austria), tracing assimilation and mineralization of 13C and 15N labels from mineral-sorbed and dissolved amino acids. Here we present data on the effects of organo-mineral sorption upon amino acid mineralization and its C:N stoichiometry. Organo-mineral sorption had a significant effect upon microbial activity, restricting C and N mineralization by both the biofilm and streamwater treatments. Distinct differences in community response were observed, with both dissolved and mineral-stabilized amino acids playing an enhanced role in the metabolism of the streamwater microbial community. Mineral-sorption of amino acids differentially affected C & N mineralization and reduced the C:N ratio of the dissolved amino acid pool. The present study demonstrates that organo-mineral complexes restrict microbial degradation

  14. Unique chemical properties of metal-carbon bonds in metal-carboranyl and metal-carboryne complexes

    Institute of Scientific and Technical Information of China (English)

    QIU ZaoZao; XIE ZuoWei

    2009-01-01

    The metal-carbon bonds in metal-carboranyl and metal-carboryne complexes behave very differently from those in classical organometallic complexes. The unique electronic and steric properties of icosahedral carboranyl moiety make the M-C bond in metal-carboranyl complexes inert toward unsaturated molecules, and on the other hand, the sterically demanding carborane cage can induce unexpected C-C coupling reactions. The M-C bonds in metal-carboryne complexes are, however, active toward various kinds of unsaturated molecules and the reactivity patterns are dependent upon the electronic configurations of the metal ions. This account provides an overview of our recent work in this area.

  15. Unique chemical properties of metal-carbon bonds in metal-carboranyl and metal-carboryne complexes

    Institute of Scientific and Technical Information of China (English)

    2009-01-01

    The metal-carbon bonds in metal-carboranyl and metal-carboryne complexes behave very differently from those in classical organometallic complexes. The unique electronic and steric properties of ico-sahedral carboranyl moiety make the M-C bond in metal-carboranyl complexes inert toward unsaturated molecules, and on the other hand, the sterically demanding carborane cage can induce unexpected C-C coupling reactions. The M-C bonds in metal-carboryne complexes are, however, active toward various kinds of unsaturated molecules and the reactivity patterns are dependent upon the electronic configurations of the metal ions. This account provides an overview of our recent work in this area.

  16. Functionalized granular activated carbon and surface complexation with chromates and bi-chromates in wastewater.

    Science.gov (United States)

    Singha, Somdutta; Sarkar, Ujjaini; Luharuka, Pallavi

    2013-03-01

    Cr(VI) is present in the aqueous medium as chromate (CrO4(2-)) and bi-chromate (HCrO4(-)). Functionalized granular activated carbons (FACs) are used as adsorbents in the treatment of wastewaters containing hexavalent chromium. The FACs are prepared by chemical modifications of granular activated carbons (GACs) using functionalizing agents like HNO3, HCl and HF. The Brunauer, Emmett and Teller surface areas of FAC-HCl (693.5m(2)/g), FAC-HNO3 (648.8m(2)/g) and FAC-HF (726.2m(2)/g) are comparable to the GAC (777.7m(2)/g). But, the adsorption capacity of each of the FAC-HNO3, FAC-HCl and FAC-HF is found to be higher than the GAC. The functional groups play an important role in the adsorption process and pH has practically no role in this specific case. The FACs have hydrophilic protonated external surfaces in particular, along with the functional surface sites capable to make complexes with the CrO4(2-) and HCrO4(-) present. Surface complex formation is maximized in the order FAC-HNO3>FAC-HF>FAC-HCl, in proportion to the total surface acidity. This is also confirmed by the well-known pseudo second-order kinetic model. Physi-sorption equilibrium isotherms are parameterized by using standard Freundlich and Langmuir models. Langmuir fits better. The formation of surface complexes with the functional groups and hexavalent chromium is also revealed in the images of field emission scanning electron micrograph; energy dispersive X-ray spectroscopy and Fourier transform infrared spectroscopy analysis after adsorption. The intra-particle diffusion is not the only rate-controlling factor. The Boyd's film diffusion model fits very well with R(2) as high as 98.1% for FAC-HNO3. This result demonstrates that the functionalization of the GAC by acid treatments would increase the diffusion rate, predominantly with a boundary layer diffusion effect. Copyright © 2013 Elsevier B.V. All rights reserved.

  17. A selective colorimetric Hg2+ probe featuring a styryl dithiaazacrown containing platinum (II) terpyridine complex through modulation of the relative strength of ICT and MLCT transitions.

    Science.gov (United States)

    Chung, Sung-Kuang; Tseng, Yong-Ren; Chen, Chan-Yu; Sun, Shih-Sheng

    2011-04-04

    A series of platinum(II) terpyridine complexes featuring an aminostilbene donor-acceptor framework was synthesized. The complex with a dithiaazacrown moiety exhibits a highly sensitive and selective colorimetric response to a Hg(2+) cation through modulation of the relative strength of ICT and MLCT transitions. The results from (1)H NMR titration suggest the existence of a weak Pt(II)···Hg(II) metallophilic interaction at low Hg(2+) concentration.

  18. "Drawing with nanotubes": creating nanowires with complex geometries by pulsed electrodeposition on self-organized carbon nanotube patterns.

    Science.gov (United States)

    Yarden, Tohar S; Joselevich, Ernesto

    2010-11-10

    We present a new approach for the creation of nanowires with well-defined complex geometries by electrodeposition onto self-organized single-walled carbon nanotubes. The concept is demonstrated by generation of continuous Au nanowires with various geometries, including parallel arrays, serpentines, and coils. The generality of this approach is further illustrated by synthesizing Bi(2)Te(3) nanowires. Our concept of "drawing with nanotubes" offers to combine different material properties with complex geometries on the route to new functional nanosystems.

  19. Characterization of complex (B + C) diffusion layers formed on chromium and nickel-based low-carbon steel

    Energy Technology Data Exchange (ETDEWEB)

    Pertek, A.; Kulka, M

    2002-12-30

    Combined surface hardening with boron and carbon was used for low-carbon chromium and nickel-based steels. The microstructure, boron contents, carbon profiles and chosen properties of borided layers produced on the carburized steels have been examined. These complex (B+C) layers are termed borburized layers. The microhardness profiles and wear resistance of these layers have been studied. In the microstructure of the borocarburized layer two zones have been observed: iron borides (FeB+Fe{sub 2}B) and a carburized layer. The depth (70-125 {mu}m) and microhardness (1500-1800 HV) of iron borides zone have been found. The carbon content (1.2-1.94 wt.%) and microhardness (700-950 HV) beneath iron borides zone have been determined. The microhardness gradient in borocarburized layer has been reduced in comparison with the only borided layer. An increase of distance from the surface is accompanied by a decrease of carbon content and microhardness in the carburized zone. The carbon and microhardness profiles of borided, carburized and borocarburized layers have been presented. A positive influence of complex layers (B+C) on the wear resistance was determined. The wear resistance of the borocarburized layer was determined to be greater in comparison with that for only borided or only carburized layers.

  20. Degraded tropical rain forests possess valuable carbon storage opportunities in a complex, forested landscape

    Science.gov (United States)

    Alamgir, Mohammed; Campbell, Mason J.; Turton, Stephen M.; Pert, Petina L.; Edwards, Will; Laurance, William F.

    2016-01-01

    Tropical forests are major contributors to the terrestrial global carbon pool, but this pool is being reduced via deforestation and forest degradation. Relatively few studies have assessed carbon storage in degraded tropical forests. We sampled 37,000 m2 of intact rainforest, degraded rainforest and sclerophyll forest across the greater Wet Tropics bioregion of northeast Australia. We compared aboveground biomass and carbon storage of the three forest types, and the effects of forest structural attributes and environmental factors that influence carbon storage. Some degraded forests were found to store much less aboveground carbon than intact rainforests, whereas others sites had similar carbon storage to primary forest. Sclerophyll forests had lower carbon storage, comparable to the most heavily degraded rainforests. Our findings indicate that under certain situations, degraded forest may store as much carbon as intact rainforests. Strategic rehabilitation of degraded forests could enhance regional carbon storage and have positive benefits for tropical biodiversity. PMID:27435389

  1. Degraded tropical rain forests possess valuable carbon storage opportunities in a complex, forested landscape

    Science.gov (United States)

    Alamgir, Mohammed; Campbell, Mason J.; Turton, Stephen M.; Pert, Petina L.; Edwards, Will; Laurance, William F.

    2016-07-01

    Tropical forests are major contributors to the terrestrial global carbon pool, but this pool is being reduced via deforestation and forest degradation. Relatively few studies have assessed carbon storage in degraded tropical forests. We sampled 37,000 m2 of intact rainforest, degraded rainforest and sclerophyll forest across the greater Wet Tropics bioregion of northeast Australia. We compared aboveground biomass and carbon storage of the three forest types, and the effects of forest structural attributes and environmental factors that influence carbon storage. Some degraded forests were found to store much less aboveground carbon than intact rainforests, whereas others sites had similar carbon storage to primary forest. Sclerophyll forests had lower carbon storage, comparable to the most heavily degraded rainforests. Our findings indicate that under certain situations, degraded forest may store as much carbon as intact rainforests. Strategic rehabilitation of degraded forests could enhance regional carbon storage and have positive benefits for tropical biodiversity.

  2. Degraded tropical rain forests possess valuable carbon storage opportunities in a complex, forested landscape.

    Science.gov (United States)

    Alamgir, Mohammed; Campbell, Mason J; Turton, Stephen M; Pert, Petina L; Edwards, Will; Laurance, William F

    2016-07-20

    Tropical forests are major contributors to the terrestrial global carbon pool, but this pool is being reduced via deforestation and forest degradation. Relatively few studies have assessed carbon storage in degraded tropical forests. We sampled 37,000 m(2) of intact rainforest, degraded rainforest and sclerophyll forest across the greater Wet Tropics bioregion of northeast Australia. We compared aboveground biomass and carbon storage of the three forest types, and the effects of forest structural attributes and environmental factors that influence carbon storage. Some degraded forests were found to store much less aboveground carbon than intact rainforests, whereas others sites had similar carbon storage to primary forest. Sclerophyll forests had lower carbon storage, comparable to the most heavily degraded rainforests. Our findings indicate that under certain situations, degraded forest may store as much carbon as intact rainforests. Strategic rehabilitation of degraded forests could enhance regional carbon storage and have positive benefits for tropical biodiversity.

  3. THE INFLUENCE OF THE COMPLEX CHEMICAL ADDITIVE CONTAINING THE STRUCTURED CARBON NANOMATERIAL ON PROPERTIES OF CEMENT

    Directory of Open Access Journals (Sweden)

    O. Yu. Sheyda

    2015-01-01

    Full Text Available The paper presents results of investigations on influence of domestic complex chemical additive containing structured carbon nanomaterial and characterized by a combination effect (curing acceleration and plasticizing on cement and cement stone properties. The purpose of the investigations, on the one hand, has been to confirm efficacy of УКД-1additive from the perspective for increasing the rate of gain, strength growth of cement concrete and additive influence on setting time with the purpose to preserve molding properties of concrete mixes in time, and on the other hand, that is to assess “mechanism” of the УКД-1 additive action in the cement concrete. The research results have revealed regularities in changes due to the additive of water requirements and time period of the cement setting. The reqularities are considered as a pre-requisite for relevant changes in molding properties of the concrete mixes. The paper also experimentally substantiates the possibility to decrease temperature of cement concrete heating with the УДК-1 additive. It has been done with the purpose to save energy resources under production conditions. In addition to this the paper proves the efficiency of the additive which is expressed in strength increase of cement stone up to 20–40 % in the rated age (28 days that is considered as a basis for strength growth of cement concrete. The paper confirms a hypothesis on physical nature of this phenomenon because the X-ray phase analysis method has shown that there are no changes in morphology of portland cement hydration products under the action of the additive agent containing a structured carbon nanomaterial. Results of theoretical and experimental investigations on УКД-1 additive efficiency have been proved by industrial approbation while fabricating precast concrete products and construction of monolithic structures under plant industrial conditions (Minsk, SS “Stroyprogress” JSC MAPID and on

  4. Formation and annealing of metastable (interstitial oxygen)-(interstitial carbon) complexes in n- and p-type silicon

    CERN Document Server

    Makarenko, L F; Lastovskii, S B; Murin, L I; Moll, M; Pintilie, I

    2014-01-01

    It is shown experimentally that, in contrast to the stable configuration of (interstitial carbon)-(interstitial oxygen) complexes (CiOi), the corresponding metastable configuration (CiOi{*}) cannot be found in n-Si based structures by the method of capacitance spectroscopy. The rates of transformation CiOi{*} -> CiOi are practically the same for both n- and p-Si with a concentration of charge carriers of no higher than 10(13) cm(-3). It is established that the probabilities of the simultaneous formation of stable and metastable configurations of the complex under study in the case of the addition of an atom of interstitial carbon to an atom of interstitial oxygen is close to 50\\%. This is caused by the orientation dependence of the interaction potential of an atom of interstitial oxygen with an interstitial carbon atom, which diffuses to this oxygen atom.

  5. Further evidence for charge transfer complexes in brown carbon aerosols from excitation-emission matrix fluorescence spectroscopy.

    Science.gov (United States)

    Phillips, Sabrina M; Smith, Geoffrey D

    2015-05-14

    The light-absorbing fraction of organic molecules in ambient aerosols, known as "brown carbon," is an important yet poorly characterized component. Despite the fact that brown carbon could alter the radiative forcing of aerosols significantly, identification of specific chromophores has remained challenging. We recently demonstrated that charge transfer (CT) complexes formed in organic molecules could be responsible for a large fraction of absorption observed in water-extracted ambient particulate matter.1 In the present study, we use excitation-emission matrix fluorescence spectroscopy to further corroborate the importance of CT complexes in defining aerosol optical properties. Monotonically increasing and decreasing quantum yields, decreasing Stokes shifts, and red-shifting emission maxima are observed from ambient particulate matter collected in Athens, Georgia, strongly suggesting that a superposition of independent chromophores is not sufficient to explain brown carbon absorption and fluorescence. Instead, we show that a model in which such chromophores are energetically coupled to a dense manifold of CT complexes is consistent with all of the observations. Further, we suggest that a significant fraction of the observed fluorescence originates from CT complexes and that their contribution to brown carbon absorption is likely greater than we reported previously.

  6. Trace element geochemistry of Amba Dongar carbonatite complex, India: Evidence for fractional crystallization and silicate-carbonate melt immiscibility

    Indian Academy of Sciences (India)

    Jyotiranjan S Ray; P N Shukla

    2004-12-01

    Carbonatites are believed to have crystallized either from mantle-derived primary carbonate magmas or from secondary melts derived from carbonated silicate magmas through liquid immiscibility or from residual melts of fractional crystallization of silicate magmas. Although the observed coexistence of carbonatites and alkaline silicate rocks in most complexes, their coeval emplacement in many, and overlapping initial 87Sr/86Sr and 143Nd/144Nd ratios are supportive of their cogenesis; there have been few efforts to devise a quantitative method to identify the magmatic processes. In the present study we have made an attempt to accomplish this by modeling the trace element contents of carbonatites and coeval alkaline silicate rocks of Amba Dongar complex, India. Trace element data suggest that the carbonatites and alkaline silicate rocks of this complex are products of fractional crystallization of two separate parental melts. Using the available silicate melt-carbonate melt partition coefficients for various trace elements, and the observed data from carbonatites, we have tried to simulate trace element distribution pattern for the parental silicate melt. The results of the modeling not only support the hypothesis of silicate-carbonate melt immiscibility for the evolution of Amba Dongar but also establish a procedure to test the above hypothesis in such complexes.

  7. Evolution of multi-mineral formation evaluation using LWD data in complex carbonates offshore Brazil

    Energy Technology Data Exchange (ETDEWEB)

    Ferraris, Paolo; Borovskaya, Irina [Schlumberger, Houston, TX (United States)

    2012-07-01

    Petrophysical Formation Evaluation using Logging While Drilling (LWD) measurements is a new requisite when drilling in carbonates reservoirs offshore Brazil. These reservoirs are difficult to characterize due to an unusual mixture of the minerals constituting the matrix and affecting rock texture. As wells are getting deeper and more expensive, an early identification of the drilled targets potential is necessary for valuable decisions. Brazil operators have been especially demanding towards service providers, pushing for development of suitable services able to positively identify and quantify not only the presence of hydrocarbons but also their flowing capability. In addition to the standard gamma ray / resistivity / porosity and density measurements, three new measurements have proven to be critical to evaluate complex carbonate formations: Nuclear Magnetic Resonance (NMR), Spectroscopy and Capture Cross-Section (sigma). Under appropriate logging conditions, NMR data provides lithology independent porosity, bound and free fluids fractions, reservoir texture and permeability. Capture Spectroscopy allows assessment of mineral composition in terms of calcite, dolomite, quartz and clay fractions, and in addition highlights presence of other heavier minerals. Finally, sigma allows performing a volumetric formation evaluation without requiring custom optimization of the classical exponents used in all forms of resistivity saturation equations. All these new measurements are inherently statistical and if provided by wireline after drilling the well they may result in significant usage of rig time. When acquired simultaneously while drilling they have three very clear advantages: 1) no extra rig time, 2) improved statistics due to long formation exposure (drilling these carbonates is a slow process and rate of penetration (ROP) rarely exceeds 10 m/hr), 3) less invasion effect and better hole condition. This paper describes the development of two LWD tools performing the

  8. Synthesis and reactivity towards diiodine of palladium(II) and platinum(II) complexes with non-cyclic and cyclic ligands (C6H3{CH=NR1R2}2-2,6)-. End-on diiodine-platinum(II) bonding in macrocyclic [PtI(C6H3{CH2NMe(CH2)7MeNCH2}-2,6)(h1-I2)

    NARCIS (Netherlands)

    Koten, G. van; Beek, J.A.M. van; Dekker, G.P.C.M.; Wissing, E.; Zoutberg, M.C.; Stam, C.H.

    1990-01-01

    Several new organo-platinum(II) and -palladium(II) complexes [MX(C{6}H{3}{CH{2}NR}1{R}2{}{2}-2, 6)] (X = halide, M = Pt, Pd; R}1{ = R}2{ = Et; R}2{ = Me, R}1{ = }t{Bu, M = Pt: R}2{ = Me, R}1{ = Ph) have been synthesized from [PtCl{2}(SEt{2}){2}] or [PdCl{2}(COD)] (COD = 1, 5-cyclooctadiene) by react

  9. Synthesis and reactivity towards diiodine of palladium(II) and platinum(II) complexes with non-cyclic and cyclic ligands (C6H3{CH=NR1R2}2-2,6)-. End-on diiodine-platinum(II) bonding in macrocyclic [PtI(C6H3{CH2NMe(CH2)7MeNCH2}-2,6)(h1-I2)

    NARCIS (Netherlands)

    Koten, G. van; Beek, J.A.M. van; Dekker, G.P.C.M.; Wissing, E.; Zoutberg, M.C.; Stam, C.H.

    1990-01-01

    Several new organo-platinum(II) and -palladium(II) complexes [MX(C{6}H{3}{CH{2}NR}1{R}2{}{2}-2, 6)] (X = halide, M = Pt, Pd; R}1{ = R}2{ = Et; R}2{ = Me, R}1{ = }t{Bu, M = Pt: R}2{ = Me, R}1{ = Ph) have been synthesized from [PtCl{2}(SEt{2}){2}] or [PdCl{2}(COD)] (COD = 1, 5-cyclooctadiene) by

  10. Synthesis and reactivity towards diiodine of palladium(II) and platinum(II) complexes with non-cyclic and cyclic ligands (C6H3{CH=NR1R2}2-2,6)-. End-on diiodine-platinum(II) bonding in macrocyclic [PtI(C6H3{CH2NMe(CH2)7MeNCH2}-2,6)(h1-I2)

    NARCIS (Netherlands)

    Koten, G. van; Beek, J.A.M. van; Dekker, G.P.C.M.; Wissing, E.; Zoutberg, M.C.; Stam, C.H.

    1990-01-01

    Several new organo-platinum(II) and -palladium(II) complexes [MX(C{6}H{3}{CH{2}NR}1{R}2{}{2}-2, 6)] (X = halide, M = Pt, Pd; R}1{ = R}2{ = Et; R}2{ = Me, R}1{ = }t{Bu, M = Pt: R}2{ = Me, R}1{ = Ph) have been synthesized from [PtCl{2}(SEt{2}){2}] or [PdCl{2}(COD)] (COD = 1, 5-cyclooctadiene) by react

  11. Study of new complexes of uranium and comba radical. I.- Complexes defective in sodium carbonate; Estudio de nuevos complejos entre el uranio y el radical CDMBA. I. Complejos con defectos de carbonato sodico

    Energy Technology Data Exchange (ETDEWEB)

    Vera Palomino, J.; Galiano Sedano, J. A.; Parellada Bellod, R.; Bellido Gonzalez, A.

    1975-07-01

    Some complexes formed in presence of defect of sodium carbonate with respect to the stoichiometric ratio (U): (C0{sub 3}) = 1:3 are studied. This ratio corresponds to the main complex which is responsible for the uranium extraction with CDMBAC organic solutions and from U(VI) aqueous solutions with an excess of sodium carbonate. (Author) 10 refs.

  12. Evidence of different stoichiometries for the limiting carbonate complexes of lanthanides(3); Mise en evidence d'un changement de stoechiometrie du complexe carbonate limite au sein de la serie des lanthanides(3)

    Energy Technology Data Exchange (ETDEWEB)

    Philippini, V

    2007-12-15

    Two stoichiometries have been proposed by different laboratories to interpret measurements on the limiting carbonate complexes of An{sup 3+} and Ln{sup 3+} cations. The study of the solubility of double carbonates (AlkLn(CO{sub 3}){sub 2},xH{sub 2}O) in concentrated carbonate solutions at room temperature and high ionic strengths has shown that on the one hand the lightest lanthanides (La and Nd) form Ln(CO{sub 3}){sub 4}{sup 5-} whereas the heaviest (Eu and Dy) form Ln(CO{sub 3}){sub 3}{sup 3-} in the studied chemical conditions, and on the other hand, that the kinetics of precipitation of double carbonates depends on the alkali metal and the lanthanide ions. The existence of two stoichiometries for the limiting carbonate complexes was confirmed by capillary electrophoresis hyphenated to an inductively coupled plasma mass spectrometer (CE-ICP-MS), used to extend the study to the whole series of lanthanides (except Ce, Pm and Yb). Two behaviours have been put forward comparing the electrophoretic mobilities: La to Tb form Ln(CO{sub 3}){sub 4}{sup 5-} while Dy to Lu form Ln(CO{sub 3}){sub 3}{sup 3-}. Measurements by time resolved laser fluorescence spectroscopy (TRLFS) on Eu(III) indicate small variations of the geometry of Eu(CO{sub 3}){sub 3}{sup 3-} complex, specially with Cs{sup +}. Although analogies are currently used among the 4f-block trivalent elements, different aqueous speciations are evidenced in concentrated carbonate solutions across the lanthanide series. (author)

  13. Characterisation of three regimes of collapsing Arctic ice complex deposits on the SE Laptev Sea coast using biomarkers and dual carbon isotopes

    NARCIS (Netherlands)

    Sanchez-Garcia, Laura; Vonk, Jorien; Charkin, Alexander; Kosmach, Denis; Dudarev, Oleg; Semiletov, Igor; Gustafsson, Örjan

    2014-01-01

    Arctic amplification of climate warming is intensifying the thaw and coastal erosion of the widespread and carbon-rich Siberian Ice Complex Deposits (ICD). Despite the potential for altering long-term carbon dynamics in the Arctic, the susceptibility of organic carbon (OC) to degradation as the ICD

  14. Simplifying the complexity of a coupled carbon turnover and pesticide degradation model

    Science.gov (United States)

    Marschmann, Gianna; Erhardt, André H.; Pagel, Holger; Kügler, Philipp; Streck, Thilo

    2016-04-01

    The mechanistic one-dimensional model PECCAD (PEsticide degradation Coupled to CArbon turnover in the Detritusphere; Pagel et al. 2014, Biogeochemistry 117, 185-204) has been developed as a tool to elucidate regulation mechanisms of pesticide degradation in soil. A feature of this model is that it integrates functional traits of microorganisms, identifiable by molecular tools, and physicochemical processes such as transport and sorption that control substrate availability. Predicting the behavior of microbially active interfaces demands a fundamental understanding of factors controlling their dynamics. Concepts from dynamical systems theory allow us to study general properties of the model such as its qualitative behavior, intrinsic timescales and dynamic stability: Using a Latin hypercube method we sampled the parameter space for physically realistic steady states of the PECCAD ODE system and set up a numerical continuation and bifurcation problem with the open-source toolbox MatCont in order to obtain a complete classification of the dynamical system's behaviour. Bifurcation analysis reveals an equilibrium state of the system entirely controlled by fungal kinetic parameters. The equilibrium is generally unstable in response to small perturbations except for a small band in parameter space where the pesticide pool is stable. Time scale separation is a phenomenon that occurs in almost every complex open physical system. Motivated by the notion of "initial-stage" and "late-stage" decomposers and the concept of r-, K- or L-selected microbial life strategies, we test the applicability of geometric singular perturbation theory to identify fast and slow time scales of PECCAD. Revealing a generic fast-slow structure would greatly simplify the analysis of complex models of organic matter turnover by reducing the number of unknowns and parameters and providing a systematic mathematical framework for studying their properties.

  15. Organomineral Complexation at the Nanoscale: Iron Speciation and Soil Carbon Stabilization

    Science.gov (United States)

    Coward, E.; Thompson, A.; Plante, A. F.

    2016-12-01

    Much of the uncertainty in the biogeochemical behavior of soil carbon (C) in tropical ecosystems derives from an incomplete understanding of soil C stabilization processes. The 2:1 phyllosilicate clays often associated with temperate organomineral complexation are largely absent in tropical soils due to extensive weathering. In contrast, these soils contain an abundance of Fe- and Al-containing short-range-order (SRO) mineral phases capable of C stabilization through sorption or co-precipitation, largely enabled by high specific surface area (SSA). SRO-mediated organomineral associations may thus prove a critical, yet matrix-selective, driver of the long-term C stabilization capacity observed in tropical soils. Characterizing the interactions between inherently heterogeneous organic matter and amorphous mineralogy presses the limits of current analytical techniques. This work pairs inorganic selective dissolution with high-resolution assessment of Fe speciation to determine the contribution of extracted mineral phases to the mineral matrix, and to C stabilization capacity. Surface (0-20 cm) samples were taken from 20 quantitative soil pits within the Luquillo Critical Zone Observatory in northeast Puerto Rico stratified across granodioritic and volcaniclastic parent materials. 57Fe-Mössbauer spectroscopy (MBS) and x-ray diffraction (XRD) before and after Fe-SOM extraction were used to assess changes in the mineralogical matrix associated with SOM dissolution, while N2-BET sorption was used to determine the contributions of the extractable phases to SSA. Results indicate (1) selective extraction of soil C produces significant shifts in Fe phase distribution, (2) SRO minerals contribute substantially to SSA, and (3) SRO minerals appear protected by more crystalline phases via physical mechanisms, rather than dissolution-dependent chemical bonds. This nanoscale characterization of Fe-C complexes thus provides evidence for both anticipated mineral-organic and

  16. The complex analytical method for assessment of passive smokers' exposure to carbon monoxide.

    Science.gov (United States)

    Czogala, Jan; Goniewicz, Maciej Lukasz

    2005-01-01

    Carbon monoxide (CO) is one of the toxic constituents in tobacco smoke. The aim of the study was to evaluate a complex analytical method that allows quantification of the exposure of passive smokers to CO. The exposed volunteers were placed in the model room where portions of cigarettes (5, 10, or 15 cigarettes every 30 or 60 min over 4 h) were smoked using a homemade smoking machine. The concentrations of CO and of the ventilation marker (methane) were monitored for the duration of each experiment. CO and methane were analyzed on-line using GC-FID with methanization. Carboxyhemoglobin (COHb) was analyzed twice: just before and after the experiment. After hemolysis of a 100-microL blood sample, CO was quantitatively released by adding 10% K3[Fe(CN)6] inside a small reactor and under stable pressure transported through a microtube with an absorbing agent on a chromatography loop. The proposed analytical method allows us to quantify exposure of passive smokers by measuring the dose-effect correlation. We observed that increasing COHb levels were directly correlated with the CO concentration in the air, but were also intermediately correlated with the frequency and number of smoked cigarettes and with the ventilation coefficient.

  17. Electrochemical sensor for ranitidine determination based on carbon paste electrode modified with oxovanadium (IV) salen complex.

    Science.gov (United States)

    Raymundo-Pereira, Paulo A; Teixeira, Marcos F S; Fatibello-Filho, Orlando; Dockal, Edward R; Bonifácio, Viviane Gomes; Marcolino, Luiz H

    2013-10-01

    The preparation and electrochemical characterization of a carbon paste electrode modified with the N,N-ethylene-bis(salicyllideneiminato)oxovanadium (IV) complex ([VO(salen)]) as well as its application for ranitidine determination are described. The electrochemical behavior of the modified electrode for the electroreduction of ranitidine was investigated using cyclic voltammetry, and analytical curves were obtained for ranitidine using linear sweep voltammetry (LSV) under optimized conditions. The best voltammetric response was obtained for an electrode composition of 20% (m/m) [VO(salen)] in the paste, 0.10 mol L(-1) of KCl solution (pH 5.5 adjusted with HCl) as supporting electrolyte and scan rate of 25 mV s(-1). A sensitive linear voltammetric response for ranitidine was obtained in the concentration range from 9.9×10(-5) to 1.0×10(-3) mol L(-1), with a detection limit of 6.6×10(-5) mol L(-1) using linear sweep voltammetry. These results demonstrated the viability of this modified electrode as a sensor for determination, quality control and routine analysis of ranitidine in pharmaceutical formulations.

  18. Electroless deposition of bis(4'-(4-Pyridyl)-2,2':6',2''-terpyridine)iron(II) thiocyanate complex onto carbon nanotubes modified glassy carbon electrode: application to simultaneous determination of ascorbic acid, dopamine and uric acid

    OpenAIRE

    Kamyabi,M. A; Narimani,O; Monfared,H. H

    2011-01-01

    A glassy carbon (GC) electrode modified by multi-walled carbon nanotubes (MWNTs) and bis(pyterpy)iron(II) thiocyanate complex (pyterpy = 4'-(4-pyridyl)-2,2':6',2''-terpyridine) was investigated by voltammetric methods in acetate buffer solution (pH 5). Performances of the iron(II)-complex/MWNTs modified electrode were evaluated with differential pulse voltammetry and scanning electron microscopy (SEM). The modified glassy carbon electrode shows an excellent electrochemical response for ascorb...

  19. PALADYN v1.0, a comprehensive land surface-vegetation-carbon cycle model of intermediate complexity

    Science.gov (United States)

    Willeit, Matteo; Ganopolski, Andrey

    2016-10-01

    PALADYN is presented; it is a new comprehensive and computationally efficient land surface-vegetation-carbon cycle model designed to be used in Earth system models of intermediate complexity for long-term simulations and paleoclimate studies. The model treats in a consistent manner the interaction between atmosphere, terrestrial vegetation and soil through the fluxes of energy, water and carbon. Energy, water and carbon are conserved. PALADYN explicitly treats permafrost, both in physical processes and as an important carbon pool. It distinguishes nine surface types: five different vegetation types, bare soil, land ice, lake and ocean shelf. Including the ocean shelf allows the treatment of continuous changes in sea level and shelf area associated with glacial cycles. Over each surface type, the model solves the surface energy balance and computes the fluxes of sensible, latent and ground heat and upward shortwave and longwave radiation. The model includes a single snow layer. Vegetation and bare soil share a single soil column. The soil is vertically discretized into five layers where prognostic equations for temperature, water and carbon are consistently solved. Phase changes of water in the soil are explicitly considered. A surface hydrology module computes precipitation interception by vegetation, surface runoff and soil infiltration. The soil water equation is based on Darcy's law. Given soil water content, the wetland fraction is computed based on a topographic index. The temperature profile is also computed in the upper part of ice sheets and in the ocean shelf soil. Photosynthesis is computed using a light use efficiency model. Carbon assimilation by vegetation is coupled to the transpiration of water through stomatal conductance. PALADYN includes a dynamic vegetation module with five plant functional types competing for the grid cell share with their respective net primary productivity. PALADYN distinguishes between mineral soil carbon, peat carbon, buried

  20. Clay:organic-carbon and organic carbon as determinants of the soil physical properties: reassessment of the Complexed Organic Carbon concept

    Science.gov (United States)

    Matter, Adrien; Johannes, Alice; Boivin, Pascal

    2016-04-01

    Soil Organic Carbon (SOC) is well known to largely determine the soil physical properties and fertility. Total porosity, structural porosity, aeration, structural stability among others are reported to increase linearly with increasing SOC in most studies. Is there an optimal SOC content as target in soil management, or is there no limit in physical fertility improvement with SOC? Dexter et al. (2008) investigated the relation between clay:SOC ratio and the physical properties of soils from different databases. They observed that the R2 of the relation between SOC and the physical properties were maximized when considering the SOC fraction limited to a clay:SOC ratio of 10. They concluded that this fraction of the SOC was complexed, and that the additional SOC was not influencing the physical properties as strongly as the complexed one. In this study, we reassessed this approach, on a database of 180 undisturbed soil samples collected from cambiluvisols of the Swiss Plateau, on an area of 2400 km2, and from different soil uses. The physical properties were obtained with Shrinkage Analysis, which involved the parameters used in Dexter et al., 2008. We used the same method, but detected biases in the statistical approach, which was, therefore, adapted. We showed that the relation between the bulk density and SOC was changing with the score of visual evaluation of the structure (VESS) (Ball et al., 2007). Therefore, we also worked only on the "good" structures according to VESS. All shrinkage parameters were linearly correlated to SOC regardless of the clay:SOC ratio, with R2 ranging from 0.45 to 0.8. Contrarily to Dexter et al. (2008), we did not observed an optimum in the R2 of the relation when considering a SOC fraction based on the clay:SOC ratio. R2 was increasing until a Clay:SOC of about 7, where it reached, and kept, its maximum value. The land use factor was not significant. The major difference with the former study is that we worked on the same soil group

  1. A novel non-enzymatic hydrogen peroxide sensor based on single walled carbon nanotubes-manganese complex modified glassy carbon electrode

    Energy Technology Data Exchange (ETDEWEB)

    Salimi, Abdollah, E-mail: absalimi@uok.ac.i [Department of Chemistry, University of Kurdistan, P.O. Box 416, Sanandaj (Iran, Islamic Republic of); Research Center for Nanotechnology, University of Kurdistan, P.O. Box 416, Sanandaj (Iran, Islamic Republic of); Mahdioun, Monierosadat; Noorbakhsh, Abdollah [Department of Chemistry, University of Kurdistan, P.O. Box 416, Sanandaj (Iran, Islamic Republic of); Abdolmaleki, Amir [Department of Chemistry, Isfahan University of Technology, Isfahan, 84156/83111 (Iran, Islamic Republic of); Ghavami, Raoof [Department of Chemistry, University of Kurdistan, P.O. Box 416, Sanandaj (Iran, Islamic Republic of)

    2011-03-30

    A simple procedure was developed to prepare a glassy carbon (GC) electrode modified with single wall carbon nanotubes (SWCNTs) and phenazine derivative of Mn-complex. With immersing the GC/CNTs modified electrode into Mn-complex solution for a short period of time 20-100 s, a stable thin layer of the complex was immobilized onto electrode surface. Modified electrode showed a well defined redox couples at wide pH range (1-12). The surface coverages and heterogeneous electron transfer rate constants (k{sub s}) of immobilized Mn-complex were approximately 1.58 x 10{sup -10} mole cm{sup -2} and 48.84 s{sup -1}. The modified electrode showed excellent electrocatalytic activity toward H{sub 2}O{sub 2} reduction. Detection limit, sensitivity, linear concentration range and k{sub cat} for H{sub 2}O{sub 2} were, 0.2 {mu}M and 692 nA {mu}M{sup -1} cm{sup -2}, 1 {mu}M to 1.5 mM and 7.96({+-}0.2) x 10{sup 3} M{sup -1} s{sup -1}, respectively. Compared to other modified electrodes, this electrode has many advantageous such as remarkable catalytic activity, good reproducibility, simple preparation procedure and long term stability.

  2. Highly microporous carbons derived from a complex of glutamic acid and zinc chloride for use in supercapacitors

    Science.gov (United States)

    Dong, Xiao-Ling; Lu, An-Hui; He, Bin; Li, Wen-Cui

    2016-09-01

    The selection of carbon precursor is an important factor when designing carbon materials. In this study, a complex derived from L-glutamic acid and zinc chloride was used to prepare highly microporous carbons via facile pyrolysis. L-glutamic acid, a new carbon precursor with nitrogen functionality, coordinated with zinc chloride resulted in a homogeneous distribution of Zn2+ on the molecular level. During pyrolysis, the evaporation of the in situ formed zinc species creates an abundance of micropores together with the inert gases. The obtained carbons exhibit high specific surface area (SBET: 1203 m2 g-1) and a rich nitrogen content (4.52 wt%). In excess of 89% of the pore volume consists of micropores with pore size ranging from 0.5 to 1.2 nm. These carbons have been shown to be suitable for use as supercapacitor electrodes, and have been tested in 6 M KOH where a capacitance of 217 F g-1 was achieved at a current density of 0.5 A g-1. A long cycling life of 30 000 cycles was achieved at a current density of 1 A g-1, with only a 9% loss in capacity. The leakage current through a two-electrode device was measured as 2.3 μA per mg of electrode and the self-discharge characteristics were minimal.

  3. Reconstruction of Holocene carbon dynamics in a large boreal peatland complex, southern Finland

    Science.gov (United States)

    Mathijssen, Paul J. H.; Väliranta, Minna; Korrensalo, Aino; Alekseychik, Pavel; Vesala, Timo; Rinne, Janne; Tuittila, Eeva-Stiina

    2016-06-01

    Holocene peatland development and associated carbon (C) dynamics were reconstructed for a southern boreal Finnish peatland complex with fen and bog areas. In order to assess the role of local factors and long-term allogenic climate forcing in peatland development patterns, we studied a total of 18 peat cores and reconstructed vertical peat growth and lateral peat area expansion rates, the C accumulation rate (CAR), past vegetation composition and past methane (CH4) fluxes. We combined fossil plant data with measured contemporary CH4 flux - vegetation relationship data to reconstruct CH4 fluxes over time. When these reconstructions were added to the CAR estimations, a more complete picture of Holocene-scale C dynamics was achieved. Basal peat ages showed that expansion of the peat area was rapid between 11,000 and 8000 cal. BP, but decreased during the dry mid-Holocene and is probably currently limited by basal topography. A similar pattern was observed for peat growth and CAR in the fen core, whereas in the bog core CAR increased after ombrotrophication, i.e. after 4400 cal. BP. The effect of fire on vegetation and CAR was more conspicuous at the bog site than at the fen site. The CH4 flux reconstructions showed that during the Holocene CH4 emissions at the fen site decreased from 19 ± 15 to 16 ± 8 g CH4 m-2 yr-1 and at the bog site from 20 ± 15 to 14 ± 8 g CH4 m-2 yr-1. Our results suggest that a combination of changing climate, fire events and local conditions have modified the autogenic peatland development and C dynamics.

  4. Basin-scale Modeling of Geological Carbon Sequestration: Model Complexity, Injection Scenario and Sensitivity Analysis

    Science.gov (United States)

    Huang, X.; Bandilla, K.; Celia, M. A.; Bachu, S.

    2013-12-01

    Geological carbon sequestration can significantly contribute to climate-change mitigation only if it is deployed at a very large scale. This means that injection scenarios must occur, and be analyzed, at the basin scale. Various mathematical models of different complexity may be used to assess the fate of injected CO2 and/or resident brine. These models span the range from multi-dimensional, multi-phase numerical simulators to simple single-phase analytical solutions. In this study, we consider a range of models, all based on vertically-integrated governing equations, to predict the basin-scale pressure response to specific injection scenarios. The Canadian section of the Basal Aquifer is used as a test site to compare the different modeling approaches. The model domain covers an area of approximately 811,000 km2, and the total injection rate is 63 Mt/yr, corresponding to 9 locations where large point sources have been identified. Predicted areas of critical pressure exceedance are used as a comparison metric among the different modeling approaches. Comparison of the results shows that single-phase numerical models may be good enough to predict the pressure response over a large aquifer; however, a simple superposition of semi-analytical or analytical solutions is not sufficiently accurate because spatial variability of formation properties plays an important role in the problem, and these variations are not captured properly with simple superposition. We consider two different injection scenarios: injection at the source locations and injection at locations with more suitable aquifer properties. Results indicate that in formations with significant spatial variability of properties, strong variations in injectivity among the different source locations can be expected, leading to the need to transport the captured CO2 to suitable injection locations, thereby necessitating development of a pipeline network. We also consider the sensitivity of porosity and

  5. Carbon-carbon bond cleavage of 1,2-hydroxy ethers b7 vanadium(V) dipicolinate complexes

    Energy Technology Data Exchange (ETDEWEB)

    Hanson, Susan K [Los Alamos National Laboratory; Gordon, John C [Los Alamos National Laboratory; Thorn, David L [Los Alamos National Laboratory; Scott, Brian L [Los Alamos National Laboratory; Baker, R Tom [Los Alamos National Laboratory

    2009-01-01

    The development of alternatives to current petroleum-based fuels and chemicals is becoming increasingly important due to concerns over climate change, growing world energy demand, and energy security issues. Using non-food derived biomass to produce renewable feedstocks for chemicals and fuels is a particularly attractive possibility. However, the majority of biomass is in the form of lignocellulose, which is often not fully utilized due to difficulties associated with breaking down both lignin and cellulose. Recently, a number of methods have been reported to transform cellulose directly into more valuable materials such as glucose, sorbitol, 5-(chloromethyl)furfural, and ethylene glycol. Less progress has been made with selective transformations of lignin, which is typically treated in paper and forest industries by kraft pulping (sodium hydroxide/sodium sulfide) or incineration. Our group has begun investigating aerobic oxidative C-C bond cleavage catalyzed by dipicolinate vanadium complexes, with the idea that a selective C-C cleavage reaction of this type could be used to produce valuable chemicals or intermediates from cellulose or lignin. Lignin is a randomized polymer containing methoxylated phenoxy propanol units. A number of different linkages occur naturally; one of the most prevalent is the {beta}-O-4 linkage shown in Figure 1, containing a C-C bond with 1,2-hydroxy ether substituents. While the oxidative C-C bond cleavage of 1,2-diols has been reported for a number of metals, including vanadium, iron, manganese, ruthenium, and polyoxometalate complexes, C-C bond cleavage of 1,2-hydroxy ethers is much less common. We report herein vanadium-mediated cleavage of C-C bonds between alcohol and ether functionalities in several lignin model complexes. In order to explore the scope and potential of vanadium complexes to effect oxidative C-C bond cleavage in 1,2-hydroxy ethers, we examined the reactivity of the lignin model complexes pinacol monomethyl ether (A

  6. Electrocatalytic O2 Reduction at a Bio-inspired Mononuclear Copper Phenolato Complex Immobilized on a Carbon Nanotube Electrode.

    Science.gov (United States)

    Gentil, Solène; Serre, Doti; Philouze, Christian; Holzinger, Michael; Thomas, Fabrice; Le Goff, Alan

    2016-02-12

    An original copper-phenolate complex, mimicking the active center of galactose oxidase, featuring a pyrene group was synthesized. Supramolecular pi-stacking allows its efficient and soft immobilization at the surface of a Multi-Walled Carbon Nanotube (MWCNT) electrode. This MWCNT-supported galactose oxidase model exhibits a 4 H(+)/4 e(-) electrocatalytic activity towards oxygen reduction at a redox potential of 0.60 V vs. RHE at pH 5.

  7. Novel Platinum(II) compounds modulate insulin-degrading enzyme activity and induce cell death in neuroblastoma cells.

    Science.gov (United States)

    Tundo, Grazia R; Sbardella, Diego; De Pascali, Sandra A; Ciaccio, Chiara; Coletta, Massimo; Fanizzi, Francesco P; Marini, Stefano

    2015-01-01

    The properties of three novel Platinum(II) compounds toward the insulin-degrading enzyme (IDE) enzymatic activity have been investigated under physiological conditions. The rationale of this study resides on previous observations that these compounds, specifically designed and synthesized by some of us, induce apoptosis in various cancer cell lines, whereas IDE has been proposed as a putative oncogene involved in neuroblastoma onset and progression. Two of these compounds, namely [PtCl(O,O'-acac)(DMSO)] and [Pt(O,O'-acac)(γ-acac)(DMS)], display a modulatory behavior, wherefore activation or inhibition of IDE activity occurs over different concentration ranges (suggesting the existence of two binding sites on the enzyme). On the other hand, [Pt(O,O'-acac)(γ-acac)(DMSO)] shows a typical competitive inhibitory pattern, characterized by a meaningful affinity constant (K i  = 0.95 ± 0.21 μM). Although all three compounds induce cell death in neuroblastoma SHSY5Y cells at concentrations exceeding 2 μM, the two modulators facilitate cells' proliferation at concentrations ≤ 1.5 μM, whereas the competitive inhibitor [Pt(O,O'-acac)(γ-acac)(DMSO)] only shows a pro-apoptotic activity at all investigated concentrations. These features render the [Pt(O,O'-acac)(γ-acac)(DMSO)] a promising "lead compound" for the synthesis of IDE-specific inhibitors (not characterized yet) with therapeutic potentiality.

  8. Mechanistic information on the reductive elimination from cationic trimethylplatinum(IV) complexes to form carbon-carbon bonds.

    Science.gov (United States)

    Procelewska, Joanna; Zahl, Achim; Liehr, Günter; van Eldik, Rudi; Smythe, Nicole A; Williams, B Scott; Goldberg, Karen I

    2005-10-31

    Cationic complexes of the type fac-[(L(2))Pt(IV)Me(3)(pyr-X)][OTf] (pyr-X = 4-substituted pyridines; L(2) = diphosphine, viz., dppe = bis(diphenylphosphino)ethane and dppbz = o-bis(diphenylphosphino)benzene; OTf = trifluoromethanesulfonate) undergo C-C reductive elimination reactions to form [L(2)Pt(II)Me(pyr-X)][OTf] and ethane. Detailed studies indicate that these reactions proceed by a two-step pathway, viz., initial reversible dissociation of the pyridine ligand from the cationic complex to generate a five-coordinate Pt(IV) intermediate, followed by irreversible concerted C-C bond formation. The reaction is inhibited by pyridine. The highly positive values for DeltaS()(obs) = +180 +/- 30 J K(-1) mol(-1), DeltaH(obs) = 160 +/- 10 kJ mol(-1), and DeltaV()(obs) = +16 +/- 1 cm(3) mol(-1) can be accounted for in terms of significant bond cleavage and/or partial reduction from Pt(IV) to Pt(II) in going from the ground to the transition state. These cationic complexes have provided the first opportunity to carry out detailed studies of C-C reductive elimination from cationic Pt(IV) complexes in a variety of solvents. The absence of a significant solvent effect for this reaction provides strong evidence that the C-C reductive coupling occurs from an unsaturated five-coordinate Pt(IV) intermediate rather than from a six-coordinate Pt(IV) solvento species.

  9. Carbon-water Cycling in the Critical Zone: Understanding Ecosystem Process Variability Across Complex Terrain

    Energy Technology Data Exchange (ETDEWEB)

    Barnard, Holly [Univ. of Colorado, Boulder, CO (United States); Brooks, Paul [Univ. of Utah, Salt Lake City, UT (United States); Univ. of Arizona, Tucson, AZ (United States)

    2016-06-16

    One of the largest knowledge gaps in environmental science is the ability to understand and predict how ecosystems will respond to future climate variability. The links between vegetation, hydrology, and climate that control carbon sequestration in plant biomass and soils remain poorly understood. Soil respiration is the second largest carbon flux of terrestrial ecosystems, yet there is no consensus on how respiration will change as water availability and temperature co-vary. To address this knowledge gap, we use the variation in soil development and topography across an elevation and climate gradient on the Front Range of Colorado to conduct a natural experiment that enables us to examine the co-evolution of soil carbon, vegetation, hydrology, and climate in an accessible field laboratory. The goal of this project is to further our ability to combine plant water availability, carbon flux and storage, and topographically driven hydrometrics into a watershed scale predictive model of carbon balance. We hypothesize: (i) landscape structure and hydrology are important controls on soil respiration as a result of spatial variability in both physical and biological drivers: (ii) variation in rates of soil respiration during the growing season is due to corresponding shifts in belowground carbon inputs from vegetation; and (iii) aboveground carbon storage (biomass) and species composition are directly correlated with soil moisture and therefore, can be directly related to subsurface drainage patterns.

  10. A computational study on novel carbon-based lithium materials for hydrogen storage and the role of carbon in destabilizing complex metal hydrides

    Science.gov (United States)

    Ghouri, Mohammed Minhaj

    materials with varying amounts of hydrogen. A detailed analysis of the heats of reactions of these materials using different reaction schemes is performed and based on the promising thermodynamic and gravimetric storage density, LiC4Be2H5 is divulged as a promising novel carbon based lithium material. In the later part, this dissertation performs a detailed study on the effect of carbon when it is used as a dopant in four different well known complex hydrides, lithium beryllium hydride (Li2BeH4), lithium borohydride (LiBH4), lithium aluminum hydride (LiAlH 4) and sodium borohydride (NaBH4). Initially, the unit cells of the crystal structure are fully resolved using the plane-wave pseudopotential implementation of DFT. The supercells of each of these are then constructed and optimized. Varying amounts of carbon is introduced as impurity in these crystals in different sites such as the top, subsurface and the bulk of the crystal lattice. Using the electronic structure calculations, it is established that (i) C-Be-H, C-B-H or C-Al-H compounds are formed respectively in the cases of Li2BeH4, LiBH4 and LiAlH4 when carbon is doped in them; (ii) and carbon dopant causes a decrease in the bond strengths of Be-H, B-H and Al-H in respective cases. This reduction in the bond strengths combined with the fact that there is a decrease in the ionic interaction between the cation and the anionic hydride units of these complex hydrides causes a destabilization effect.

  11. An investigation of groundwater organics, soil minerals, and activated carbon on the complexation, adsorption, and separation of technetium-99

    Energy Technology Data Exchange (ETDEWEB)

    Gu, B. [Oak Ridge National Lab., TN (United States). Environmental Sciences Div.; Dowlen, K.E. [Oak Ridge Associated Universities, TN (United States)

    1996-01-01

    This report summarizes studies on the interactions of technetium-99 (Tc) with different organic compounds and soil minerals under both oxidizing and reducing conditions. The report is divided into four parts and includes (1) effect of natural organic matter (NOM) on the complexation and solubility of Tc, (2) complexation between Tc and trichloroethylene (TCE) in aqueous solutions, (3) adsorption of Tc on soil samples from Paducah Gaseous Diffusion Plant (PGDP), and (4) adsorption and separation of Tc on activated carbon. Various experimental techniques were applied to characterize and identify Tc complexation with organic compounds and TCE, including liquid-liquid extraction, membrane filtration, size exclusion, and gel chromatography. Results indicate, within the experimental error, Tc (as pertechnetate, TcO{sub 4}) did not appear to form complexes with groundwater or natural organic matter under both atmospheric and reducing conditions. However, Tc can form complexes with certain organic compounds or specific functional groups such as salicylate. Tc did not appear to form complexes with TCE in aqueous solution.Both liquid-liquid extraction and high performance liquid chromatography (HPLC) gave no indication Tc was complexed with TCE. The correlations between Tc and TCE concentrations in monitoring wells at PGDP may be a coincidence because TCE was commonly used as a decontamination reagent. Once TCE and Tc entered the groundwater, they behaved similarly because both TcO{sub 4}{sup {minus}} and TCE are poorly adsorbed by soils. An effective remediation technique to remove TcO{sub 4}{sup {minus}} from PGDP contaminated groundwater is needed. One possibility is the use of an activated carbon adsorption technique developed in this study.

  12. Uptake of dissolved organic carbon-complexed ⁶⁵Cu by the green mussel Perna viridis.

    Science.gov (United States)

    Zhong, Huan; Evans, Douglas; Wang, Wen-Xiong

    2012-02-21

    Stable Cu isotope ((65)Cu) was complexed with various representative dissolved organic carbon (DOC) types, including coastal seawater DOC, fulvic acid (FA), cyanobacteria spirulina (SP) DOC, histidine (His), cysteine (Cys), and lipophilic diethyl dithiocarbamate (DDC) at different concentrations. The uptake of these dissolved Cu species by the coastal green mussel Perna viridis was quantified for the first time. Copper complexed with different DOC types were taken up in some measure by mussels, depending on the DOC types. However, complexation generally reduced Cu uptake as compared to that of inorganic Cu species, and DOC type-specific negative relationships were found between DOC levels and Cu uptake. Strong Cu binding sites (including His and organic sulfur functional groups) within DOC appeared to control the inhibitory effects of DOC on Cu uptake, possibly due to the competitive binding of Cu between the dissolved phase and biological membranes. Therefore, differences in strong Cu binding site levels may explain the differences in bioavailability of Cu complexed with different types of DOC. At the same time, the variations in Cu-DOC uptake may also be partly attributed to the absorption of Cu-DOC complexes, especially for the small Cu-DOC complexes (e.g., Cu-Cys, Cu-His, or Cu-DDC). Our study highlights the importance of considering the specificity of Cu-DOC complexes when assessing biological exposure to dissolved Cu in natural waters, especially during events, such as phytoplankton bloom periods, that could modify DOC composition and concentrations.

  13. The complex environment of the bright carbon star TX Piscium as probed by spectro-astrometry

    Science.gov (United States)

    Hron, J.; Uttenthaler, S.; Aringer, B.; Klotz, D.; Lebzelter, T.; Paladini, C.; Wiedemann, G.

    2015-12-01

    Context. Stars on the asymptotic giant branch (AGB) show broad evidence of inhomogeneous atmospheres and circumstellar envelopes. These have been studied by a variety of methods on various angular scales. In this paper we explore the envelope of the well-studied carbon star TX Psc by the technique of spectro-astrometry. Aims: We explore the potential of this method for detecting asymmetries around AGB stars. Methods: We obtained CRIRES observations of several CO Δv = 1 lines near 4.6 μm and HCN lines near 3 μm in 2010 and 2013. These were then searched for spectro-astrometric signatures. For the interpretation of the results, we used simple simulated observations. Results: Several lines show significant photocentre shifts with a clear dependence on position angle. In all cases, tilde-shaped signatures are found where the positive and negative shifts (at PA 0°) are associated with blue and weaker red components of the lines. The shifts can be modelled with a bright blob 70 mas to 210 mas south of the star with a flux of several percent of the photospheric flux. We estimate a lower limit of the blob temperature of 1000 K. The blob may be related to a mass ejection as found for AGB stars or red supergiants. We also consider the scenario of a companion object. Conclusions: Although there is clear spectro-astrometric evidence of a rather prominent structure near TX Psc, it does not seem to relate to the other evidence of asymmetries, so no definite explanation can be given. Our data thus underline the very complex structure of the environment of this star, but further observations that sample the angular scales out to a few hundred milli-arcseconds are needed to get a clearer picture. Based on observations made with ESO telescopes at La Silla Paranal Observatory under programme IDs 386.D-0091 and 091.D-0094.Appendix A is available in electronic form at http://www.aanda.org

  14. Dinitrogen cleavage and functionalization by carbon monoxide promoted by a hafnium complex.

    Science.gov (United States)

    Knobloch, Donald J; Lobkovsky, Emil; Chirik, Paul J

    2010-01-01

    Molecular nitrogen (N(2)) and carbon monoxide (CO) have the two strongest bonds in chemistry and present significant challenges in developing new transformations that exploit these two abundant feedstocks. At the core of this objective is the discovery of transition-metal compounds that promote the six-electron reductive cleavage of N(2) at ambient temperature and pressure and also promote new nitrogen-element bond formation. Here we show that an organometallic hafnium compound induces N(2) cleavage on the addition of CO, with a simultaneous assembly of new nitrogen-carbon and carbon-carbon bonds. Subsequent addition of a weak acid liberates oxamide, which demonstrates that an important agrochemical can be synthesized directly from N(2) and CO. These studies introduce an alternative paradigm for N(2) cleavage and functionalization in which the six-electron reductive cleavage is promoted by both the transition metal and the incoming ligand, CO, used for the new bond formations.

  15. Matrix Isolation FTIR and AB Initio Studies on the Conformations of Dimethyl and Diethyl Carbonate and Their Complexes with Water

    Science.gov (United States)

    Kar, Bishnu Prasad; Ramanathan, N.; Sundararajan, K.; Viswanathan, K. S.

    2011-06-01

    Dimethyl carbonate (DMC) and diethyl carbonate (DEC) have been studied for their conformations using matrix isolation infrared spectroscopy and ab initio computations. In addition to the above studies, the complexes of the two compounds with water have also been studied. The experiments were corroborated with ab initio calculations at the B3LYP/6-31++G** level. The organic carbonates were trapped in argon and nitrogen matrixes using an effusive source maintained at two different temperatures; i.e. room temperature and 170°C. In addition the matrix was also deposited using a supersonic jet source. These experiments were performed to alter the relative population of the various conformations, to aid us in the assignments of the vibrational features. The conformation of DMC corresponding to the global minimum of DMC was found to be a cis-cis conformer where the two methyl groups are found to be at cis position with respect to the carbonyl oxygen. The next higher energy conformer corresponded to a cis-trans structure with a near trans-near trans structure being the highest energy conformer. In our experimental matrix isolation spectra of DMC, we were able to assign features due to the cis-cis and cis-trans conformers. The features of the higher energy cis-trans conformer was confirmed with our experiments using the elevated temperature effusive source and the supersonic source. DEC displays a richer conformational landscape due to the presence of a longer carbon chain. The computational and experimental indicate that the ground state conformer for this compound is one in which carbon attached to oxygen adopts a cis configuration with respect to the carbonyl oxygen, while the terminal carbon adopts an anti conformation. A detailed study of the conformational picture of DEC will be presented. In addition to the above conformational studies, 1:1 hydrogen bonded complexes of DMC and DEC with water were also observed in the matrix, which was corroborated by our

  16. Activation of C-H bonds of arenes: selectivity and reactivity in bis(pyridyl) platinum(II) complexes.

    Science.gov (United States)

    Zhang, Fenbao; Kirby, Christopher W; Hairsine, Douglas W; Jennings, Michael C; Puddephatt, Richard J

    2005-10-19

    The reaction of [PtMe2(NN)] and B(C6F5)3/H2O in CF3CH2OH with arenes Ar-H gives [PtAr{HOB(C6F5)3}(LL)] if the bis(pyridyl) ligand NN forms a six-membered, but not five-membered, chelate ring; methyl-substituted arenes give selectivity for metalation of meta > para > ortho, but methoxy-substituted arenes give ortho > meta, para.

  17. DNA interstrand cross-links of an antitumor trinuclear platinum(II) complex: thermodynamic analysis and chemical probing.

    Science.gov (United States)

    Malina, Jaroslav; Farrell, Nicholas P; Brabec, Viktor

    2011-06-06

    The trinuclear platinum compound [{trans-PtCl(NH(3))(2)}(2)(μ-trans-Pt(NH(3))(2){NH(2)(CH(2))(6)NH(2)}(2))](4+) (BBR3464) belongs to the polynuclear class of platinum-based anticancer agents. These agents form in DNA long-range (Pt,Pt) interstrand cross-links, whose role in the antitumor effects of BBR3464 predominates. Our results show for the first time that the interstrand cross-links formed by BBR3464 between two guanine bases in opposite strands separated by two base pairs (1,4-interstrand cross-links) exist as two distinct conformers, which are not interconvertible, not only if these cross-links are formed in the 5'-5', but also in the less-usual 3'-3' direction. Analysis of the conformers by differential scanning calorimetry, chemical probes of DNA conformation, and minor groove binder Hoechst 33258 demonstrate that each of the four conformers affects DNA in a distinctly different way and adopts a different conformation. The results also support the thesis that the molecule of antitumor BBR3464 when forming DNA interstrand cross-links may adopt different global structures, including different configurations of the linker chain of BBR3464 in the minor groove of DNA. Our findings suggest that the multiple DNA interstrand cross-links available to BBR3464 may all contribute substantially to its cytotoxicity.

  18. Electrocatalytic and simultaneous determination of isoproterenol, uric acid and folic acid at molybdenum (VI) complex-carbon nanotube paste electrode

    Energy Technology Data Exchange (ETDEWEB)

    Beitollahi, Hadi, E-mail: h.beitollahi@yahoo.com [Environment Department, Research Institute of Environmental Sciences, International Center for Science, High Technology and Environmental Sciences, Kerman (Iran, Islamic Republic of); Sheikhshoaie, Iran [Department of Chemistry, Faculty of Science, Shahid Bahonar University of Kerman, Kerman 76175-133 (Iran, Islamic Republic of)

    2011-11-30

    Highlights: > A molybdenum (VI) complex-carbon nanotube paste electrode have been fabricated. > This electrode reduced the oxidation potential of isoproterenol by about 175 mV. > It resolved the voltammetric waves of isoproterenol, uric acid and folic acid. - Abstract: This paper describes the development, electrochemical characterization and utilization of a novel modified molybdenum (VI) complex-carbon nanotube paste electrode for the electrocatalytic determination of isoproterenol (IP). The electrochemical profile of the proposed modified electrode was analyzed by cyclic voltammetry (CV) that showed a shift of the oxidation peak potential of IP at 175 mV to less positive value, compared with an unmodified carbon paste electrode. Differential pulse voltammetry (DPV) in 0.1 M phosphate buffer solution (PBS) at pH 7.0 was performed to determine IP in the range from 0.7 to 600.0 {mu}M, with a detection limit of 35.0 nM. Then the modified electrode was used to determine IP in an excess of uric acid (UA) and folic acid (FA) by DPV. Finally, this method was used for the determination of IP in some real samples.

  19. Variation in soil carbon dioxide efflux at two spatial scales in a topographically complex boreal forest

    Science.gov (United States)

    Kelsey, Katharine C.; Wickland, Kimberly P.; Striegl, Rob; Neff, Jason C.

    2012-01-01

    Carbon dynamics of high-latitude regions are an important and highly uncertain component of global carbon budgets, and efforts to constrain estimates of soil-atmosphere carbon exchange in these regions are contingent on accurate representations of spatial and temporal variability in carbon fluxes. This study explores spatial and temporal variability in soilatmosphere carbon dynamics at both fine and coarse spatial scales in a high-elevation, permafrost-dominated boreal black spruce forest. We evaluate the importance of landscape-level investigations of soil-atmosphere carbon dynamics by characterizing seasonal trends in soil-atmosphere carbon exchange, describing soil temperature-moisture-respiration relations, and quantifying temporal and spatial variability at two spatial scales: the plot scale (0–5 m) and the landscape scale (500–1000 m). Plot-scale spatial variability (average variation on a given measurement day) in soil CO2 efflux ranged from a coefficient of variation (CV) of 0.25 to 0.69, and plot-scale temporal variability (average variation of plots across measurement days) in efflux ranged from a CV of 0.19 to 0.36. Landscape-scale spatial and temporal variability in efflux was represented by a CV of 0.40 and 0.31, respectively, indicating that plot-scale spatial variability in soil respiration is as great as landscape-scale spatial variability at this site. While soil respiration was related to soil temperature at both the plot- and landscape scale, landscape-level descriptions of soil moisture were necessary to define soil respiration-moisture relations. Soil moisture variability was also integral to explaining temporal variability in soil respiration. Our results have important implications for research efforts in high-latitude regions where remote study sites make landscape-scale field campaigns challenging.

  20. Complexity

    CERN Document Server

    Gershenson, Carlos

    2011-01-01

    The term complexity derives etymologically from the Latin plexus, which means interwoven. Intuitively, this implies that something complex is composed by elements that are difficult to separate. This difficulty arises from the relevant interactions that take place between components. This lack of separability is at odds with the classical scientific method - which has been used since the times of Galileo, Newton, Descartes, and Laplace - and has also influenced philosophy and engineering. In recent decades, the scientific study of complexity and complex systems has proposed a paradigm shift in science and philosophy, proposing novel methods that take into account relevant interactions.

  1. The Oligocene carbonate platform of the Zagros Basin, SW Iran: An assessment of highly-complex geological heritage

    Science.gov (United States)

    Habibi, Tahereh; Ruban, Dmitry A.

    2017-05-01

    North Africa and the Middle East possess rich geological heritage, but the latter is yet to be fully identified and described. The Oligocene carbonate platform of the Zagros Basin in southwest Iran, which corresponds to the lower part of the Asmari Formation, has significant potential for geoconservation and geotourism. The types of the geological heritage, their value, and the possible geosites have been assessed. The studied deposits are interesting because of lithology (carbonate rocks), fossils (larger foraminifera, other microfossils, diverse marine invertebrates, fish microremains, and trace fossils), biostratigraphical developments, facies (homoclinal carbonate ramp) and signature of global events (glacioeustatic fluctuations), and outstanding hydrocarbon resources. The five main geological heritage types are sedimentary, palaeontological, stratigraphical, palaeogeographical, and economical, from which the palaeontological, palaeogeographical, and economical types are of global rank. The Khollar and Kavar sections in the Fars Province of Iran are recommended as geosites suitable for research, education, and tourism. The high complexity of the geological heritage linked to the Oligocene carbonate platform of the Zagros Basin implies the phenomenon of geodiversity should be understood with regard to the relationships between types and their values.

  2. Synthesis and evaluation of multi-wall carbon nanotube–paclitaxel complex as an anti-cancer agent

    Science.gov (United States)

    Ghasemvand, Fariba; Biazar, Esmaeil; Tavakolifard, Sara; Khaledian, Mohammad; Rahmanzadeh, Saeid; Momenzadeh, Daruosh; Afroosheh, Roshanak; Zarkalami, Faezeh; Shabannezhad, Marjan; Hesami Tackallou, Saeed; Massoudi, Nilofar; Heidari Keshel, Saeed

    2016-01-01

    Aim: The aim of this study was to design multi-walled carbon nanotubes (MWCNTs) loaded with paclitaxel (PTX) anti-cancer drug and investigate its anti-cancerous efficacy of human gastric cancer. Background: Carbon nanotubes (CNTs) represent a novel nano-materials applied in various fields such as drug delivery due to their unique chemical properties and high drug loading. Patients and methods: In this study, multi-walled carbon nanotubes (MWCNTs) pre-functionalized covalently with a paclitaxel (PTX) as an anti-cancer drug and evaluated by different analyses including, scanning electron microscope (SEM), particle size analyzer and cellular analyses. Results: A well conjugated of anti-cancer drug on the carbon nanotube surfaces was shown. This study demonstrates that the MWCN-PTX complex is a potentially useful system for delivery of anti-cancer drugs. The flow cytometry, CFU and MTT assay results have disclosed that MWCNT/PTXs might promote apoptosis in MKN-45 gastric adenocarcinoma cell line. Conclusion: According to results, our simple method can be designed a candidate material for chemotherapy. It has presented a few bio-related applications including, their successful use as a nano-carriers for drug transport. PMID:27458512

  3. Correction: A binary catalyst system of a cationic Ru-CNC pincer complex with an alkali metal salt for selective hydroboration of carbon dioxide.

    Science.gov (United States)

    Ng, Chee Koon; Wu, Jie; Hor, T S Andy; Luo, He-Kuan

    2016-12-22

    Correction for 'A binary catalyst system of a cationic Ru-CNC pincer complex with an alkali metal salt for selective hydroboration of carbon dioxide' by Chee Koon Ng et al., Chem. Commun., 2016, 52, 11842-11845.

  4. Theory of complex fluids in the warm-dense-matter regime, and application to phase-transitions in liquid carbon

    CERN Document Server

    Dharma-wardana, M W C

    2016-01-01

    Using data from recent laser-shock experiments and related density-functional molecular-dynamics simulations on carbon, we demonstrate that the ionic structures predicted within the neutral-pseudo-atom approach for a complex liquid in the warm-dense matter regime are in good agreement with available data, even where transient covalent bonding dominates ionic correlations. Evidence for an unusual phase transition of a liquid $\\to$ vapor with an abrupt decrease in ionization occurring simultaneously is presented. Here a covalently-bonded metallic-liquid, i.e., carbon of density 1.0 g/cm$^3$, transits to a disordered mono-atomic fluid at 7 eV. Other transitions where the mean ionization $Z$ drops abruptly are also uncovered

  5. Formation of complex Al-N-C layer in aluminium by successive carbon and nitrogen implantation

    Energy Technology Data Exchange (ETDEWEB)

    Uglov, V.V.; Cherenda, N.N. E-mail: info@research.bsu.unibel.by; Khodasevich, V.V.; Sokol, V.A.; Abramov, I.I.; Danilyuk, A.L.; Wenzel, A.; Gerlach, J.; Rauschenbach, B

    1999-01-01

    The results of Auger electron spectroscopy and transmission electron microscopy of the surface layer of aluminium after successive implantation by carbon and nitrogen ions are presented in this work. The energy of implanted ions is 40 keV. The implantation dose varies in the range (3.3-6.5)x10{sup 17} ions/cm{sup 2}. The findings show that successive implantation leads to the formation of two main layers in aluminium. The first layer is AlNC{sub x} (0carbon atoms form bonds with nitrogen atoms. The second layer contains disoriented Al{sub 4}C{sub 3} precipitates and carbon atoms migrated from the first layer. The mechanism of migration is discussed.

  6. Formation of complex Al-N-C layer in aluminium by successive carbon and nitrogen implantation

    Science.gov (United States)

    Uglov, V. V.; Cherenda, N. N.; Khodasevich, V. V.; Sokol, V. A.; Abramov, I. I.; Danilyuk, A. L.; Wenzel, A.; Gerlach, J.; Rauschenbach, B.

    1999-01-01

    The results of Auger electron spectroscopy and transmission electron microscopy of the surface layer of aluminium after successive implantation by carbon and nitrogen ions are presented in this work. The energy of implanted ions is 40 keV. The implantation dose varies in the range (3.3-6.5) × 10 17 ions/cm 2. The findings show that successive implantation leads to the formation of two main layers in aluminium. The first layer is AlNC x (0 < x < 0.5) layer with violated hcp. AlN structure, where carbon atoms form bonds with nitrogen atoms. The second layer contains disoriented Al 4C 3 precipitates and carbon atoms migrated from the first layer. The mechanism of migration is discussed.

  7. A platinum complex that binds non-covalently to DNA and induces cell death via a different mechanism than cisplatin.

    Science.gov (United States)

    Suntharalingam, Kogularamanan; Mendoza, Oscar; Duarte, Alexandra A; Mann, David J; Vilar, Ramon

    2013-05-01

    Cisplatin and some of its derivatives have been shown to be very successful anticancer agents. Their main mode of action has been proposed to be via covalent binding to DNA. However, one of the limitations of these drugs is their poor activity against some tumours due to intrinsic or acquired resistance. Therefore, there is interest in developing complexes with different binding modes and mode of action. Herein we present a novel platinum(ii)-terpyridine complex (1) which interacts non-covalently with DNA and induces cell death via a different mechanism than cisplatin. The interaction of this complex with DNA was studied by UV/Vis spectroscopic titrations, fluorescent indicator displacement (FID) assays and circular dichroism (CD) titrations. In addition, computational docking studies were carried out with the aim of establishing the complex's binding mode. These experimental and computational studies showed the complex to have an affinity constant for DNA of ∼10(4) M(-1), a theoretical free energy of binding of -10.83 kcal mol(-1) and selectivity for the minor groove of DNA. Long-term studies indicated that 1 did not covalently bind (or nick) DNA. The cancer cell antiproliferative properties of this platinum(ii) complex were probed in vitro against human and murine cell lines. Encouragingly the platinum(ii) complex displayed selective toxicity for the cancerous (U2OS and SH-SY5Y) and proliferating NIH 3T3 cell lines. Further cell based studies were carried out to establish the mode of action. Cellular uptake studies demonstrated that the complex is able to penetrate the cell membrane and localize to the nucleus, implying that genomic DNA could be a cellular target. Detailed immunoblotting studies in combination with DNA-flow cytometry showed that the platinum(ii) complex induced cell death in a manner consistent with necrosis.

  8. Synthesis of Novel Porphyrin and its Complexes Covalently Linked to Multi-Walled Carbon Nanotubes and Study of their Spectroscopy

    Directory of Open Access Journals (Sweden)

    Jin Jun

    2009-01-01

    Full Text Available Abstract Novel covalent porphyrin and its complexes (Co2+, Zn2+ functionalized multi-walled carbon nanotubes (MWNTs have been successfully synthesized by the reaction of the carboxyl on the surface of MWNTs which was synthesized to use carbon radicals generated by the thermal decomposition of azodiisobutyronitrile (AIBN with 5-p-hydroxyphenyl-10,15,20-triphenyl-porphyrin and its complexes (Co2+, Zn2+. Three resulting nanohybrids were characterized by spectroscopy (FT-IR, Raman, and UV-vis, TGA, and TEM. The quality of porphyrin attached to the MWNTs was determined from thermogravimeric analysis (TGA of the MWNTs, which showed a weight loss of about 60%. The Raman and absorption spectroscopy data showed that the electronic properties of modified MWNTs were mostly retained, without damaging their one-dimensional electronic properties. From fluorescence measurements, it was observed that the porphyrin and its complexes (Co2+, Zn2+ were nearly quenched by MWNTs, indicating that this covalently modified mode facilitated the effective energy or electron transfer between the excited porphyrin moiety and the extended π-system of MWNTs.

  9. Hydration properties of lanthanoid(III) carbonate complexes in liquid water determined by polarizable molecular dynamics simulations.

    Science.gov (United States)

    Martelli, Fausto; Jeanvoine, Yannick; Vercouter, Thomas; Beuchat, César; Vuilleumier, Rodolphe; Spezia, Riccardo

    2014-02-28

    In this work we have studied the structure and dynamics of complexes formed by three and four carbonates and a central lanthanoid(III) ion in liquid water by means of polarizable molecular dynamics simulations. With this aim we have developed a force field employing an extrapolation procedure that was previously developed for lanthanoid(III) aqua ions and then we have validated it against DFT-based data. In this way we were able to shed light on properties of the whole series, finding some similarities and differences across the series, and to help in interpreting experiments on those systems. We found that the bi-dentate tri-carbonate complexes are the most stable for all the atoms, but a variation of the number of water molecules in the first ion shell, and the associated exchange dynamics, is observed from lighter to heavier elements. On the other hand, for four-carbonate systems only one water molecule is observed in the first shell, with 10-20% probability, for La(III) and Ce(III), while for the rest of the series it seems impossible for a water molecule to enter the first ion shell in the presence of such an excess of carbonate ligands. Finally, the good performance of our extrapolation procedure, based on ionic radii, makes us confident in extending such approaches to study the structure and dynamics of other systems in solution containing Ln(III) and An(III) ions. This parametrization method results particularly useful since it does not need expensive quantum chemistry calculations for all the atoms in the series.

  10. Platinum(II) phenanthroimidazole G-quadruplex ligand induces selective telomere shortening in A549 cancer cells.

    Science.gov (United States)

    Mancini, Johanna; Rousseau, Philippe; Castor, Katherine J; Sleiman, Hanadi F; Autexier, Chantal

    2016-02-01

    Telomere maintenance, achieved by the binding of protective shelterin capping proteins to telomeres and by either telomerase or a recombination-based alternative lengthening of telomere (ALT) mechanism, is critical for cell proliferation and survival. Extensive telomere shortening or loss of telomere integrity activates DNA damage checkpoints, leading to cell senescence or death. Although telomerase upregulation is an attractive target for anti-cancer therapy, the lag associated with telomere shortening and the potential activation of ALT pose a challenge. An alternative approach is to modify telomere interactions with binding proteins (telomere uncapping). G-quadruplex ligands stabilize structures generated from single-stranded G-rich 3'-telomere end (G-quadruplex) folding, which in principle, cannot be elongated by telomerase, thus leading to telomere shortening. Ligands can also mediate rapid anti-proliferative effects by telomere uncapping. We previously reported that the G-quadruplex ligand, phenylphenanthroimidazole ethylenediamine platinum(II) (PIP), inhibits telomerase activity in vitro[47]. In the current study, a long-term seeding assay showed that PIP significantly inhibited the seeding capacity of A549 lung cancer cells and to a lesser extent primary MRC5 fibroblast cells. Importantly, treatment with PIP caused a significant dose- and time-dependent decrease in average telomere length of A549 but not MRC5 cells. Moreover, cell cycle analysis revealed a significant increase in G1 arrest upon treatment of A549 cells, but not MRC5 cells. Both apoptosis and cellular senescence may contribute to the anti-proliferative effects of PIP. Our studies validate the development of novel and specific therapeutic ligands targeting telomeric G-quadruplex structures in cancer cells.

  11. Inducing porosity and growing carbon nanofibers in ferroin perchlorate: An example of morphological transitions in coordination complexes

    Science.gov (United States)

    Avraham, Efrat Shawat; Fleker, Ohad; Benisvy, Laurent; Oakes, Landon; Pint, Cary L.; Nessim, Gilbert D.

    2017-09-01

    Inducing porosity in solid coordination complex crystals, which are an important class of catalysts, is critical for many applications where a high surface area is required. However, unlike metal organic frameworks (MOFs), fabrication of porous coordination crystals remains a significant challenge. Here we demonstrate a simple method to produce and modulate porosity in coordination complex crystals using ferroin perchlorate, a model system that combines a common ionic complex with a very reactive counter-ion. Using thermal chemical vapor deposition (CVD), we show that by annealing ferroin perchlorate crystals at 350 °C under a flow of ethylene, hydrogen, argon, and oxygen, we induced pores in the crystal. We demonstrate that small amounts of oxygen, which may combine with hydrogen to form water, are essential for pore formation. We also demonstrate that pore size and density can be easily controlled by varying the ethylene flow. Upon raising the annealing temperature to 500 °C, we observed a second transition in which carbon nanofibers (CNFs) grew from the porous crystal. This approach represents a simple and effective method for the synthesis of porous materials with good control over pore size and density. It also enables the synthesis of complex networks of nanostructures (in our case CNFs) by simply varying process parameters such as temperature and gas flows. This represents an important advance for the fabrication of porous coordination complex crystals.

  12. Building complex hybrid carbon architectures by covalent interconnections: graphene-nanotube hybrids and more.

    Science.gov (United States)

    Lv, Ruitao; Cruz-Silva, Eduardo; Terrones, Mauricio

    2014-05-27

    Graphene is theoretically a robust two-dimensional (2D) sp(2)-hybridized carbon material with high electrical conductivity and optical transparency. However, due to the existence of grain boundaries and defects, experimentally synthesized large-area polycrystalline graphene sheets are easily broken and can exhibit high sheet resistances; thus, they are not suitable as flexible transparent conductors. As described in this issue of ACS Nano, Tour et al. circumvented this problem by proposing and synthesizing a novel hybrid structure that they have named "rebar graphene", which is composed of covalently interconnected carbon nanotubes (CNTs) with graphene sheets. In this particular configuration, CNTs act as "reinforcing bars" that not only improve the mechanical strength of polycrystalline graphene sheets but also bridge different crystalline domains so as to enhance the electrical conductivity. This report seems to be only the tip of the iceberg since it is also possible to construct novel and unprecedented hybrid carbon architectures by establishing covalent interconnections between CNTs with graphene, thus yielding graphene-CNT hybrids, three-dimensional (3D) covalent CNT networks, 3D graphene networks, etc. In this Perspective, we review the progress of these carbon hybrid systems and describe the challenges that need to be overcome in the near future.

  13. Fundamental reactivity of the Metal-Carbon bond in cyclometalated PNC-complexes

    NARCIS (Netherlands)

    Jongbloed, L.S.

    2016-01-01

    The activation of C-H bonds by transition metals and the reactivity of the corresponding metal-carbon bond are interesting research topics form different point of views. Catalytic C-H bond functionalization has emerged as a highly active research area for the development of green construction of Car

  14. Fundamental reactivity of the Metal-Carbon bond in cyclometalated PNC-complexes

    NARCIS (Netherlands)

    L.S. Jongbloed

    2016-01-01

    The activation of C-H bonds by transition metals and the reactivity of the corresponding metal-carbon bond are interesting research topics form different point of views. Catalytic C-H bond functionalization has emerged as a highly active research area for the development of green construction of Car

  15. From simple to complex prebiotic chemistry in a carbon-rich universe

    Science.gov (United States)

    Lage, C.; Janot-Pacheco, E.; Domiciano de Souza, A.; Suárez, O.; Bendjoya, P.; Gadotti, D. A.

    2012-09-01

    It is well known that the main components of important biomolecules are quite common not only in the Solar System, but also in other planetary systems and in the Galactic ISM. The ubiquitous presence of C in the Universe and the unique carbon chemical properties and carbon bonding thermodynamics supports the spontaneous self-replication of monomers into larger polymers, yielding the formation of large molecules. The detection of an ever increasing number of organic molecules in the interstellar medium (ISM) by radio-telescopes and chemical analysis of meteorites boosted astrochemical theories on radiation-induced chemistry, supported by laboratory experiments. In this scenario of exogenous origin of carbon compounds, polyaromatic hydrocarbons (PAHs) may represent a resilient way of accumulating carbon as a robust cosmic reservoir. Consisting of a family of compounds with fused aromatic rings, the abundances of its larger members (50-100 carbon atoms) were estimated to be on top scores just after H2 and CO. PAHs have been detected in the ISM, in star-forming regions, ~14% of low-mass premainsequence stars, and, remarkably, in some 54% of intermediate mass stars. They have also been detected by SPITZER in distant galaxies up to z = 3. PAHs were promptly photolysed into a family of radicals if exposed to UV and oxygen-bearing molecules in laboratory. The presence of oxygenbearing molecules was shown in the laboratory to bring aromatic rings into an unstable chemistry leading to the production of e.g. alcohols, ketones and ether radicals. It has already been observed that carbon-and oxygen-rich stellar envelopes give rise to richer carbon chemistry. It appears very tempting to think that key prebiotic fragments should appear along planetary formation as C-O reaction byproducts such as methanol (CH3OH), formaldehyde (H2CO) and also simpler hydrocarbons as methyl acetylene (CH3CCH). Under an Astrobiology perspective it is plausible to map PAHs and oxygen compounds

  16. Electro-Thermal and Semiconductivity Behaviour of Natural Sintered Complex Carbonate Ore for Thermo-Technological Applications

    OpenAIRE

    Loutfy H. Madkour

    2014-01-01

    The polymetal (Zn, Pb, Fe, Ca, Mg, Cd, Ba, Ni, Ti, and SiO2) complex Umm-Gheig carbonate ore is subjected to sintering treatment at 573, 773, 973 and 1273 K respectively for four hours. Chemical, spectral, X-ray and differential thermal analyses are applied for the native ore as well as for the samples preheated and sintered. The current versus applied DC voltage (I–V) characteristics, bulk density (Db), percent shrinkage (%S), activation energy (Ea) and energy gap (Eg) are established for th...

  17. Complex

    African Journals Online (AJOL)

    CLEMENT O BEWAJI

    Schiff bases and their complex compounds have been studied for their .... establishing coordination of the N–(2 – hydroxybenzyl) - L - α - valine Schiff base ..... (1967); “Spectrophotometric Identification of Organic Compounds”, Willey, New.

  18. High-resolution structure of human carbonic anhydrase II complexed with acetazolamide reveals insights into inhibitor drug design.

    Science.gov (United States)

    Sippel, Katherine H; Robbins, Arthur H; Domsic, John; Genis, Caroli; Agbandje-McKenna, Mavis; McKenna, Robert

    2009-10-01

    The crystal structure of human carbonic anhydrase II (CA II) complexed with the inhibitor acetazolamide (AZM) has been determined at 1.1 A resolution and refined to an R(cryst) of 11.2% and an R(free) of 14.7%. As observed in previous CA II-inhibitor complexes, AZM binds directly to the zinc and makes several key interactions with active-site residues. The high-resolution data also showed a glycerol molecule adjacent to the AZM in the active site and two additional AZMs that are adventitiously bound on the surface of the enzyme. The co-binding of AZM and glycerol in the active site demonstrate that given an appropriate ring orientation and substituents, an isozyme-specific CA inhibitor may be developed.

  19. METALLOPROTEINS. A tethered niacin-derived pincer complex with a nickel-carbon bond in lactate racemase.

    Science.gov (United States)

    Desguin, Benoît; Zhang, Tuo; Soumillion, Patrice; Hols, Pascal; Hu, Jian; Hausinger, Robert P

    2015-07-03

    Lactic acid racemization is involved in lactate metabolism and cell wall assembly of many microorganisms. Lactate racemase (Lar) requires nickel, but the nickel-binding site and the role of three accessory proteins required for its activation remain enigmatic. We combined mass spectrometry and x-ray crystallography to show that Lar from Lactobacillus plantarum possesses an organometallic nickel-containing prosthetic group. A nicotinic acid mononucleotide derivative is tethered to Lys(184) and forms a tridentate pincer complex that coordinates nickel through one metal-carbon and two metal-sulfur bonds, with His(200) as another ligand. Although similar complexes have been previously synthesized, there was no prior evidence for the existence of pincer cofactors in enzymes. The wide distribution of the accessory proteins without Lar suggests that it may play a role in other enzymes.

  20. Noncovalent interactions between a trinuclear monofunctional platinum complex and human serum albumin.

    Science.gov (United States)

    Wang, Yanqing; Wang, Xiaoyong; Wang, Jing; Zhao, Yongmei; He, Weijiang; Guo, Zijian

    2011-12-19

    Interactions between platinum complexes and human serum albumin (HSA) play crucial roles in the metabolism, distribution, and efficacy of platinum-based anticancer drugs. Polynuclear monofunctional platinum(II) complexes represent a new class of anticancer agents that display distinct molecular characters of pharmacological action from those of cisplatin. In this study, the interaction between a trinuclear monofunctional platinum(II) complex, [Pt(3)LCl(3)](ClO(4))(3) (L = N,N,N',N',N",N"-hexakis(2-pyridylmethyl)-1,3,5-tris(aminomethyl)benzene) (1), and HSA was investigated using ultraviolet-visible spectroscopy, Fourier transform infrared spectroscopy, circular dichroism spectroscopy, fluorescence spectroscopy, molecular docking, and inductively coupled plasma mass spectrometry. The spectroscopic and thermodynamic data show that the interaction is a spontaneous process with the estimated enthalpy and entropy changes being 14.6 kJ mol(-1) and 145.5 J mol(-1) K(-1), respectively. The reactive sites of HSA to complex 1 mainly locate within its hydrophobic cavity in domain II. Noncovalent actions such as π-π stacking and hydrophobic bonding are the primary contributors to the interaction between HSA and complex 1, which is different from the scenario for cisplatin in similar conditions. The results suggest that the connection between complex 1 and HSA is reversible, and therefore the cytotoxic activity of the complex could be preserved during blood circulation.

  1. Determination of carbon number distributions of complex phthalates by gas chromatography-mass spectrometry with ammonia chemical ionization.

    Science.gov (United States)

    Di Sanzo, Frank P; Lim, Peniel J; Han, Wenning W

    2015-01-01

    An assay method for phthalate esters with a complex mixture of isomer of varying carbon numbers, such as di-isononyl phthalate (DINP) and di-isodecyl phthalate (DIDP), using gas chromatography-mass spectrometry (GC-MS) positive chemical ionization (PCI) with 5% ammonia in methane is described. GC-MS-PCI-NH3, unlike GC-MS electron ionization (EI) (GC-MS-EI) that produces generally m/z 149 ion as the main base peak and low intensity M(+) peaks, produces higher intensity (M + 1) ions that allow the determination of total (R + R') carbon number distributions based on the various R and R' alkyl groups of the di-esters moiety. The technique allows distinguishing among the various commercial DINP and DIDP plasticizers. The carbon number distributions are determined in the acceptable range of 85 mole percent (m/m). Several examples of analysis made on commercial DINP and DIDP are presented. The use of only 5% instead of 100% ammonia simplifies use of GC-MS-PCI-NH3 but still produces sufficient M + 1 ion intensities that are appropriate for the assay. In addition, use of low concentrations of ammonia mitigates potential safety aspects related to use of ammonia and provides less corrosion for the instrument hardware.

  2. Electrocatalytic Study of Carbon Dioxide Reduction By Co(TPPCl Complex

    Directory of Open Access Journals (Sweden)

    Khalaf Alenezi

    2016-01-01

    Full Text Available Carbon dioxide (CO2 is notorious for being a greenhouse gas and is the most important cause of global warming. However, it can be converted into useful products as it is a source of carbon. Reduction of CO2 is therefore an attractive research topic for many chemists. Different methods of electrocatalytic reduction of CO2 have been reported previously. Since CO2 is very stable, the direct electroreduction of CO2 into CO requires high potential at −2.2 V versus Ag/AgCl. In this work, CO2 reduction was carried out by the photoelectrocatalysis of CO2 in the presence of cobalt(IIItetraphenylporphyrin [Co(TPPCl] at −1.85 V with a current efficiency of 71%. At illuminated p-type silicon photocathode, the reduction of CO2 into CO was performed at a potential of 300 mV which is positive. However, at the same conditions, potential of −1.55 V with a current efficiency of ca 65% is required for the carbon electrode.

  3. Carbon Nanotube Container: Complexes of C50H10 with Small Molecules.

    Science.gov (United States)

    Dodziuk, Helena; Korona, Tatiana; Lomba, Enrique; Bores, Cecilia

    2012-11-13

    The stability of complexes of a recently synthetized (Scott et al. J. Am. Chem. Soc.2011, 134, 107) opened nanocontainer C50H10 with several guest molecules, H2, N2, CO, HCN, H2O, CO2, CS2, H2S, C2H2, NH3, CH4, CH3CN, CH3OH, CH3CCH, 2-butyne, methyl halides, and with noble gas atoms, has been examined by means of symmetry-adapted perturbation theory of intermolecular interactions, which fully incorporates all important energy components, including a difficult dispersion term. All complexes under scrutiny have been found stable for all studied guests at 0 K, but entropic effects cause many of them to dissociate into constituent molecules under standard conditions. The estimation of temperature at which the Gibbs free energy ΔG = 0 revealed that the recently observed (Scott et al. J. Am. Chem. Soc.2011, 134, 107) complex CS2@C50H10 is the most stable at room temperature while the corresponding complexes with HCN and Xe guests should decompose at ca. 310 K and that with CO2 at room temperature (ca. 300 K). In agreement with the ΔG estimation, molecular dynamics simulations performed in vacuum for the CS2@C50H10 complex predicted that the complex is stable but decomposes at ca. 350 K. The MD simulations in CHCl3 solution showed that the presence of solvent stabilizes the CS2@C50H10 complex in comparison to vacuum. Thus, for the complexes obtained in solution the CO2 gas responsible for the greenhouse effect could be stored in the C50H10 nanotube.

  4. Electron and ligand transfer reactions between cyclometallated platinum(II) compounds and thallium(III) carboxylates

    NARCIS (Netherlands)

    Koten, G. van; Ploeg, A.F.M.J. van der; Vrieze, K.

    1982-01-01

    Reaction of trans-[(2-Me{2}NCH{2}C{6}H{4}{2}Pt}I{}I{] with Tl}I{}I{}I{(O{2}CR){3} (R = Me, i-Pr) gave direct elimination of Tl}I{(O{2}CR) and formation of the oxidative addition product [(2-Me{2}NCH{2}C{6}H{4}){2}Pt}I{}V{ (O{2}CR){2}], in two isomeric forms. A structure with the carbon ligands in tr

  5. Electron and ligand transfer reactions between cyclometallated platinum(II) compounds and thallium(III) carboxylates

    NARCIS (Netherlands)

    Koten, G. van; Ploeg, A.F.M.J. van der; Vrieze, K.

    1982-01-01

    Reaction of trans-[(2-Me{2}NCH{2}C{6}H{4}{2}Pt}I{}I{] with Tl}I{}I{}I{(O{2}CR){3} (R = Me, i-Pr) gave direct elimination of Tl}I{(O{2}CR) and formation of the oxidative addition product [(2-Me{2}NCH{2}C{6}H{4}){2}Pt}I{}V{ (O{2}CR){2}], in two isomeric forms. A structure with the carbon ligands in

  6. The effect of pH on the complexation of Cd, Ni and Zn by dissolved organic carbon from leachate-polluted groundwater

    DEFF Research Database (Denmark)

    Christensen, J. B.; Christensen, Thomas Højlund

    2000-01-01

    Complexation of cadmium (Cd), nickel (Ni) and zinc (Zn) by dissolved organic carbon (DOC) in leachate-polluted groundwater was measured using a resin equilibrium method. Metal-DOC complexation was measured at di€erent DOC concentrations over a range of pH values . The results were compared...

  7. Half-sandwich rhodium poly-chalcogenide complexes and a carbon insertion into Te-Te bond

    Institute of Scientific and Technical Information of China (English)

    2002-01-01

    Treatment of CptRh(PMe3)Cl2(1) (Cpt = 5(- tBu2C5H3) with [Et4N]2Se6 in DMF solution leads to the formation of cyclo-tetraselenido half-sandwich rhodium complexes CptRh(PMe3)(Se4) (2). The elimination of 2 with excess of nBu3P results in cyclo-diselenido rhodium complex CptRh(PMe3)(Se2) (3). 1 reacts with [nBu4N]2Te5 in DMF solution to yield cyclo-ditellurido rhodium complex CptRh (PMe3)(Te2) (4) in which carbon atom from CH2Cl2 can be inserted into Te-Te bond to form CptRh(PMe3)(TeCH2Te) (5). The new complexes 2-5 have been characterized by their IR, EI-MS, and 1H, 13C, 31P, 103Rh NMR spectra as well as elemental analysis.

  8. Dinuclear and Trinuclear Nickel Complexes as Effective Catalysts for Alternating Copolymerization on Carbon Dioxide and Cyclohexene Oxide.

    Science.gov (United States)

    Tsai, Chen-Yen; Cheng, Fu-Yin; Lu, Kuan-Yeh; Wu, Jung-Tsu; Huang, Bor-Hunn; Chen, Wei-An; Lin, Chu-Chieh; Ko, Bao-Tsan

    2016-08-15

    A series of novel nickel complexes 1-9 supported by NNO-tridentate Schiff-base derivatives have been synthesized and characterized. Treatment of the pro-ligands [L(1)-H = 2,4-di-tert-butyl-6-(((2-(dimethylamino)ethyl)imino)methyl)phenol, L(2)-H = 2-(((2-(dimethylamino)ethyl)imino)methyl)-4,6-bis(2-phenylpropan-2-yl)phenol, L(3)-H = 2-(((2-(dimethylamino)ethyl)imino)methyl)phenol] with Ni(OAc)2·4H2O in refluxing ethanol afforded mono- or bimetallic nickel complexes {[(L(1))Ni(OAc)] (1); (L(2))Ni(OAc)] (2); (L(3))2Ni2(OAc)2(H2O)] (3)}. Alcohol-solvated trimetallic nickel acetate complexes {[(L(3))2Ni3(OAc)4(MeOH)2] (4); (L(3))2Ni3(OAc)4(EtOH)2] (5)} could be generated from the reaction of L(3)-H and anhydrous nickel(II) acetate with a ratio of 2:3 in refluxing anhydrous MeOH or EtOH. The reaction of nickel acetate tetrahydrate and L(4)-H to L(6)-H [L(4)-H = 2-(((2-(dimethylamino)ethyl)imino)methyl)-5-methoxyphenol, L(5)-H = 2-(((2-(dimethylamino)ethyl)imino)methyl)-4-methoxy-phenol, L(6)-H = 2-(((2-(dimethylamino)ethyl)imino)(phenyl)methyl)phenol] produced, respectively, the alcohol-free trinuclear nickel complexes {[(L(4))2Ni3(OAc)4] (7); [(L(5))2Ni3(OAc)4] (8); [(L(6))2Ni3(OAc)4] (9)} with the same ratio in refluxing EtOH under the atmospheric environment. Interestingly, recrystallization of [(L(3))2Ni3(OAc)4(MeOH)] (4) or [(L(3))2Ni3(OAc)4(EtOH)] (5) in the mixed solvent of CH2Cl2/hexane gives [(L(3))2Ni3(OAc)4] (6), which is isostructural with analogues 7-9. All bi- and trimetallic nickel complexes exhibit efficient activity and good selectivity for copolymerization of CO2 with cyclohexene oxide, resulting in copolymers with a high alternating microstructure possessing ≥99% carbonate-linkage content. This is the first example to apply well-defined trinuclear nickel complexes as efficient catalysts for the production of perfectly alternating poly(cyclohexene carbonate).

  9. Novel encapsulation method for probiotics using an interpolymer complex in supercriticial carbon dioxide

    CSIR Research Space (South Africa)

    Moolman, FS

    2006-10-01

    Full Text Available industry for protection and controlled release of drugs. However, its application in probiotics is limited due to the typical use of solvents, temperature and/or water and the presence of oxygen in the encapsulation process. Supercritical carbon dioxide... (scCO2) is an interesting alternative solvent – its critical point is at 31.1 ºC and 73.8 bar (Lide, 2003) and one can avoid the use of solvents, water and high temperatures. Unfortunately scCO2 is not a very good solvent for most polymers...

  10. Bioinspired photoelectric conversion system based on carbon-quantum-dot-doped dye-semiconductor complex.

    Science.gov (United States)

    Ma, Zheng; Zhang, Yong-Lai; Wang, Lei; Ming, Hai; Li, Haitao; Zhang, Xing; Wang, Fang; Liu, Yang; Kang, Zhenhui; Lee, Shuit-Tong

    2013-06-12

    Compared to nature's photoelectric conversion processes, artificial devices are still far inferior in efficiency and stability. Inspired by light absorption and resonance energy transfer processes of chlorophyll, we developed a highly efficient photoelectric conversion system by introducing Carbon quantum dots (CQDs) as an electron transfer intermediary. Compared with conventional dye-sensitized semiconductor systems, the present CQD-doped system showed significantly higher photoelectric conversion efficiency, as much as 7 times that without CQDs. The CQD-doped dye/semiconductor system may provide a powerful approach to the development of highly efficient photoelectric devices.

  11. Synthesis and Analysis of the Structure, Diffusion and Cytotoxicity of Heterocyclic Platinum(IV) Complexes.

    Science.gov (United States)

    Macias, Freddy J; Deo, Krishant M; Pages, Benjamin J; Wormell, Paul; Clegg, Jack K; Zhang, Yingjie; Li, Feng; Zheng, Gang; Sakoff, Jennette; Gilbert, Jayne; Aldrich-Wright, Janice R

    2015-11-16

    We have developed six dihydroxidoplatinum(IV) compounds with cytotoxic potential. Each derived from active platinum(II) species, these complexes consist of a heterocyclic ligand (HL) and ancillary ligand (AL) in the form [Pt(HL)(AL)(OH)2](2+), where HL is a methyl-functionalised variant of 1,10-phenanthroline and AL is the S,S or R,R isomer of 1,2-diaminocyclohexane. NMR characterisation and X-ray diffraction studies clearly confirmed the coordination geometry of the octahedral platinum(IV) complexes. The self-stacking of these complexes was determined using pulsed gradient stimulated echo nuclear magnetic resonance. The self-association behaviour of square planar platinum(II) complexes is largely dependent on concentration, whereas platinum(IV) complexes do not aggregate under the same conditions, possibly due to the presence of axial ligands. The cytotoxicity of the most active complex, exhibited in several cell lines, has been retained in the platinum(IV) form.

  12. Catalytic hydrogenation of carbon monoxide to alkenes over partially degraded iron-cobalt complexes

    NARCIS (Netherlands)

    Snel, R.

    1989-01-01

    Complex-derived iron-cobalt alloy catalysts have been studied under conditions similar to those normally prevailing in industry. Despite reports in the literature indicating unusual selectivities with iron-cobalt alloy catalysts under atmospheric pressure conditions, no deviations from normal select

  13. Characterization of Ketoprofen/Methyl-β-Cyclodextrin Complexes Prepared Using Supercritical Carbon Dioxide

    Directory of Open Access Journals (Sweden)

    Mauro Banchero

    2013-01-01

    Full Text Available Complexes of methyl-β-cyclodextrin and ketoprofen, a crystalline anti-inflammatory drug with poor water solubility, have been prepared for the first time in the presence of supercritical CO2 at 40°C and 20 MPa. The supercritical treatment allows these pharmaceutical formulations to be prepared without the use of any auxiliary agents or organic solvents. The treated samples were characterized through differential scanning calorimetry, X-ray diffractometry, and the Fourier transform infrared spectroscopy to exclude the presence of crystalline drug and check the formation of the complexes. The increase of the drug dissolution rate was investigated performing in vitro release tests in aqueous solutions. The results showed that the supercritical treatment can be an efficient method to obtain inclusion complexes with enhanced release kinetics. The operating methods of the release tests, that is, the “tablet method” or the “dispersed amount method,” affected both the dissolution rate and its dependence on the drug amount in the samples. On the contrary, the variation of the pH of the dissolution medium did not show any effect on the release rate of the supercritical complexes.

  14. Lanthanide Complexes with Multidentate Oxime Ligands as Single-Molecule Magnets and Atmospheric Carbon Dioxide Fixation Systems.

    Science.gov (United States)

    Hołyńska, Małgorzata; Clérac, Rodolphe; Rouzières, Mathieu

    2015-09-14

    The synthesis, structure, and magnetic properties of five lanthanide complexes with multidentate oxime ligands are described. Complexes 1 and 2 (1: [La2 (pop)2 (acac)4 (CH3 OH)], 2: [Dy2 (pop)(acac)5 ]) are synthesized from the 2-hydroxyimino-N-[1-(2-pyridyl)ethylidene]propanohydrazone (Hpop) ligand, while 3, 4, and 5 (3: [Dy2 (naphthsaoH)2 (acac)4 H(OH)]⋅0.85 CH3 CN⋅1.58 H2 O; 4: [Tb2 (naphthsaoH)2 (acac)4 H(OH)]⋅0.52 CH3 CN⋅1.71 H2 O; 5: [La6 (CO3 )2 (naphthsao)5 (naphthsaoH)0.5 (acac)8 (CO3 )0.5 (CH3 OH)2.76 H5.5 (H2 O)1.24 ]⋅2.39 CH3 CN⋅0.12 H2 O) contain 1-(1-hydroxynaphthalen-2-yl)-ethanone oxime (naphthsaoH2 ). In 1-4, dinuclear [Ln2 ] complexes crystallize, whereas hexanuclear La(III) complex 5 is formed after fixation of atmospheric carbon dioxide. Dy(III) -based complexes 2 and 3 display single-molecule-magnet properties with energy barriers of 27 and 98 K, respectively. The presence of a broad and unsymmetrical relaxation mode observed in the ac susceptibility data for 3 suggest two different dynamics of the magnetization which might be a consequence of independent relaxation processes of the two different Dy(3+) ions.

  15. Manganese(III) Schiff base complexes: chemistry relevant to the copolymerization of epoxides and carbon dioxide.

    Science.gov (United States)

    Darensbourg, Donald J; Frantz, Eric B

    2007-07-23

    Schiff base complexes of the form (acacen)Mn(III)X (acacen = N,N'-bis(acetylacetone)-1,2-ethylenediimine), where X = OAc, Cl, or N(3), have been evaluated for their ability to couple CO(2) and cyclohexene oxide in the presence of a variety of cocatalysts to provide cyclic or polycarbonates. These complexes proved to be ineffective at catalyzing this process; however, valuable information related to the coordination chemistry of these manganese Schiff bases was elucidated. Of importance, mechanistic findings as revealed by comprehensive studies involving structurally related (salen)CrX and (salen)CoX complexes strongly support the requirement of six-coordinate metal species for the effective copolymerization of CO(2) and epoxides. In the case of these Mn(III) complexes, it was determined that in chloroform or toluene solution a five-coordinate species was greatly favored over a six-coordinate species even in the presence of 20 equiv or more of various Lewis bases. Significantly epoxide monomers such as propylene oxide and cyclohexene oxide displayed no tendency to bind to these (acacen)MnX derivatives, even when used as solvents. Only in the case of excessive quantities of heterocyclic amines such as pyridine, DMAP, and DBU was spectral evidence of a six-coordinate Mn derivative observed in solution. X-ray crystal structures are provided for many of the complexes involved in this study, including the one-dimensional polymeric structures of [(acacen)MnOAc x 2H(2)O](n), [(acacen)MnN(3)](n) (mu(1,3)-N(3)), and a rare mixed bridging species [(acacen)MnN(3)](n) (mu(1,3)-N(3)/mu(1,1)-N(3)). In addition, a structure was obtained in which the unit cell contains both a (acacen)MnN(3)(DMAP) and a (acacen)MnN(3) species.

  16. Visible-Light Photoredox Catalysis: Selective Reduction of Carbon Dioxide to Carbon Monoxide by a Nickel N-Heterocyclic Carbene-Isoquinoline Complex

    Energy Technology Data Exchange (ETDEWEB)

    Thoi, VanSara; Kornienko, Nick; Margarit, C; Yang, Peidong; Chang, Christopher

    2013-06-07

    The solar-driven reduction of carbon dioxide to value-added chemical fuels is a longstanding challenge in the fields of catalysis, energy science, and green chemistry. In order to develop effective CO2 fixation, several key considerations must be balanced, including (1) catalyst selectivity for promoting CO2 reduction over competing hydrogen generation from proton reduction, (2) visible-light harvesting that matches the solar spectrum, and (3) the use of cheap and earth-abundant catalytic components. In this report, we present the synthesis and characterization of a new family of earth-abundant nickel complexes supported by N-heterocyclic carbene amine ligands that exhibit high selectivity and activity for the electrocatalytic and photocatalytic conversion of CO2 to CO. Systematic changes in the carbene and amine donors of the ligand have been surveyed, and [Ni(Prbimiq1)]2+ (1c, where Prbimiq1 = bis(3-(imidazolyl)isoquinolinyl)propane) emerges as a catalyst for electrochemical reduction of CO2 with the lowest cathodic onset potential (Ecat = 1.2 V vs SCE). Using this earth-abundant catalyst with Ir(ppy)3 (where ppy = 2-phenylpyridine) and an electron donor, we have developed a visible-light photoredox system for the catalytic conversion of CO2 to CO that proceeds with high selectivity and activity and achieves turnover numbers and turnover frequencies reaching 98,000 and 3.9 s1, respectively. Further studies reveal that the overall efficiency of this solar-to-fuel cycle may be limited by the formation of the active Ni catalyst and/or the chemical reduction of CO2 to CO at the reduced nickel center and provide a starting point for improved photoredox systems for sustainable carbon-neutral energy conversion.

  17. Enhancing Carbon Fixation by Metabolic Engineering: A Model System of Complex Network Modulation

    Energy Technology Data Exchange (ETDEWEB)

    Dr. Gregory Stephanopoulos

    2008-04-10

    In the first two years of this research we focused on the development of a DNA microarray for transcriptional studies in the photosynthetic organism Synechocystis and the elucidation of the metabolic pathway for biopolymer synthesis in this organism. In addition we also advanced the molecular biological tools for metabolic engineering of biopolymer synthesis in Synechocystis and initiated a series of physiological studies for the elucidation of the carbon fixing pathways and basic central carbon metabolism of these organisms. During the last two-year period we focused our attention on the continuation and completion of the last task, namely, the development of tools for basic investigations of the physiology of these cells through, primarily, the determination of their metabolic fluxes. The reason for this decision lies in the importance of fluxes as key indicators of physiology and the high level of information content they carry in terms of identifying rate limiting steps in a metabolic pathway. While flux determination is a well-advanced subject for heterotrophic organisms, for the case of autotrophic bacteria, like Synechocystis, some special challenges had to be overcome. These challenges stem mostly from the fact that if one uses {sup 13}C labeled CO{sub 2} for flux determination, the {sup 13}C label will mark, at steady state, all carbon atoms of all cellular metabolites, thus eliminating the necessary differentiation required for flux determination. This peculiarity of autotrophic organisms makes it imperative to carry out flux determination under transient conditions, something that had not been accomplished before. We are pleased to report that we have solved this problem and we are now able to determine fluxes in photosynthetic organisms from stable isotope labeling experiments followed by measurements of label enrichment in cellular metabolites using Gas Chromatography-Mass Spectrometry. We have conducted extensive simulations to test the method and

  18. Antitumor activities and interaction with DNA of oxaliplatin-type platinum complexes with linear or branched alkoxyacetates as leaving groups.

    Science.gov (United States)

    Yin, Runting; Gou, Shaohua; Liu, Xia; Lou, Liguang

    2011-08-01

    Five oxaliplatin-typed platinum complexes containing trans-1R, 2R-diaminocyclohexane chelating platinum cores, characteristic of linear or branched alkoxycarboxylates as leaving groups, were biologically evaluated. These compounds showed higher antitumor activity, lower toxicity in vivo than cisplatin or oxaliplatin. And the results revealed that the antitumor activity and interaction with DNA of these compounds were highly related to the nature of leaving groups. Among these complexes, 5a, cis-(trans-1R, 2R-diaminocyclohexane) bis (2-tert-butoxyacetate) platinum(II), showed the highest antitumor activity and the lowest toxicity.

  19. Binding of kinetically inert metal ions to RNA: the case of platinum(II).

    Science.gov (United States)

    Chapman, Erich G; Hostetter, Alethia A; Osborn, Maire F; Miller, Amanda L; DeRose, Victoria J

    2011-01-01

    In this chapter several aspects of Pt(II) are highlighted that focus on the properties of Pt(II)-RNA adducts and the possibility that they influence RNA-based processes in cells. Cellular distribution of Pt(II) complexes results in significant platination of RNA, and localization studies find Pt(II) in the nucleus, nucleolus, and a distribution of other sites in cells. Treatment with Pt(II) compounds disrupts RNA-based processes including enzymatic processing, splicing, and translation, and this disruption may be indicative of structural changes to RNA or RNA-protein complexes. Several RNA-Pt(II) adducts have been characterized in vitro by biochemical and other methods. Evidence for Pt(II) binding in non-helical regions and for Pt(II) cross-linking of internal loops has been found. Although platinated sites have been identified, there currently exists very little in the way of detailed structural characterization of RNA-Pt(II) adducts. Some insight into the details of Pt(II) coordination to RNA, especially RNA helices, can be gained from DNA model systems. Many RNA structures, however, contain complex tertiary folds and common, purine-rich structural elements that present suitable Pt(II) nucleophiles in unique arrangements which may hold the potential for novel types of platinum-RNA adducts. Future research aimed at structural characterization of platinum-RNA adducts may provide further insights into platinum-nucleic acid binding motifs, and perhaps provide a rationale for the observed inhibition by Pt(II) complexes of splicing, translation, and enzymatic processing.

  20. A Photoactivatable Platinum(IV) Complex Targeting Genomic DNA and Histone Deacetylases.

    Science.gov (United States)

    Kasparkova, Jana; Kostrhunova, Hana; Novakova, Olga; Křikavová, Radka; Vančo, Ján; Trávníček, Zdeněk; Brabec, Viktor

    2015-11-23

    We report toxic effects of a photoactivatable platinum(IV) complex conjugated with suberoyl-bis-hydroxamic acid in tumor cells. The conjugate exerts, after photoactivation, two functions: activity as both a platinum(II) anticancer drug and histone deacetylase (HDAC) inhibitor in cancer cells. This approach relies on the use of a Pt(IV) pro-drug, acting by two independent mechanisms of biological action in a cooperative manner, which can be selectively photoactivated to a cytotoxic species in and around a tumor, thereby increasing selectivity towards cancer cells. These results suggest that this strategy is a valuable route to design new platinum agents with higher efficacy for photodynamic anticancer chemotherapy.

  1. Kinetics of the Removal of Chromium Complex Dye from Aqueous Solutions Using Activated Carbons and Polymeric Adsorbent

    Directory of Open Access Journals (Sweden)

    Eglė Kazlauskienė

    2011-04-01

    Full Text Available The kinetics of the removal of chromium complex dye (Lanasyn Navy M-DNL from aqueous solutions using polymeric adsorbent Macronet MN 200 (MN 200 as an alternative option for activated carbon Norit RB 0.8 CC (AC was studied in the batch system. The residual colour of dye solution treated with AC or MN 200 strongly depends on solution pH with lower values at acidic pH when a positively charged surface net is favourable for the adsorption of the dye anion. The removal of dye using MN 200 was found relatively higher than that using AC. The pseudo-second order and intraparticle diffusion models agreed well with experimental data. The parameters of these models were studied as a function of temperature and adsorbent nature.Article in Lithuanian

  2. Hierarchically-Porous Carbon Derived from a Large-Scale Iron-based Organometallic Complex for Versatile Energy Storage.

    Science.gov (United States)

    Fan, Chao-Ying; Li, Huan-Huan; Wang, Hai-Feng; Sun, Hai-Zhu; Wu, Xing-Long; Zhang, Jing-Ping

    2016-06-22

    Inspired by the preparation of the hierarchically-porous carbon (HPC) derived from metal organic frameworks (MOFs) for energy storage, in this work, a simple iron-based metal- organic complex (MOC), which was simpler and cheaper compared with the MOF, was selected to achieve versatile energy storage. The intertwined 1 D nanospindles and enriched-oxygen doping of the HPC was obtained after one-step carbonization of the MOC. When employed in lithium-ion batteries, the HPC exhibited reversible capacity of 778 mA h g(-1) after 60 cycles at 50 mA g(-1) . Moreover, the HPC maintained a capacity of 188 mA h g(-1) after 400 cycles at 100 mA g(-1) as the anode material in a sodium-ion battery. In addition, the HPC served as the cathode matrix for evaluation of a lithium-sulfur battery. The general preparation process of the HPC is commercial, which is responsible for the large-scale production for its practical application. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  3. A highly efficient nano-cluster artificial peroxidase and its direct electrochemistry on a nano complex modified glassy carbon electrode.

    Science.gov (United States)

    Hong, Jun; Wang, Wei; Huang, Kun; Yang, Wei-Yun; Zhao, Ying-Xue; Xiao, Bao-Lin; Gao, Yun-Fei; Moosavi-Movahedi, Zainab; Ghourchian, Hedayatollah; Moosavi-Movahedi, Ali Akbar

    2012-01-01

    A nano-cluster with highly efficient peroxide activity was constructed based on nafion (NF) and cytochrome c (Cyt c). UV-Vis spectrometry and transmission electron microscopy (TEM) methods were utilized for characterization of the nano-structured enzyme or artificial peroxidase (AP). The nano-cluster was composed of a Chain-Ball structure, with an average ball size of about 40 nm. The Michaelis-Menten (K(m)) and catalytic rate (k(cat)) constants of the AP were determined to be 2.5 ± 0.4 µM and 0.069 ± 0.001 s(-1), respectively, in 50 mM PBS at pH 7.0. The catalytic efficiency of the AP was evaluated to be 0.028 ± 0.005 µM(-1) s(-1), which was 39 ± 5% as efficient as the native horseradish peroxidase (HRP). The AP was also immobilized on a functional multi-wall carbon nanotube (MWNCTs)-gold colloid nanoparticles (AuNPs) nano-complex modified glassy carbon (GC) electrode. The cyclic voltammetry of AP on the nano complex modified GC electrode showed a pair of well-defined redox peaks with a formal potential (E°') of -45 ± 2 mV (vs. Ag/AgCl) at a scan rate of 0.05 V/s. The heterogeneous electron transfer rate constant (k(s)) was evaluated to be 0.65 s(-1). The surface concentration of electroactive AP on GC electrode (Γ) was 7 × 10(-10) mol cm(-2). The apparent Michaelis-Menten constant (K(m)(app)) was 0.23 nM.

  4. Spatial and seasonal variabilities of the stable carbon isotope composition of soil CO2 concentration and flux in complex terrain

    Science.gov (United States)

    Liang, Liyin L.; Riveros-Iregui, Diego A.; Risk, David A.

    2016-09-01

    Biogeochemical processes driving the spatial variability of soil CO2 production and flux are well studied, but little is known about the variability in the spatial distribution of the stable carbon isotopes that make up soil CO2, particularly in complex terrain. Spatial differences in stable isotopes of soil CO2 could indicate fundamental differences in isotopic fractionation at the landscape level and may be useful to inform modeling of carbon cycling over large areas. We measured the spatial and seasonal variabilities of the δ13C of soil CO2 (δS) and the δ13C of soil CO2 flux (δP) in a subalpine forest ecosystem located in the Rocky Mountains of Montana. We found consistently more isotopically depleted values of δS and δP in low and wet areas of the landscape relative to steep and dry areas. Our results suggest that the spatial patterns of δS and δP are strongly mediated by soil water and soil respiration rate. More interestingly, our analysis revealed different temporal trends in δP across the landscape; in high landscape positions δP became more positive, whereas in low landscape positions δP became more negative with time. These trends might be the result of differential dynamics in the seasonality of soil moisture and its effects on soil CO2 production and flux. Our results suggest concomitant yet independent effects of water on physical (soil gas diffusivity) and biological (photosynthetic discrimination) processes that mediate δS and δP and are important when evaluating the δ13C of CO2 exchanged between soils and the atmosphere in complex terrain.

  5. A sensing mechanism for the detection of carbon nanotubes using selective photoluminescent probes based on ionic complexes with organic dyes

    Institute of Scientific and Technical Information of China (English)

    Petro Lutsyk; Raz Arif; Jan Hruby; Anatolii Bukivskyi; Olexander Vinijchuk; Mykola Shandura; Viktor Yakubovskyi

    2016-01-01

    The multifunctional properties of carbon nanotubes (CNTs) make them a powerful platform for unprecedented innovations in a variety of practical applications.As a result of the surging growth of nanotechnology,nanotubes present a potential problem as an environmental pollutant,and as such,an efficient method for their rapid detection must be established.Here,we propose a novel type of ionic sensor complex for detecting CNTs-an organic dye that responds sensitively and selectively to CNTs with a photoluminescent signal.The complexes are formed through Coulomb attractions between dye molecules with uncompensated charges and CNTs covered with an ionic surfactant in water.We demonstrate that the photoluminescent excitation of the dye can be transferred to the nanotubes,resulting in selective and strong amplification (up to a factor of 6) of the light emission from the excitonic levels of CNTs in the near-infrared spectral range,as experimentally observed via excitation-emission photoluminescence (PL) mapping.The chirality of the nanotubes and the type of ionic surfactant used to disperse the nanotubes both strongly affect the amplification;thus,the complexation provides sensing selectivity towards specific CNTs.Additionally,neither similar uncharged dyes nor CNTs covered with neutral surfactant form such complexes.As model organic molecules,we use a family of pelymethine dyes with an easily tailorable molecular structure and,consequently,tunable absorbance and PL characteristics.This provides us with a versatile tool for the controllable photonic and electronic engineering of an efficient probe for CNT detection.

  6. Suzuki-Miyaura, Mizoroki-Heck carbon-carbon coupling and hydrogenation reactions catalysed by PdII and RhI complexes containing cyclodiphosphazane cis-{tBuNP(OC6H4OMe-)}2

    Indian Academy of Sciences (India)

    Sasmita Mohanty; Maravanji S Balakrishna

    2010-03-01

    The catalytic activity of the palladium complex cis-[PdCl2{(tBuNP(OC6H4OMe-))2- }2] (2) containing cis-{tBuNP(OC6H4OMe-)}2 (1) in Suzuki-Miyaura and Mizoroki-Heck carbon-carbon cross coupling reactions is described. The compound 2 also displays very high activity in Mizoroki-Heck coupling reactions. The rhodium(I) complex [RhCl(COD){(tBuNP(OC6H4OMe-))2- }] (3) acts as an excellent catalyst for the hydrogenation of several terminal olefins.

  7. Mild, reversible reaction of iridium(III) amido complexes with carbon dioxide.

    Science.gov (United States)

    Dobereiner, Graham E; Wu, Jianguo; Manas, Michael G; Schley, Nathan D; Takase, Michael K; Crabtree, Robert H; Hazari, Nilay; Maseras, Feliu; Nova, Ainara

    2012-09-17

    Unlike some other Ir(III) hydrides, the aminopyridine complex [(2-NH(2)-C(5)NH(4))IrH(3)(PPh(3))(2)] (1-PPh(3)) does not insert CO(2) into the Ir-H bond. Instead 1-PPh(3) loses H(2) to form the cyclometalated species [(κ(2)-N,N-2-NH-C(5)NH(4))IrH(2)(PPh(3))(2)] (2-PPh(3)), which subsequently reacts with CO(2) to form the carbamato species [(κ(2)-O,N-2-OC(O)NH-C(5)NH(4))IrH(2)(PPh(3))(2)] (10-PPh(3)). To study the insertion of CO(2) into the Ir-N bond of the cyclometalated species, a family of compounds of the type [(κ(2)-N,N-2-NR-C(5)NH(4))IrH(2)(PR'(3))(2)] (R = H, R' = Ph (2-PPh(3)); R = H, R' = Cy (2-PCy(3)); R = Me, R' = Ph (4-PPh(3)); R = Ph, R' = Ph (5-PPh(3)); R = Ph, R' = Cy (5-PCy(3))) and the pyrimidine complex [(κ(2)-N,N-2-NH-C(4)N(2)H(3))IrH(2)(PPh(3))(2)] (6-PPh(3)) were prepared. The rate of CO(2) insertion is faster for the more nucleophilic amides. DFT studies suggest that the mechanism of insertion involves initial nucleophilic attack of the nitrogen lone pair of the amide on CO(2) to form an N-bound carbamato complex, followed by rearrangement to the O-bound species. CO(2) insertion into 1-PPh(3) is reversible in the presence of H(2) and treatment of 10-PPh(3) with H(2) regenerates 1-PPh(3), along with Ir(PPh(3))(2)H(5).

  8. An X-Ray Photoelectron Spectroscopy (XPS) Study of Activated Carbons Impregnated with Some Organocopper Complexes

    Science.gov (United States)

    1993-10-01

    organocuivre ont dte imprdgn~s & la surface du charbon activd, et la composition de la surface du charbon imprdgn6 a dt examinee par spectroscopie...F/Cu et du C/Cu a pu fitre calcule. Ii a dtd trouvd que trois de ces * complexes dtaient soit instables ou ddcomposds & la surface du charbon . Cette...surface composition analysis, there was actually a higher concentration of Cu(I) than Cu(II), the original impregnant. It has been mentioned in an

  9. Dry season limnological conditions and basin geology exhibit complex relationships with δ13C and δ15N of carbon sources in four Neotropical floodplains.

    Science.gov (United States)

    Zaia Alves, Gustavo H; Hoeinghaus, David J; Manetta, Gislaine I; Benedito, Evanilde

    2017-01-01

    Studies in freshwater ecosystems are seeking to improve understanding of carbon flow in food webs and stable isotopes have been influential in this work. However, variation in isotopic values of basal production sources could either be an asset or a hindrance depending on study objectives. We assessed the potential for basin geology and local limnological conditions to predict stable carbon and nitrogen isotope values of six carbon sources at multiple locations in four Neotropical floodplain ecosystems (Paraná, Pantanal, Araguaia, and Amazon). Limnological conditions exhibited greater variation within than among systems. δ15N differed among basins for most carbon sources, but δ13C did not (though high within-basin variability for periphyton, phytoplankton and particulate organic carbon was observed). Although δ13C and δ15N values exhibited significant correlations with some limnological factors within and among basins, those relationships differed among carbon sources. Regression trees for both carbon and nitrogen isotopes for all sources depicted complex and in some cases nested relationships, and only very limited similarity was observed among trees for different carbon sources. Although limnological conditions predicted variation in isotope values of carbon sources, we suggest the resulting models were too complex to enable mathematical corrections of source isotope values among sites based on these parameters. The importance of local conditions in determining variation in source isotope values suggest that isotopes may be useful for examining habitat use, dispersal and patch dynamics within heterogeneous floodplain ecosystems, but spatial variability in isotope values needs to be explicitly considered when testing ecosystem models of carbon flow in these systems.

  10. GLUT1-mediated selective tumor targeting with fluorine containing platinum(II) glycoconjugates.

    Science.gov (United States)

    Liu, Ran; Fu, Zheng; Zhao, Meng; Gao, Xiangqian; Li, Hong; Mi, Qian; Liu, Pengxing; Yang, Jinna; Yao, Zhi; Gao, Qingzhi

    2017-06-13

    Increased glycolysis and overexpression of glucose transporters (GLUTs) are physiological characteristics of human malignancies. Based on the so-called Warburg effect, 18flurodeoxyglucose-positron emission tomography (FDG-PET) has successfully developed as clinical modality for the diagnosis and staging of many cancers. To leverage this glucose transporter mediated metabolic disparity between normal and malignant cells, in the current report, we focus on the fluorine substituted series of glucose, mannose and galactose-conjugated (trans-R,R-cyclohexane-1,2-diamine)-2-flouromalonato-platinum(II) complexes for a comprehensive evaluation on their selective tumor targeting. Besides highly improved water solubility, these sugar-conjugates presented improved cytotoxicity than oxaliplatin in glucose tranporters (GLUTs) overexpressing cancer cell lines and exhibited no cross-resistance to cisplatin. For the highly water soluble glucose-conjugated complex (5a), two novel in vivo assessments were conducted and the results revealed that 5a was more efficacious at a lower equitoxic dose (70% MTD) than oxaliplatin (100% MTD) in HT29 xenograft model, and it was significantly more potent than oxaliplatin in leukemia-bearing DBA/2 mice as well even at equimolar dose levels (18% vs 90% MTD). GLUT inhibitor mediated cell viability analysis, GLUT1 knockdown cell line-based cytotoxicity evaluation, and platinum accumulation study demonstrated that the cellular uptake of the sugar-conjugates was regulated by GLUT1. The higher intrinsic DNA reactivity of the sugar-conjugates was confirmed by kinetic study of platinum(II)-guanosine adduct formation. The mechanistic origin of the antitumor effect of the fluorine complexes was found to be forming the bifunctional Pt-guanine-guanine (Pt-GG) intrastrand cross-links with DNA. The results provide a rationale for Warburg effect targeted anticancer drug design.

  11. Characteristics and distribution patterns of reef complexes on the carbonate platform margin in deep water areas:the western South China Sea

    Institute of Scientific and Technical Information of China (English)

    CHEN Ping; DU Xuebin; LI Xushen; WANG Yahui; LU Yongchao; ZHONG Zehong; CHEN Lei; ZUO Qianmei; MA Yiquan; WANG Chao

    2015-01-01

    As a potential oil and gas reservoir, reef complexes have been a research focus from petroleum geologists for a long time. There are favorable conditions for the development of reef complexes in the South China Sea; however, their internal structures, evolution and distribution are still poorly understood. Based on 2D and 3D seismic data, the internal structures and evolution patterns of the reef complexes on the carbonate platform margin in the deep water areas over the western South China Sea were studied in detail. The result shows that two types of reef complexes, i.e., fault controlling platform margin reef complexes and ramp reef complexes have been developed in the study area. The reef complexes have independent or continuous mound or lenticular seismic reflections, with three internal structures (i.e., aggrading, prograding and retrograding structures). There are different growth rates during the evolution of the reef complexes, resulting in the formation of catch-up reefs, keep-up reefs and quick step reefs. The study also reveals that different platform margin reef complexes have different internal structures and distributions, because of the different platform types. These results may be applied to the exploration and prediction of carbonate platform margin reef complexes in other areas that are similar to the study area.

  12. The complex environment of the bright carbon star TX Psc as probed by spectro-astrometry

    CERN Document Server

    Hron, J; Aringer, B; Klotz, D; Lebzelter, T; Paladini, C; Wiedemann, G

    2015-01-01

    Context: Stars on the asymptotic giant branch (AGB) show broad evidence of inhomogeneous atmospheres and circumstellar envelopes. These have been studied by a variety of methods on various angular scales. In this paper we explore the envelope of the well-studied carbon star TX Psc by the technique of spectro-astrometry. Aims: We explore the potential of this method for detecting asymmetries around AGB stars. Methods:We obtained CRIRES observations of several CO $\\Delta$v=1 lines near 4.6 $\\mu$m and HCN lines near 3 $\\mu$m in 2010 and 2013. These were then searched for spectro-astrometric signatures. For the interpretation of the results, we used simple simulated observations. Results: Several lines show significant photocentre shifts with a clear dependence on position angle. In all cases, tilde-shaped signatures are found where the positive and negative shifts (at PA 0deg) are associated with blue and weaker red components of the lines. The shifts can be modelled with a bright blob 70 mas to 210 mas south of...

  13. Conformational Mobility of GOx Coenzyme Complex on Single-Wall Carbon Nanotubes

    Directory of Open Access Journals (Sweden)

    Yu Kang

    2008-12-01

    Full Text Available A critical issue in bioelectrochemical applications that use electrodes modified by Single Wall Carbon Nanotubes (SWCNTs is to ensure high activity of the catalytic site of an immobilized enzyme protein interacting with nanomaterials. Since Flavin Adenine Dinucleotide (FAD, a coenzyme of glucose oxidase (GOx, is the active center of the catalytic site, conformation of which could determine the activity of enzyme, it is important to understand the dynamic mechanism of its conformational mobility while GOx is adsorbed on SWCNTs with multiple orientations. However, this dynamic mechanism still remains unclear at the atomic level due to the coenzyme being embedded in the apo-GOx and the limitations of appropriate experimental methods. In this study, a molecular dynamics (MD simulation was performed to investigate the conformational mobility mechanism of the coenzyme. The trajectory and the interaction energy clearly indicate that the adsorption of GOx onto SWCNTs plays an important role in the conformational mobility of the coenzyme, and its mobility is greatly affected by the distribution of water molecules due to it being hydrophobic.

  14. Complex mountain terrain and disturbance history drive variation in forest aboveground live carbon density in the western Oregon Cascades, USA.

    Science.gov (United States)

    Zald, Harold S J; Spies, Thomas A; Seidl, Rupert; Pabst, Robert J; Olsen, Keith A; Steel, E Ashley

    2016-04-15

    was also affected by finer scale topographic conditions associated with sheltered sites. Past wildfires only had a small influence on current ALC density, which may be a result of long times since fire and/or prevalence of non-stand replacing fire. Our results indicate that forest ALC density depends on a suite of multi-scale environmental drivers mediated by complex mountain topography, and that these relationships are dependent on stand age. The high and context-dependent spatial variability of forest ALC density has implications for quantifying forest carbon stores, establishing upper bounds of potential carbon sequestration, and scaling field data to landscape and regional scales.

  15. In vitro platelet activation, aggregation and platelet-granulocyte complex formation induced by surface modified single-walled carbon nanotubes.

    Science.gov (United States)

    Fent, János; Bihari, Péter; Vippola, Minnamari; Sarlin, Essi; Lakatos, Susan

    2015-08-01

    Surface modification of single-walled carbon nanotubes (SWCNTs) such as carboxylation, amidation, hydroxylation and pegylation is used to reduce the nanotube toxicity and render them more suitable for biomedical applications than their pristine counterparts. Toxicity can be manifested in platelet activation as it has been shown for SWCNTs. However, the effect of various surface modifications on the platelet activating potential of SWCNTs has not been tested yet. In vitro platelet activation (CD62P) as well as the platelet-granulocyte complex formation (CD15/CD41 double positivity) in human whole blood were measured by flow cytometry in the presence of 0.1mg/ml of pristine or various surface modified SWCNTs. The effect of various SWCNTs was tested by whole blood impedance aggregometry, too. All tested SWCNTs but the hydroxylated ones activate platelets and promote platelet-granulocyte complex formation in vitro. Carboxylated, pegylated and pristine SWCNTs induce whole blood aggregation as well. Although pegylation is preferred from biomedical point of view, among the samples tested by us pegylated SWCNTs induced far the most prominent activation and a well detectable aggregation of platelets in whole blood.

  16. Electro-oxidation of chlorophenols at glassy carbon electrodes modified with polyNi(II)complexes

    Energy Technology Data Exchange (ETDEWEB)

    Berrios, Cristhian [Facultad de Quimica y Biologia, Departamento de Ciencias del Ambiente, Universidad de Santiago de Chile (USACh), casilla 40, correo 33, Santiago (Chile); Marco, Jose F.; Gutierrez, Claudio [Instituto de Quimica Fisica ' Rocasolano' , CSIC, C. Serrano, 119, 28006, Madrid (Spain); Ureta-Zanartu, Maria Soledad [Facultad de Quimica y Biologia, Departamento de Ciencias del Ambiente, Universidad de Santiago de Chile (USACh), casilla 40, correo 33, Santiago (Chile)], E-mail: soledad.ureta@usach.cl

    2009-11-01

    The effect of the ligand macrocycle (phenylporphyrin (PP) or phthalocyanine (Pc)) and of the ligand substituent (-NH{sub 2} or -SO{sub 3}{sup -}) on the catalytic activity for the electro-oxidation in a pH 11 buffer electrolyte of 2- and 4-chlorophenol (2-CP and 4-CP), 2,4- and 2,6-dichlorophenol (2,4-DCP and 2,6-DCP), 2,4,6-trichlorophenol (2,4,6-TCP), and pentachlorophenol (PCP) at glassy carbon electrodes modified with electropolymerized Ni(II) macrocycles was studied. The polyphenolic residue deposited at the electrode surface was characterized by cyclic voltammetry, impedance measurements, ex situ Fourier transform infrared spectroscopy (FT-IR) and X-ray Photoelectron Spectroscopy (XPS). A band of aliphatic C=O stretching in the IR spectrum of the fouling film produced by potential cycling in 2,4,6-TCP indicated that the aromatic ring had been broken, yielding ketones, aldehydes and/or carboxylic acids. The sulphonated Ni(II) polymers, which showed the Ni(III)/Ni(II) process in the CV, had XP spectra typical of paramagnetic Ni(II), indicating that they contained Ni(OH){sub 2} clusters. On the contrary, the CVs of the amino Ni(II) did not show the Ni(III)/Ni(II) process at all, this process appearing only after previous activation by potential cycling, and only to a small extent. As was to be expected, the XP spectra of activated amino films corresponded to diamagnetic Ni(II), showing that the concentration of Ni(OH){sub 2} clusters was very small. The amino films were less active than the sulpho films for the oxidation of chlorophenols, in agreement with the lower concentration of Ni(OH){sub 2} clusters in the former films. For all electrodes the highest activity was observed for 2,4,6-TCP, since its oxidation yields a phenolic residue which is much more porous than those produced by the other CPs.

  17. Evidence for an early evolutionary emergence of γ-type carbonic anhydrases as components of mitochondrial respiratory complex I

    Directory of Open Access Journals (Sweden)

    Gray Michael W

    2010-06-01

    Full Text Available Abstract Background The complexity of mitochondrial complex I (CI; NADH:ubiquinone oxidoreductase has increased considerably relative to the homologous complex in bacteria. Comparative analyses of CI composition in animals, fungi and land plants/green algae suggest that novel components of mitochondrial CI include a set of 18 proteins common to all eukaryotes and a variable number of lineage-specific subunits. In plants and green algae, several purportedly plant-specific proteins homologous to γ-type carbonic anhydrases (γCA have been identified as components of CI. However, relatively little is known about CI composition in the unicellular protists, the characterizations of which are essential to our understanding of CI evolution. Results We have performed a tandem mass spectrometric characterization of CI from the amoeboid protozoon Acanthamoeba castellanii. Among the proteins identified were two γCA homologs, AcCa1 and AcCa2, demonstrating that γCA proteins are not specific to plants/green algae. In fact, through bioinformatics searches we detected γCA homologs in diverse protist lineages, and several of these homologs are predicted to possess N-terminal mitochondrial targeting peptides. Conclusions The detection of γCAs in CI of Acanthamoeba, considered to be a closer relative of animals and fungi than plants, suggests that γCA proteins may have been an ancestral feature of mitochondrial CI, rather than a novel, plant-specific addition. This assertion is supported by the presence of genes encoding γCAs in the nuclear genomes of a wide variety of eukaryotes. Together, these findings emphasize the importance of a phylogenetically broad characterization of CI for elucidating CI evolution in eukaryotes.

  18. Coupling of Carbon Dioxide with Epoxides Efficiently Catalyzed by Thioether-Triphenolate Bimetallic Iron(III) Complexes: Catalyst Structure-Reactivity Relationship and Mechanistic DFT Study

    KAUST Repository

    Della Monica, Francesco

    2016-08-25

    A series of dinuclear iron(III)I complexes supported by thioether-triphenolate ligands have been prepared to attain highly Lewis acidic catalysts. In combination with tetrabutylammonium bromide (TBAB) they are highly active catalysts in the synthesis of cyclic organic carbonates through the coupling of carbon dioxide to epoxides with the highest initial turnover frequencies reported to date for the conversion of propylene oxide to propylene carbonate for iron-based catalysts (5200h-1; 120°C, 2MPa, 1h). In particular, these complexes are shown to be highly selective catalysts for the coupling of carbon dioxide to internal oxiranes affording the corresponding cyclic carbonates in good yield and with retention of the initial stereochemical configuration. A density functional theory (DFT) investigation provides a rational for the relative high activity found for these Fe(III) complexes, showing the fundamental role of the hemilabile sulfur atom in the ligand skeleton to promote reactivity. Notably, in spite of the dinuclear nature of the catalyst precursor only one metal center is involved in the catalytic cycle. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  19. Amazon Rainforest Exchange of Carbon and Subcanopy Air Flow: Manaus LBA Site—A Complex Terrain Condition

    Directory of Open Access Journals (Sweden)

    Julio Tóta

    2012-01-01

    Full Text Available On the moderately complex terrain covered by dense tropical Amazon Rainforest (Reserva Biologica do Cuieiras—ZF2—02°36′17.1′′ S, 60°12′24.4′′ W, subcanopy horizontal and vertical gradients of the air temperature, CO2 concentration and wind field were measured for the dry and wet periods in 2006. We tested the hypothesis that horizontal drainage flow over this study area is significant and can affect the interpretation of the high carbon uptake rates reported by previous works at this site. A similar experimental design as the one by Tóta et al. (2008 was used with a network of wind, air temperature, and CO2 sensors above and below the forest canopy. A persistent and systematic subcanopy nighttime upslope (positive buoyancy and daytime downslope (negative buoyancy flow pattern on a moderately inclined slope (12% was observed. The microcirculations observed above the canopy (38 m over the sloping area during nighttime presents a downward motion indicating vertical convergence and correspondent horizontal divergence toward the valley area. During the daytime an inverse pattern was observed. The micro-circulations above the canopy were driven mainly by buoyancy balancing the pressure gradient forces. In the subcanopy space the microcirculations were also driven by the same physical mechanisms but probably with the stress forcing contribution. The results also indicated that the horizontal and vertical scalar gradients (e.g., CO2 were modulated by these micro-circulations above and below the canopy, suggesting that estimates of advection using previous experimental approaches are not appropriate due to the tridimensional nature of the vertical and horizontal transport locally. This work also indicates that carbon budget from tower-based measurement is not enough to close the system, and one needs to include horizontal and vertical advection transport of CO2 into those estimates.

  20. Complex effects of fertilization on plant and herbivore performance in the presence of a plant competitor and activated carbon.

    Directory of Open Access Journals (Sweden)

    Nafiseh Mahdavi-Arab

    Full Text Available Plant-herbivore interactions are influenced by host plant quality which in turn is affected by plant growth conditions. Competition is the major biotic and nutrient availability a major abiotic component of a plant's growth environment. Yet, surprisingly few studies have investigated impacts of competition and nutrient availability on herbivore performance and reciprocal herbivore effects on plants. We studied growth of the specialist aphid, Macrosiphoniella tanacetaria, and its host plant tansy, Tanacetum vulgare, under experimental addition of inorganic and organic fertilizer crossed with competition by goldenrod, Solidago canadensis. Because of evidence that competition by goldenrod is mediated by allelopathic compounds, we also added a treatment with activated carbon. Results showed that fertilization increased, and competition with goldenrod decreased, plant biomass, but this was likely mediated by resource competition. There was no evidence from the activated carbon treatment that allelopathy played a role which instead had a fertilizing effect. Aphid performance increased with higher plant biomass and depended on plant growth conditions, with fertilization and AC increasing, and plant competition decreasing aphid numbers. Feedbacks of aphids on plant performance interacted with plant growth conditions in complex ways depending on the relative magnitude of the effects on plant biomass and aphid numbers. In the basic fertilization treatment, tansy plants profited from increased nutrient availability by accumulating more biomass than they lost due to an increased number of aphids under fertilization. When adding additional fertilizer, aphid numbers increased so high that tansy plants suffered and showed reduced biomass compared with controls without aphids. Thus, the ecological cost of an infestation with aphids depends on the balance of effects of growth conditions on plant and herbivore performance. These results emphasize the importance

  1. Complex effects of fertilization on plant and herbivore performance in the presence of a plant competitor and activated carbon.

    Science.gov (United States)

    Mahdavi-Arab, Nafiseh; Meyer, Sebastian T; Mehrparvar, Mohsen; Weisser, Wolfgang W

    2014-01-01

    Plant-herbivore interactions are influenced by host plant quality which in turn is affected by plant growth conditions. Competition is the major biotic and nutrient availability a major abiotic component of a plant's growth environment. Yet, surprisingly few studies have investigated impacts of competition and nutrient availability on herbivore performance and reciprocal herbivore effects on plants. We studied growth of the specialist aphid, Macrosiphoniella tanacetaria, and its host plant tansy, Tanacetum vulgare, under experimental addition of inorganic and organic fertilizer crossed with competition by goldenrod, Solidago canadensis. Because of evidence that competition by goldenrod is mediated by allelopathic compounds, we also added a treatment with activated carbon. Results showed that fertilization increased, and competition with goldenrod decreased, plant biomass, but this was likely mediated by resource competition. There was no evidence from the activated carbon treatment that allelopathy played a role which instead had a fertilizing effect. Aphid performance increased with higher plant biomass and depended on plant growth conditions, with fertilization and AC increasing, and plant competition decreasing aphid numbers. Feedbacks of aphids on plant performance interacted with plant growth conditions in complex ways depending on the relative magnitude of the effects on plant biomass and aphid numbers. In the basic fertilization treatment, tansy plants profited from increased nutrient availability by accumulating more biomass than they lost due to an increased number of aphids under fertilization. When adding additional fertilizer, aphid numbers increased so high that tansy plants suffered and showed reduced biomass compared with controls without aphids. Thus, the ecological cost of an infestation with aphids depends on the balance of effects of growth conditions on plant and herbivore performance. These results emphasize the importance to investigate both

  2. Synthesis of isocoumarins through three-component couplings of arynes, terminal alkynes, and carbon dioxide catalyzed by an NHC-copper complex.

    Science.gov (United States)

    Yoo, Woo-Jin; Nguyen, Thanh V Q; Kobayashi, Shū

    2014-09-15

    A copper-catalyzed multicomponent coupling reaction between in situ generated ortho-arynes, terminal alkynes, and carbon dioxide was developed to access isocoumarins in moderate to good yields. The key to this CO2-incorporating reaction was the use of a versatile N-heterocyclic carbene/copper complex that was able to catalyze multiple transformations within the three-component reaction.

  3. Synthesis, characterization, antimicrobial activity and carbonic anhydrase enzyme inhibitor effects of salicilaldehyde-N-methyl p-toluenesulfonylhydrazone and its Palladium(II), Cobalt(II) complexes

    Science.gov (United States)

    Alyar, Saliha; Adem, Şevki

    2014-10-01

    We report the synthesis of the ligand, salicilaldehyde-N-methyl p-toluenesulfonylhydrazone (salptsmh) derived from p-toluenesulfonicacid-1-methylhydrazide (ptsmh) and its Pd(II) and Co(II) metal complexes were synthesized for the first time. The structure of the ligand and their complexes were investigated using elemental analysis, magnetic susceptibility, molar conductance and spectral (IR, NMR and LC-MS) measurements. Salptsmh has also been characterized by single crystal X-ray diffraction. 1H and 13C shielding tensors for crystal structure were calculated with GIAO/DFT/B3LYP/6-311++G(d,p) methods in CDCl3. The complexes were found to have general composition [ML2]. The results of elemental analysis showed 1:2 (metal/ligand) stoichiometry for all the complex. Magnetic and spectral data indicate a square planar geometry for Pd(II) complex and a distorted tetrahedral geometry for Co(II) complexes. The ligand and its metal chelates have been screened for their antimicrobial activities using the disk diffusion method against the selected Gram positive bacteria: Bacillus subtilis, Bacillus cereus, Staphylococcus aureus, Enterococcus faecalis, Gram negative bacteria: Eschericha coli, Pseudomonas aeruginosa, Klebsiella pneumonia. The inhibition activities of these compounds on carbonic anhydrase II (CA II) and carbonic anhydrase I (CA I) have been investigated by comparing IC50 and Ki values and it has been found that Pd(II) complex have more enzyme inhibition efficiency than salptsmh and Co(II) complex.

  4. Complexes with biologically active ligands. Part 11. Synthesis and carbonic anhydrase inhibitory activity of metal complexes of 4,5-disubstituted-3-mercapto-1,2,4-triazole derivatives.

    Science.gov (United States)

    Scozzafava, A; Cavazza, C; Supuran, C T; Saramet, I; Briganti, F; Banciu, M D

    1998-01-01

    Complexes containing five 4,5-disubstituted-3-mercapto-1,2,4-triazoles and Zn(II), Hg(II) and Cu(I) were synthesized and characterized by standard procedures (elemental analysis; IR, electronic and NMR spectroscopy, conductimetry and TG analysis). Both the thione as well as the thiolate forms of the ligands were evidenced to interact with the metal ions in the prepared complexes. The original mercaptans and their metal complexes behave as inhibitors of three carbonic anhydrase (CA) isozymes, CA I, II and IV, but did not lower intraocular pressure in rabbits in animal models of glaucoma.

  5. Complexes With Biologically Active Ligands. Part 111. Synthesis and Carbonic Anhydrase Inhibitory Activity of Metal Complexes of 4,5-Disubstituted-3-Mercapto-1,2,4-Triazole Derivatives

    Science.gov (United States)

    Scozzafava, Andrea; Cavazza, Christine; Saramet, Ioana; Briganti, Fabrizio; Banciu, Mircea D.

    1998-01-01

    Complexes containing five 4,5-disubstituted-3-mercapto-1,2,4-triazoles and Zn(II), Hg(II) and Cu(I) were synthesized and characterized by standard procedures (elemental analysis; IR, electronic and NMR spectroscopy, conductimetry and TG analysis). Both the thione as well as the thiolate forms of the ligands were evidenced to interact with the metal ions in the prepared complexes. The original mercaptans and their metal complexes behave as inhibitors of three carbonic anhydrase (CA) isozymes, CA I, II and IV, but did not lower intraocular pressure in rabbits in animal models of glaucoma. PMID:18475819

  6. Reservoir Modeling of Carbonate on Fika Field: The Challenge to Capture the Complexity of Rock and Oil Types

    Directory of Open Access Journals (Sweden)

    Erawati Fitriyani Adji

    2014-09-01

    Full Text Available DOI: 10.17014/ijog.v1i2.181The carbonate on Fika Field has a special character, because it grew above a basement high with the thickness and internal character variation. To develop the field, a proper geological model which can be used in reservoir simulation was needed. This model has to represent the complexity of the rock type and the variety of oil types among the clusters. Creating this model was challenging due to the heterogeneity of the Baturaja Formation (BRF: Early Miocene reef, carbonate platform, and breccia conglomerate grew up above the basement with a variety of thickness and quality distributions. The reservoir thickness varies between 23 - 600 ft and 3D seismic frequency ranges from 1 - 80 Hz with 25 Hz dominant frequency. Structurally, the Fika Field has a high basement slope, which has an impact on the flow unit layering slope. Based on production data, each area shows different characteristics and performance: some areas have high water cut and low cumulative production. Oil properties from several clusters also vary in wax content. The wax content can potentially build up a deposit inside tubing and flow-line, resulted in a possible disturbance to the operation. Five well cores were analyzed, including thin section and XRD. Seven check-shot data and 3D seismic Pre-Stack Time Migration (PSTM were available with limited seismic resolution. A seismic analysis was done after well seismic tie was completed. This analysis included paleogeography, depth structure map, and distribution of reservoir and basement. Core and log data generated facies carbonate distribution and rock typing, defining properties for log analysis and permeability prediction for each zone. An Sw prediction for each well was created by J-function analysis. This elaborates capillary pressure from core data, so it is very similar to the real conditions. Different stages of the initial model were done i.e. scale-up properties, data analysis, variogram modeling

  7. Electrocatalytic oxidation of 2-mercaptoethanol using modified glassy carbon electrode by MWCNT in combination with unsymmetrical manganese (II) Schiff base complexes

    Energy Technology Data Exchange (ETDEWEB)

    Mohebbi, Sajjad, E-mail: smohebbi@uok.ac.ir; Eslami, Saadat

    2015-06-15

    Highlights: • High electocatalytic efficiency and stability of modified hybrid electrode GC/MWCNTs/MnSaloph. • Direct reflection of catalytic activity of manganese complexes on electrocatalytic oxidation of 2-ME. • Decreasing overpotential and increasing catalytic peak current toward oxidation of 2-ME. • Deposition of range of novel substituted N{sub 2}O{sub 2} Saloph complexes of manganese(II) on GCE/MWCNT. • Enhancement of electrocatalytic oxidation activity upon electron donating substitutions on the Saloph. - Abstract: The performance of modified hybrid glassy carbon electrode with composite of carbon nanotubes and manganese complexes for the electrocatalytic oxidation of 2-mercaptoethanol is developed. GC electrode was modified using MWCNT and new N{sub 2}O{sub 2} unsymmetrical tetradentate Schiff base complexes of manganese namely Manganese Saloph complexes 1-5, with general formula Mn[(5-x-4-y-Sal)(5-x′-4-y′-Sal) Ph], where x, x′ = H, Br, NO{sub 2} and y, y′ = H, MeO. Direct immobilization of CNT on the surface of GCE is performed by abrasive immobilization, and then modified by manganese(II) complexes via direct deposition method. These novel modified electrodes clearly demonstrate the necessity of modifying bare carbon electrodes to endow them with the desired behavior and were identified by HRTEM. Also complexes were characterized by elemental analyses, MS, UV–vis and IR spectroscopy. Modified hybrid GC/MWCNT/MnSaloph electrode exhibits strong and stable electrocatalytic activity towards the electrooxidation of 2-mercaptoethanol molecules in comparison with bare glassy carbon electrode with advantages of very low over potential and high catalytic current. Such ability promotes the thiol’s electron transfer reaction. Also, electron withdrawing substituent on the Saloph was enhanced electrocatalytic oxidation activity.

  8. Transition Metal Complexes Coordinated by Water Soluble Phosphane Ligands: How Cyclodextrins Can Alter the Coordination Sphere?

    Directory of Open Access Journals (Sweden)

    Michel Ferreira

    2017-01-01

    Full Text Available The behaviour of platinum(II and palladium(0 complexes coordinated by various hydrosoluble monodentate phosphane ligands has been investigated by 31P{1H} NMR spectroscopy in the presence of randomly methylated β-cyclodextrin (RAME-β-CD. This molecular receptor can have no impact on the organometallic complexes, induce the formation of phosphane low-coordinated complexes or form coordination second sphere species. These three behaviours are under thermodynamic control and are governed not only by the affinity of RAME-β-CD for the phosphane but also by the phosphane stereoelectronic properties. When observed, the low-coordinated complexes may be formed either via a preliminary decoordination of the phosphane followed by a complexation of the free ligand by the CD or via the generation of organometallic species complexed by CD which then lead to expulsion of ligands to decrease their internal steric hindrance.

  9. Selection, characterisation and mapping of complex electrochemical processes at individual single-walled carbon nanotubes: the case of serotonin oxidation.

    Science.gov (United States)

    Güell, Aleix G; Meadows, Katherine E; Dudin, Petr V; Ebejer, Neil; Byers, Joshua C; Macpherson, Julie V; Unwin, Patrick R

    2014-01-01

    The electrochemical (EC) oxidation of the neurotransmitter, serotonin, at individual single-walled carbon nanotubes (SWNTs) is investigated at high resolution using a novel platform that combines flow-aligned SWNTs with atomic force microscopy, Raman microscopy, electronic conductance measurements, individual SWNT electrochemistry and high-resolution scanning electrochemical cell microscopy (SECCM). SECCM has been used to visualise the EC activity along side-wall sections of metallic SWNTs to assess the extent to which side-walls promote the electrochemistry of this complex multi-step process. Uniform and high EC activity is observed that is consistent with significant reaction at the side-wall, rather than electrochemistry being driven by defects alone. By scanning forward and reverse (trace and retrace) over the same region of a SWNT, it is also possible to assess any blocking of EC activity by serotonin oxidation reaction products. At a physiologically relevant concentration (5 μM), there is no detectable blocking of SWNTs, which can be attributed, at least in part, to the high diffusion rate to an individual, isolated SWNT in the SECCM format. At higher serotonin concentration (2 mM), oligomer formation from oxidation products is much more significant and major blocking of the EC process is observed from line profiles recorded as the SECCM meniscus moves over an SWNT. The SECCM line profile morphology is shown to be highly diagnostic of whether blocking occurs during EC processes. The studies herein add to a growing body of evidence that various EC processes at SWNTs, from simple outer sphere redox reactions to complex multi-step processes, occur readily at pristine SWNTs. The platform described is of general applicability to various types of nanostructures and nanowires.

  10. The role of canopy hydrological diversity and complexity on water balance and carbon sequestration during dry conditions: a modeling study

    Science.gov (United States)

    Lin, L.; Stewart, A.; Band, L. E.

    2016-12-01

    The importance and influence of forest to catchment hydrology have been well recognized. In the South Eastern U.S., Chapel Hill, NC, evapotranspiration by forest dominates almost 80% of the annual precipitation in long term average. Stomatal conductivity varies by tree species and its response to dry condition differently between evergreen and deciduous, and within their phonology groups. In this study, we simulated the catchment hydrology and forest ecosystem at a local catchment, Cane Creek, in the Chapel Hill triangle area using a spatially distributed, process-based hydro-ecological model, RHESSys. We incorporated characteristics of individual tree species to represent high hydrological diversity (e.g., maple, oak, pine), which has been modeled as either evergreen or deciduous (low hydrological diversity) in many studies. With tree species specifically modeled, we were able to investigate the role of tree species diversity and complexity on catchment hydrology. Local forest plant diversity, size, and density were provided by the U.S. Forest Services FIA, and tree species physiological parameters were obtained through researches at Duke Forest. High hydrological diversity canopy has higher water use and carbon sequestration than low hydrological diversity canopy. This result supports the optimality theory that emergent vegetation pattern in landscape maximizes ecosystem productivity and water use efficiency. Previous study emphasized this emergent pattern in terms of vegetation density along the hillslope gradient, and we further emphasized the emergent pattern in terms of hydrological diversity in this study.

  11. (Co-)solvent selection for single-wall carbon nanotubes: best solvents, acids, superacids and guest-host inclusion complexes.

    Science.gov (United States)

    Torrens, Francisco; Castellano, Gloria

    2011-06-01

    Analysis of 1-octanol-water, cyclohexane-water and chloroform (CHCl(3))-water partition coefficients P(o-ch-cf) allows calculation of molecular lipophilicity patterns, which show that for a given atom log P(o-ch-cf) is sensitive to the presence of functional groups. Program CDHI does not properly differentiate between non-equivalent atoms. The most abundant single-wall carbon nanotube (SWNT), (10,10), presents a relatively small aqueous solubility and large elementary polarizability, P(o-ch-cf) and kinetic stability. The SWNT solubility is studied in various solvents, finding a class of non-hydrogen-bonding Lewis bases with good solubility. Solvents group into three classes. The SWNTs in some organic solvents are cationic while in water/Triton X mixture are anionic. Categorized solubility is semiquantitatively correlated with solvent parameters. The coefficient of term β is positive while the ones of ε and V negative. The electron affinity of d-glucopyranoses (d-Glcp(n)) suggests the formation of colloids of anionic SWNTs in water. Dipole moment for d-Glcp(n)-linear increases with n until four in agreement with 18-fold helix. The I(n)(z-) and SWNT(-) are proposed to form inclusion complexes with cyclodextrin (CD) and amylose (Amy). Starch, d-Glcp, CD and Amy are proposed as SWNT co-solvents. Guests-hosts are unperturbed. A central channel expansion is suggested.

  12. Cooperative effect by monopodal silica-supported niobium com-plexes pairs enhancing catalytic cyclic carbonate production

    KAUST Repository

    D'Elia, Valerio

    2015-05-07

    Recent discoveries highlighted the activity and the intriguing mechanistic features of NbCl5 as a molecular catalyst for the cycloaddition of CO2 and epoxides under ambient conditions. This has inspired the preparation of novel silica supported Nb-species by reacting a molecular niobium precursor [NbCl5•OEt2] with silica dehydroxylated at 700 °C (SiO2-700) or at 200 oC (SiO2-200) to generate diverse surface complexes. The product of the reaction between SiO2-700 and [NbCl5•OEt2] was identified as a monopodal supported surface species [≡SiONbCl4•OEt2] (1a). The reactions of SiO2-200 with the niobium precursor, according to two different protocols, generated surface complexes 2a and 3a presenting significant, but different, populations of the monopodal surface complex along with bipodal [(≡SiO)2NbCl3•OEt2]. 93Nb SSNMR spectra of 1a-3a and 31P SSNMR on their PMe3 derivatives (1b-3b) led to the unambiguous assignment of 1a as a single site, monopodal Nb-species while 2a and 3a were found to present two distinct surface-supported components, with 2a being mostly monopodal [≡SiONbCl4•OEt2] and 3a being mostly bipodal [≡S ONbCl3•OEt2]. Double-quantum/single-quantum 31P NMR correlation experiment carried out on 2b supported the existence of vicinal Nb centers on the silica surface for this species. 1a-3a were active heterogeneous catalysts for the synthesis of propylene carbonate from CO2 and propylene oxide under mild catalytic conditions; the performance of 2a was found to significantly surpass that of 1a and 3a. With the support of a systematic DFT study carried out on model silica surfaces, the observed differences in catalytic efficiency were correlated with an unprece-dented cooperative effect between two neighboring Nb centers on the surface of 2a. This is in an excellent agreement with our previous discoveries regarding the mechanism of the NbCl5 catalyzed cycloaddition in the homogeneous phase.

  13. Enantioselective Michael reaction catalyzed by well-defined chiral ru amido complexes: isolation and characterization of the catalyst intermediate, ru malonato complex having a metal-carbon bond.

    Science.gov (United States)

    Watanabe, Masahito; Murata, Kunihiko; Ikariya, Takao

    2003-06-25

    Chiral Ru amido complexes promote asymmetric Michael addition of malonates to cyclic enones, leading to Michael adducts with excellent ee's, in which the chiral Ru amido complexes react with malonates to give isolable catalyst intermediates, chiral Ru malonato complexes bearing a metal bound C-nucleophile.

  14. MEDUSA-2.0: an intermediate complexity biogeochemical model of the marine carbon cycle for climate change and ocean acidification studies

    Directory of Open Access Journals (Sweden)

    A. Yool

    2013-02-01

    Full Text Available MEDUSA-1.0 (Model of Ecosystem Dynamics, nutrient Utilisation, Sequestration and Acidification was developed as an "intermediate complexity" plankton ecosystem model to study the biogeochemical response, and especially that of the so-called "biological pump", to anthropogenically-driven change in the World Ocean (Yool et al., 2011. The base currency in this model was nitrogen from which fluxes of organic carbon, including export to the deep ocean, were calculated by invoking fixed C:N ratios in phytoplankton, zooplankton and detritus. Since the beginning of the industrial era, the atmospheric concentration of carbon dioxide (CO2 has significantly increased above its natural, inter-glacial background concentration. Simulating and predicting the carbon cycle in the ocean in its entirety, including ventilation of CO2 with the atmosphere and the resulting impact of ocean acidification on marine ecosystems, therefore requires that both organic and inorganic carbon be afforded a full representation in the model specification. Here, we introduce MEDUSA-2.0, an expanded successor model which includes additional state variables for dissolved inorganic carbon, alkalinity, dissolved oxygen and detritus carbon (permitting variable C:N in exported organic matter, as well as a simple benthic formulation and extended parameterisations of phytoplankton growth, calcification and detritus remineralisation. A full description of MEDUSA-2.0, including its additional functionality, is provided and a multi-decadal hindcast simulation described (1860–2005, to evaluate the biogeochemical performance of the model.

  15. Platform margins, reef facies, and microbial carbonates; a comparison of Devonian reef complexes in the Canning Basin, Western Australia, and the Guilin region, South China

    Science.gov (United States)

    Shen, Jian-Wei; Webb, Gregory E.; Jell, John S.

    2008-05-01

    Devonian reef complexes were well developed in Western Australia and South China, but no detailed direct comparison has been made between reef building in the two regions. The regions differ in several respects, including tectonic, stratigraphic and palaeoceanographic-palaeogeographic settings, and the reef building styles reflect minor differences in reef builders and reef facies. Similarities and differences between the two reef complexes provide insights into the characteristics of platform margins, reef facies and microbial carbonates of both regions. Here we present a comparison of platform margin types from different stratigraphic positions in the Late Devonian reef complex of the Canning Basin, Western Australia and Middle and Late Devonian margin to marginal slope successions in Guilin, South China. Comparisons are integrated into a review of the reefal stratigraphy of both regions. Reef facies, reef complex architecture, temporal reef builder associations, 2nd order stratigraphy and platform cyclicity in the two regions were generally similar where the successions overlap temporally. However, carbonate deposition began earlier in South China. Carbonate complexes were also more widespread in South China and represent a thicker succession overall. Platforms in the Canning Basin grew directly on Precambrian crystalline basement or early Palaeozoic sedimentary rocks, but in South China, carbonate complexes developed conformably on older Devonian siliciclastic strata. Pre-Frasnian reef facies in South China had more abundant skeletal frameworks than in Canning Basin reefs of equivalent age, and Famennian shoaling margins containing various microbial reefs may have been more common and probably more diverse in South China. However, Late Devonian platform margin types have been documented more completely in the Canning Basin. Deep intra-platform troughs (deep depressions containing non-carbonate pelagic sediments — Nandan-type successions) that developed along

  16. Tumor Acidity-Induced Sheddable Polyethylenimine-Poly(trimethylene carbonate)/DNA/Polyethylene Glycol-2,3-Dimethylmaleicanhydride Ternary Complex for Efficient and Safe Gene Delivery.

    Science.gov (United States)

    Zhao, Caiyan; Shao, Leihou; Lu, Jianqing; Deng, Xiongwei; Wu, Yan

    2016-03-01

    Amphiphilic PEI derivatives/DNA complexes are widely used for DNA delivery, but they are unstable in vivo and have cytotoxicity due to the excess cationic charge. PEGylation of cationic complexes can improve sterical stability and biocompatibility. However, PEGylation significantly inhibits cellular uptake and endosomal escape. In this work, sheddable ternary complexes were developed by coating a tumor acidity-sensitive β-carboxylic amide functionalized PEG layer on the binary complexes of amphiphilic cationic polyethylenimine-poly(trimethylene carbonate) nanoparticles/DNA (PEI-PTMC/DNA). Such sheddable ternary complexes markedly reduced their nonspecific interactions with serum protein in the bloodstream and obtained minimal cytotoxicity due to the protection of the PEG shell. At the tumor site, the PEG layer was deshielded by responding to the tumor acidic microenvironment and the positively charged complexes re-exposed that had higher affinity with negatively charged cell membranes. Meanwhile the positively charged complexes facilitated endosomal escape. Accordingly, this delivery system improved the biocompatibility of gene-loaded complexes and enhanced the gene transfection efficiency. Such PEGylated complexes with the ability to deshield the PEG layer at the target tissues hold great promise for efficient and safe gene delivery in vivo.

  17. Low temperature in situ synthesis and the formation mechanism of various carbon-encapsulated nanocrystals by the electrophilic oxidation of metallocene complexes.

    Science.gov (United States)

    Liu, Boyang; Fan, Chunhua; Chen, Jianwei; Wang, Junhua; Lu, Zepeng; Ren, Jiayuan; Yu, Shuaiqin; Dong, Lihua; Li, Wenge

    2016-02-19

    The core-shell nanostructures have the advantages of combining distinctive properties of varied materials and improved properties over their single-component counterparts. Synthesis approaches for this class of nanostructures have been intensively explored, generally involving multiple steps. Here, a general and convenient strategy is developed for one-step in situ synthesis of various carbon-encapsulated nanocrystals with a core-shell structure via a solid-state reaction of metallocene complexes with (NH4)2S2O8 in an autoclave at 200 °C. A variety of near-spherical and equiaxed nanocrystals with a small median size ranging from 6.5 to 50.6 nm are prepared as inner cores, including Fe7S8, Ni3S4 and NiS, CoS, TiO2, TiO2 and S8, ZrO2, (NH4)3V(SO4)3 and VO2, Fe7S8 and Fe3O4, MoS2 and MoO2. The worm-like carbon shell provides exclusive room for hundreds of nanocrystals separated from each other, preventing nanocrystal aggregation. The synergistic effect of ammonium and a strong oxidizing anion on the electrophilic oxidation of metallocene complexes containing a metal-ligand π bond contributes to the carbon formation at low temperature. It is considered that the cyclopentadienyl ligand in a metallocene complex will decompose into highly reactive straight chain olefinic pieces and the metal-olefin π interaction enables an ordered self-assembly of olefinic pieces on nanocrystals to partially form graphitizable carbon and a core-shell structure. The high capacity, good cycling behavior and rate capability of Fe7S8@C and Ni3S4 and NiS@C electrodes are attributed to the good protection and electrical conductivity of the carbon shell.

  18. Evolution of chemical and isotopic composition of inorganic carbon in a complex semi-arid zone environment: Consequences for groundwater dating using radiocarbon

    Science.gov (United States)

    Meredith, K. T.; Han, L. F.; Hollins, S. E.; Cendón, D. I.; Jacobsen, G. E.; Baker, A.

    2016-09-01

    Estimating groundwater age is important for any groundwater resource assessment and radiocarbon (14C) dating of dissolved inorganic carbon (DIC) can provide this information. In semi-arid zone (i.e. water-limited environments), there are a multitude of reasons why 14C dating of groundwater and traditional correction models may not be directly transferable. Some include; (1) the complex hydrological responses of these systems that lead to a mixture of different ages in the aquifer(s), (2) the varied sources, origins and ages of organic matter in the unsaturated zone and (3) high evaporation rates. These all influence the evolution of DIC and are not easily accounted for in traditional correction models. In this study, we determined carbon isotope data for; DIC in water, carbonate minerals in the sediments, sediment organic matter, soil gas CO2 from the unsaturated zone, and vegetation samples. The samples were collected after an extended drought, and again after a flood event, to capture the evolution of DIC after varying hydrological regimes. A graphical method (Han et al., 2012) was applied for interpretation of the carbon geochemical and isotopic data. Simple forward mass-balance modelling was carried out on key geochemical processes involving carbon and agreed well with observed data. High values of DIC and δ13CDIC, and low 14CDIC could not be explained by a simple carbonate mineral-CO2 gas dissolution process. Instead it is suggested that during extended drought, water-sediment interaction leads to ion exchange processes within the top ∼10-20 m of the aquifer which promotes greater calcite dissolution in saline groundwater. This process was found to contribute more than half of the DIC, which is from a mostly 'dead' carbon source. DIC is also influenced by carbon exchange between DIC in water and carbonate minerals found in the top 2 m of the unsaturated zone. This process occurs because of repeated dissolution/precipitation of carbonate that is dependent on

  19. The morphology of Al-Ti-O complex oxide inclusions formed in an ultra low-carbon steel melt during the RH process

    Science.gov (United States)

    Doo, Won-Chul; Kim, Dong-Yong; Kang, Soo-Chang; Yi, Kyung-Woo

    2007-06-01

    Internal morphologies of bulk shape oxides in a melt of Ti bearing low-carbon steel were analyzed. The outer shapes of nearly spherical inclusions containing Ti were quite different from the shape of alumina inclusions that typically have a cluster form. A cross-section investigation using a polishing method and the FIB method revealed that the TiOx-Al2O3 complex oxide covers alumina clusters and that the interfaces of the alumina and complex oxide are modified as time passes.

  20. Recyclability of water-soluble ruthenium–phosphine complex catalysts in multiphase selective hydrogenation of cinnamaldehyde using toluene and pressurized carbon dioxide

    OpenAIRE

    Fujita, Shin-ichiro; Akihara, Shuji; Arai, Masahiko

    2006-01-01

    The recyclability of water-soluble ruthenium–phosphine complex catalysts was investigated in water–toluene and in water–pressurized carbon dioxide systems for selective hydrogenation of trans-cinnamaldehyde (CAL). For the first hydrogenation run, the selectivity for cinnamyl alcohol (COL) is high for both toluene and dense CO2, because of interfacial catalysis in which the reaction mainly occurs at the interface between the aqueous phase and the other toluene or dense CO2 phase. The total CAL...

  1. A new platinum complex with tryptophan: synthesis, structural characterization, DFT studies and biological assays in vitro over human tumorigenic cells.

    Science.gov (United States)

    Carvalho, Marcos A; Shishido, Silvia M; Souza, Bárbara C; de Paiva, Raphael E F; Gomes, Alexandre F; Gozzo, Fábio C; Formiga, André L B; Corbi, Pedro P

    2014-03-25

    A new platinum(II) complex with the amino acid L-tryptophan (trp), named Pt-trp, was synthesized and characterized. Elemental, thermogravimetric and ESI-QTOF mass spectrometric analyses led to the composition [Pt(C11H11N2O2)2]⋅6H2O. Infrared spectroscopic data indicate the coordination of trp to Pt(II) through the oxygen of the carboxylate group and also through the nitrogen atom of the amino group. The (13)C CP/MAS NMR spectroscopic data confirm coordination through the oxygen atom of the carboxylate group, while the (15)N CP/MAS NMR data confirm coordination of the nitrogen of the NH2 group to the metal. Density functional theory (DFT) studies were applied to evaluate the cis and trans coordination modes of trp to platinum(II). The trans isomer was shown to be energetically more stable than the cis one. The Pt-trp complex was evaluated as a cytotoxic agent against SK-Mel 103 (human melanoma) and Panc-1 (human pancreatic carcinoma) cell lines. The complex was shown to be cytotoxic over the considered cells.

  2. Combining anti-cancer drugs with artificial sweeteners: synthesis and anti-cancer activity of saccharinate (sac) and thiosaccharinate (tsac) complexes cis-[Pt(sac)2(NH3)2] and cis-[Pt(tsac)2(NH3)2].

    Science.gov (United States)

    Al-Jibori, Subhi A; Al-Jibori, Ghassan H; Al-Hayaly, Lamaan J; Wagner, Christoph; Schmidt, Harry; Timur, Suna; Baris Barlas, F; Subasi, Elif; Ghosh, Shishir; Hogarth, Graeme

    2014-12-01

    The new platinum(II) complexes cis-[Pt(sac)2(NH3)2] (sac=saccharinate) and cis-[Pt(tsac)2(NH3)2] (tsac=thiosaccharinate) have been prepared, the X-ray crystal structure of cis-[Pt(sac)2(NH3)2] x H2O reveals that both saccharinate anions are N-bound in a cis-arrangement being inequivalent in both the solid-state and in solution at room temperature. Preliminary anti-cancer activity has been assessed against A549 human alveolar type-II like cell lines with the thiosaccharinate complex showing good activity.

  3. Quinoxaline-2-carboxamide as a carrier ligand in two new platinum(II) compounds: Synthesis, crystal structure, cytotoxic activity and DNA interaction.

    Science.gov (United States)

    Marqués-Gallego, Patricia; Gamiz-Gonzalez, M Amparo; Fortea-Pérez, Francisco R; Lutz, Martin; Spek, Anthony L; Pevec, Andrej; Kozlevčar, Bojan; Reedijk, Jan

    2010-06-01

    The search for platinum compounds structurally different from cisplatin has led to two new platinum(II) compounds containing quinoxaline-2-carboxamide as a carrier ligand, i.e. cis-[Pt(qnxca)(MeCN)Cl2] (1) and the [Pt(qnxca-H)(dmso)Cl] (2). Both compounds have been synthesized and characterized using different spectroscopic methods. In addition, single-crystal structures have been determined by X-Ray diffraction for both compounds. In each case a square planar Pt(II) is present; in (1) the qnxca is monodentate and neutral, whereas in (2) the ligand has lost a hydrogen, to form the anionic chelating ligand abbreviated as qnxca-H. The biological activity of both compounds has been investigated in a panel of seven human tumour cells, displaying poor cytotoxic activity, compared to cisplatin. The interaction of the new compounds with 1 or 2 equiv. of 9-ethylguanine has been studied using (1)H NMR, (195)Pt NMR and ESI-MS spectroscopy, finding poor reactivity of 1 towards the model base, forming only the monosubstituted adduct. Surprisingly, compound 2, which is more sterically crowded, interacts more efficiently with the 9-EtG, forming a bifunctional adduct with two 9-EtG with substitution of the dmso and the chloride ligand. Unwinding studies of pUC19 plasmid DNA by compound 1 show similar unwinding properties to cisplatin.

  4. Inhibition of precipitation of carbonate apatite by trisodium citrate analysed in base of the formation of chemical complexes in growth solution

    Energy Technology Data Exchange (ETDEWEB)

    Prywer, Jolanta, E-mail: jolanta.prywer@p.lodz.pl [Institute of Physics, Lodz University of Technology, ul. Wólczańska 219, 93-005 Łódź (Poland); Olszynski, Marcin [Institute of Physics, Lodz University of Technology, ul. Wólczańska 219, 93-005 Łódź (Poland); Mielniczek-Brzóska, Ewa [Institute of Chemistry, Environment Protection and Biotechnology, Jan Długosz University of Częstochowa, ul. Armii Krajowej 13/15, 42-200 Częstochowa (Poland)

    2015-11-15

    Effect of trisodium citrate on the precipitation of carbonate apatite is studied. The experimental series are performed in the solution of artificial urine. The investigations are related to infectious urinary stones formation as carbonate apatite is one of the main components of this kind of stones. To mimic a real infection in urinary tract the aqueous ammonia solution was added to the solution of artificial urine. The spectrophotometric results demonstrate that trisodium citrate increases induction time with respect to carbonate apatite formation and decreases the efficiency of carbonate apatite precipitation. The inhibitory effect of trisodium citrate on the precipitation of carbonate apatite is explained in base of chemical speciation analysis. Such an analysis demonstrates that the inhibitory effect is mainly related with the fact that trisodium citrate binds Ca{sup 2+} ions and causes the formation of CaCit{sup −} and Ca{sub 10}(PO{sub 4}){sub 6}CO{sub 3} complexes. Trisodium citrate binds Ca{sup 2+} ions in the range of pH from 6 to 9.5 for which carbonate apatite is favored to be formed. - Highlights: • Trisodium citrate (TC) increases induction time of carbonate apatite (CA) formation. • TC decreases the efficiency of CA precipitation. • The inhibitory effect of TC is explained in base of chemical speciation analysis. • The inhibitory effect is mainly related with the fact that TC binds Ca{sup 2+} ions. • TC binds Ca{sup 2+} ions in the range of pH from 6 to 9.5 for which CA is formed.

  5. SYNTHESIS AND CHARACTERIZATION OF HIGH MOLECULAR WEIGHT POLY(1,2-PROPYLENE CARBONATE-co-1,2-CYCLOHEXYLENE CARBONATE)USING ZINC COMPLEX CATALYST

    Institute of Scientific and Technical Information of China (English)

    Jing-shu Wu; Min Xiao; Hu He; Shuan-jin Wang; Dong-mei Han; Yue-zhong Meng

    2011-01-01

    Using supported multi-component zinc dicarboxylate catalyst,poly(1,2-propylene carbonate-co-l,2-cyclohexylene carbonate) (PPCHC) was successfully synthesized from carbon dioxide (CO2) with propylene oxide (PO) and cyclohexene oxide (CHO).The conversion of epoxides dramatically increased up to 89.7% (yield:384.2 g of polymer per g of Zn) with increasing reaction temperature from 60℃ to 80℃.The optimized reaction temperature is 80℃.The chemical structure,the molecular weight,as well as thermal and mechanical properties of the resulting terpolymers were investigated extensively.When CHO feed content (mol%) is lower than 10%,the PPCHC terpolymers have number average molecular weight (Mn)ranging from 102 × 103 to 202 × 103 and molecular weight distribution (MWD) values ranging from 2.8 to 3.5.In contrast to poly(propylene carbonate) (PPC),the introduction of small amount of CHO leads to increase in the glass transition temperature from 38.0℃ to 42.6℃.Similarly,the mechanical strength of the synthesized terpolymer is greatly enhanced due to the incorporation of CHO.These improvements in mechanical and thermal properties are of importance for the practical application of PPC.

  6. The influence of dissolved H2O content in supercritical carbon dioxide to the inclusion complexes formation of ketoprofen/β-cyclodextrin

    Science.gov (United States)

    Goenawan, Joshua; Trisanti, P. N.; Sumarno

    2015-12-01

    This work studies the relation between dissolved H2O content in supercritical carbon dioxide (SC-CO2) with the formation of ketoprofen (KP)/β-cyclodextrin(CD) inclusion complexes. The process involves a physical mixture of these two compounds into contact with the supercritical carbon dioxide which had been previously saturated with H2O over a certain duration. The pressure used for saturation process is 130 bar and saturation temperature was ranged between 30 °C to 50 °C. The inclusion process was achieved by keeping it for 2 hours at 160 bar and 200 bar with inclusion temperature of 50 °C. The results enable us to suggest explanations for the inclusion formation. The inclusion complexes can be formed by contacting the dissolved H2O in SC-CO2 to the physical mixture of KP and CD. An increase in the temperature of saturation process resulted in an increase of dissolved H2O content in the supercritical carbon dioxide. The increasing levels of this water soluble resulted an increase in the inclusion complexes that has been formed. The formation of inclusion complexes includes the water molecules enhancing the emptying of the CD cavities and being replaced by KP, towards a more stable energy state. The drug release used for analyzing the dissolution rate of the KP/CD complexes. The results vary from 79,85% to 99,98% after 45 minutes which is above the rate that has been assigned by Farmakope Indonesia at 70% dissolution rate for KP. The use of SC-CO2 offers a new methods for increasing the rate of dissolution of drugs that are hydrophobic such as KP. CO2 used as a supercritical fluid because of its relatively low cost, easily obtainable supercritical conditions, and lack of toxicity. The material samples were characterized by DSC and Spectrophotometer UV-vis technique.

  7. Deposition of new thia-containing Schiff-base iron (III) complexes onto carbon nanotube-modified glassy carbon electrodes as a biosensor for electrooxidation and determination of amino acids

    Energy Technology Data Exchange (ETDEWEB)

    Saghatforoush, Lotfali [Department of Chemistry, Faculty of Science, Payame Noor University (PNU), P.O. Box 58168-45164, Khoy (Iran, Islamic Republic of); Hasanzadeh, Mohammad, E-mail: mhmmd_hasanzadeh@yahoo.co [Department of Chemistry, Faculty of Science, Payame Noor University (PNU), P.O. Box 58168-45164, Khoy (Iran, Islamic Republic of); Department of Chemistry, Faculty of Science, K.N. Toosi University of Technology (KNTU), Tehran (Iran, Islamic Republic of); Shadjou, Nasrin [Department of Chemistry, Faculty of Science, Payame Noor University (PNU), P.O. Box 58168-45164, Khoy (Iran, Islamic Republic of); Department of Chemistry, Faculty of Science, K.N. Toosi University of Technology (KNTU), Tehran (Iran, Islamic Republic of); Khalilzadeh, Balal [Department of Analytical Chemistry, Faculty of Science, Arak University, Arak (Iran, Islamic Republic of)

    2011-01-01

    Multiwall carbon nanotubes (MWCNTs) were used as an immobilization matrix to incorporate an Fe (III)-Schiff base complex as an electron-transfer mediator onto a glassy carbon electrode surface. First, the preheated glassy carbon was subjected to abrasive immobilization of MWCNTs by gently rubbing the electrode surface on filter paper supporting the carbon nanotubes. Second, the electrode surface was modified by casting 100 {mu}L of an Fe (III)-complex solution (0.01 M in ACN). The cyclic voltammograms of the modified electrode in an aqueous solution displayed a pair of well-defined, stable and nearly reversible reductive oxidation redox systems with surface confined characteristics. Combinations of unique electronic and electrocatalytic properties of MWCNTs and Fe (III)-Schiff base complexes resulted in a remarkable synergistic augmentation of the response. The electrochemical behavior and stability of the modified electrode in aqueous solutions at pH 1-9 were characterized by cyclic voltammetry. The apparent electron transfer rate constant (K{sub s}) and transfer coefficient (a) were determined by cyclic voltammetry and were approximately 7 s{sup -1} and 0.55, respectively. The modified electrodes showed excellent catalytic activity towards the oxidation of amino acids at an unusually positive potential in acidic solution. They also displayed inherent stability at a wide pH range, fast response time, high sensitivity, low detection limit and had a remarkably positive potential oxidation of amino acids that decreased the effect of interferences in analysis. The linear concentration range, limits of detection (LOD), limits of quantization (LOQ) and relative standard deviation of the proposed sensor for the amino acid detection were 1-55,000, 1.10-13.70, 2.79-27.14 and 1.30-5.11, respectively.

  8. Cage-Like Porous Carbon with Superhigh Activity and Br2 -Complex-Entrapping Capability for Bromine-Based Flow Batteries.

    Science.gov (United States)

    Wang, Chenhui; Lai, Qinzhi; Xu, Pengcheng; Zheng, Daoyuan; Li, Xianfeng; Zhang, Huamin

    2017-06-01

    Bromine-based flow batteries receive wide attention in large-scale energy storage because of their attractive features, such as high energy density and low cost. However, the Br2 diffusion and relatively low activity of Br2 /Br(-) hinder their further application. Herein, a cage-like porous carbon (CPC) with specific pore structure combining superhigh activity and Br2 -complex-entrapping capability is designed and fabricated. According to the results of density functional theory (DFT) calculation, the pore size of the CPC (1.1 nm) is well designed between the size of Br(-) (4.83 Å), MEP(+) (9.25 Å), and Br2 complex (MEPBr3 12.40 Å), wherein Br(-) is oxidized to Br2 , which forms a Br2 complex with the complexing agent immediately and is then entrapped in the cage via pore size exclusion. In addition, the active sites produced during the carbon dioxide activation process dramatically accelerate the reaction rate of Br2 /Br(-) . In this way, combining a high Br2 -entrapping-capability and high specific surface areas, the CPC shows very impressive performance. The zinc bromine flow battery assembled with the prepared CPC shows a Coulombic efficiency of 98% and an energy efficiency of 81% at the current density of 80 mA cm(-2) , which are among the highest values ever reported. © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  9. Synthesis, characterization and in vitro inhibition of metal complexes of pyrazole based sulfonamide on human erythrocyte carbonic anhydrase isozymes I and II.

    Science.gov (United States)

    Büyükkıdan, Nurgün; Büyükkıdan, Bülent; Bülbül, Metin; Kasımoğulları, Rahmi; Mert, Samet

    2017-12-01

    Sulfonamides represent an important class of biologically active compounds. A sulfonamide possessing carbonic anhydrase (CA) inhibitory properties obtained from a pyrazole based sulfonamide, ethyl 1-(3-nitrophenyl)-5-phenyl-3-((5-sulfamoyl-1,3,4-thiadiazol-2-yl)carbamoyl)-1H-pyrazole-4-carboxylate (1), and its metal complexes with the Ni(II) for (2), Cu(II) for (3) and Zn(II) for (4) have been synthesized. The structures of metal complexes (2-4) were established on the basis of their elemental analysis, (1)H NMR, IR, UV-Vis and MS spectral data. The inhibition of two human carbonic anhydrase (hCA, EC 4.2.1.1) isoenzymes I and II, with 1 and synthesized complexes (2-4) and acetazolamide (AAZ) as a control compound was investigated in vitro by using the hydratase and esterase assays. The complexes 2, 3 and 4 showed inhibition constant in the range 0.1460-0.3930 µM for hCA-I and 0.0740-0.0980 µM for hCA-II, and they had effective more inhibitory activity on hCA-I and hCA-II than corresponding free ligand 1 and than AAZ.

  10. Free Energy Minimization Calculation of Complex Chemical Equilibria. Reduction of Silicon Dioxide with Carbon at High Temperature.

    Science.gov (United States)

    Wai, C. M.; Hutchinson, S. G.

    1989-01-01

    Discusses the calculation of free energy in reactions between silicon dioxide and carbon. Describes several computer programs for calculating the free energy minimization and their uses in chemistry classrooms. Lists 16 references. (YP)

  11. MEDUSA-2.0: an intermediate complexity biogeochemical model of the marine carbon cycle for climate change and ocean acidification studies

    Science.gov (United States)

    Yool, A.; Popova, E. E.; Anderson, T. R.

    2013-10-01

    MEDUSA-1.0 (Model of Ecosystem Dynamics, nutrient Utilisation, Sequestration and Acidification) was developed as an "intermediate complexity" plankton ecosystem model to study the biogeochemical response, and especially that of the so-called "biological pump", to anthropogenically driven change in the World Ocean (Yool et al., 2011). The base currency in this model was nitrogen from which fluxes of organic carbon, including export to the deep ocean, were calculated by invoking fixed C:N ratios in phytoplankton, zooplankton and detritus. However, due to anthropogenic activity, the atmospheric concentration of carbon dioxide (CO2) has significantly increased above its natural, inter-glacial background. As such, simulating and predicting the carbon cycle in the ocean in its entirety, including ventilation of CO2 with the atmosphere and the resulting impact of ocean acidification on marine ecosystems, requires that both organic and inorganic carbon be afforded a more complete representation in the model specification. Here, we introduce MEDUSA-2.0, an expanded successor model which includes additional state variables for dissolved inorganic carbon, alkalinity, dissolved oxygen and detritus carbon (permitting variable C:N in exported organic matter), as well as a simple benthic formulation and extended parameterizations of phytoplankton growth, calcification and detritus remineralisation. A full description of MEDUSA-2.0, including its additional functionality, is provided and a multi-decadal spin-up simulation (1860-2005) is performed. The biogeochemical performance of the model is evaluated using a diverse range of observational data, and MEDUSA-2.0 is assessed relative to comparable models using output from the Coupled Model Intercomparison Project (CMIP5).

  12. MEDUSA-2.0: an intermediate complexity biogeochemical model of the marine carbon cycle for climate change and ocean acidification studies

    Directory of Open Access Journals (Sweden)

    A. Yool

    2013-10-01

    Full Text Available MEDUSA-1.0 (Model of Ecosystem Dynamics, nutrient Utilisation, Sequestration and Acidification was developed as an "intermediate complexity" plankton ecosystem model to study the biogeochemical response, and especially that of the so-called "biological pump", to anthropogenically driven change in the World Ocean (Yool et al., 2011. The base currency in this model was nitrogen from which fluxes of organic carbon, including export to the deep ocean, were calculated by invoking fixed C:N ratios in phytoplankton, zooplankton and detritus. However, due to anthropogenic activity, the atmospheric concentration of carbon dioxide (CO2 has significantly increased above its natural, inter-glacial background. As such, simulating and predicting the carbon cycle in the ocean in its entirety, including ventilation of CO2 with the atmosphere and the resulting impact of ocean acidification on marine ecosystems, requires that both organic and inorganic carbon be afforded a more complete representation in the model specification. Here, we introduce MEDUSA-2.0, an expanded successor model which includes additional state variables for dissolved inorganic carbon, alkalinity, dissolved oxygen and detritus carbon (permitting variable C:N in exported organic matter, as well as a simple benthic formulation and extended parameterizations of phytoplankton growth, calcification and detritus remineralisation. A full description of MEDUSA-2.0, including its additional functionality, is provided and a multi-decadal spin-up simulation (1860–2005 is performed. The biogeochemical performance of the model is evaluated using a diverse range of observational data, and MEDUSA-2.0 is assessed relative to comparable models using output from the Coupled Model Intercomparison Project (CMIP5.

  13. Synthesis, characterization, and biological activity of platinum II, III, and IV pivaloamidine complexes.

    Science.gov (United States)

    Sinisi, Marilù; Gandin, Valentina; Saltarella, Teresa; Intini, Francesco P; Pacifico, Concetta; Marzano, Christine; Natile, Giovanni

    2014-10-01

    Imino ligands have proven to be able to activate the trans geometry of platinum(II) complexes towards antitumor activity. These ligands, like aromatic N-donor heterocycles, have a planar shape but, different from the latter, have still an H atom on the coordinating nitrogen which can be involved in H-bond formation. Three classes of imino ligands have been extensively investigated: iminoethers (HN=C(R)OR'), ketimines (HN=CRR'), and amidines (HN=C(R)NR'R″). The promising efficacy of the platinum compounds with amidines (activity comparable to that of cisplatin for cis complexes and much greater than that of transplatin for trans complexes) prompted us to extend the investigation to amidine complexes with a bulkier organic residue (R = t-Bu). The tert-butyl group can confer greater affinity for lipophilic environments, thus potentiating the cellular uptake of the compound. In the present study we describe the synthesis and characterization of pivaloamidine complexes of platinum(II), (cis and trans-[PtCl2(NH3){Z-HN=C(t-Bu)NH2}] and cis and trans-[PtCl2{Z-HN=C(t-Bu)NH2}2]), platinum(III) ([Pt2Cl4{HN=C(t-Bu)NH}2(NH3)2]), and platinum(IV) (trans-[PtCl4(NH3){Z-HN=C(t-Bu)NH2}] and trans-[PtCl4{Z-HN=C(t-Bu)NH2}2]). The cytotoxicity of all new Pt complexes was tested toward a panel of cultured cancer cell lines, including cisplatin and multidrug resistant variants. In addition, cellular uptake and DNA binding, perturbations of cell cycle progression, induction of apoptosis, and p53 activation were investigated for the most promising compound trans-[PtCl2(NH3){Z-HN=C(t-Bu)NH2}]. Remarkably, the latter complex was able to overcome both acquired and intrinsic cisplatin resistance.

  14. Determination of porosity and facies trends in a complex carbonate reservoir, by using 3-D seismic, borehole tools, and outcrop geology

    Energy Technology Data Exchange (ETDEWEB)

    Zacharakis, T.G. Jr.; Comet, J.N.; Murillo, A.A. [Respol Exploracion, S.A., Madrid (Spain)] [and others

    1996-08-01

    Mesozoic carbonate reservoirs are found in the Mediterranean Sea, off the east coast of Spain. A wide variation of porosities are found in the core samples and logs: vuggy, breccia, fractures, and cavern porosity. In addition, complex Tertiary carbonate geometries include olistostromes, breccia bodies, and reef buildups, which are found on top of Mesozoic carbonates. Predicting the porosity trends within these oil productive reservoirs requires an understanding of how primary porosity was further enhanced by secondary processes, including fractures, karstification, and dolomitization in burial conditions. Through an extensive investigation of field histories, outcrop geology, and seismic data, a series of basic reservoir styles have been identified and characterized by well log signature and seismic response. The distribution pattern of the different reservoirs styles is highly heterogeneous, but by integrating subsurface data and outcrop analogs, it is possible to distinguish field-scale and local patterns of both vertical and local variations in reservoir properties. Finally, it is important to quantify these reservoir properties through the study of seismic attributes, such as amplitude variations, and log responses at the reservoir interval. By incorporating 3-D seismic data, through the use of seismic inversion, it is possible to predict porosity trends. Further, the use of geostatistics can lead to the prediction of reservoir development within the carbonate facies.

  15. Carbon-carbon cross-coupling reactions catalyzed by a two-coordinate nickel(II)-bis(amido) complex via observable Ni(I) , Ni(II) , and Ni(III) intermediates.

    Science.gov (United States)

    Lipschutz, Michael I; Tilley, T Don

    2014-07-01

    Recently, the development of more sustainable catalytic systems based on abundant first-row metals, especially nickel, for cross-coupling reactions has attracted significant interest. One of the key intermediates invoked in these reactions is a Ni(III) -alkyl species, but no such species that is part of a competent catalytic cycle has yet been isolated. Herein, we report a carbon-carbon cross-coupling system based on a two-coordinate Ni(II) -bis(amido) complex in which a Ni(III) -alkyl species can be isolated and fully characterized. This study details compelling experimental evidence of the role played by this Ni(III) -alkyl species as well as those of other key Ni(I) and Ni(II) intermediates. The catalytic cycle described herein is also one of the first examples of a two-coordinate complex that competently catalyzes an organic transformation, potentially leading to a new class of catalysts based on the unique ability of first-row transition metals to accommodate two-coordinate complexes.

  16. Comparison of the effects of the oral anticancer platinum(IV) complexes oxoplatin and metabolite cis-diammine-tetrachlorido-platinum(IV) on global gene expression of NCI-H526 cells.

    Science.gov (United States)

    Olszewski, Ulrike; Ulsperger, Ernst; Geissler, Klaus; Hamilton, Gerhard

    2011-01-01

    Platinum(IV) coordination complexes like oxoplatin (cis,cis,trans-diammine-dichlorido-dihydroxido-platinum[IV]) show high stability and therefore can be utilized orally for outpatient care. Although oxoplatin is capable of binding directly to DNA after prolonged incubation, platinum(IV) agents are considered to be largely inert prodrugs that are converted to highly cytotoxic platinum(II) compounds by reducing substances, enzymes, or microenviron-mental conditions. Reaction of oxoplatin with 0.1 M hydrogen chloride mimicking gastric acid yields cis-diammine-tetrachlorido-platinum(IV) (DATCP[IV]), which exhibits two-fold increased activity. The presence of chlorides as ligands in the axial position results in a high reduction potential that favors transformation to platinum(II) complexes. In this study, the intracellular effect of the highly reactive tetrachlorido derivative was investigated in comparison with an equipotent dose of cisplatin. Genome-wide expression profiling of NCI-H526 small cell lung cancer cells treated with these platinum species revealed clear differences in the expression pattern of affected genes and concerned cellular pathways between DATCP(IV) and cisplatin. Application of DATCP(IV) resulted in extensive downregulation of protein and ATP synthesis, cell cycle regulation, and glycolysis, in contrast to cisplatin, which preferentially targeted glutathione conjugation, pyruvate metabolism, citric acid cycle, and the metabolism of amino acids and a range of carbohydrates. Thus, the oxoplatin metabolite DATCP(IV) constitutes a potent cytotoxic derivative that may be produced by gastric acid or acidic areas prevailing in larger solid tumors, depending on the respective pharmaceutical formulation of oxoplatin. Furthermore, DATCP(IV) exhibits intracellular effects that are clearly different from the expected reduced product cisplatin(II). In conclusion, activation of the platinum(IV) complex oxoplatin seems to involve the generation of a cytotoxic

  17. The formation mechanism of fluorescent metal complexes at the Li(x)Ni(0.5)Mn(1.5)O(4-δ)/carbonate ester electrolyte interface.

    Science.gov (United States)

    Jarry, Angélique; Gottis, Sébastien; Yu, Young-Sang; Roque-Rosell, Josep; Kim, Chunjoong; Cabana, Jordi; Kerr, John; Kostecki, Robert

    2015-03-18

    Electrochemical oxidation of carbonate esters at the Li(x)Ni(0.5)Mn(1.5)O(4-δ)/electrolyte interface results in Ni/Mn dissolution and surface film formation, which negatively affect the electrochemical performance of Li-ion batteries. Ex situ X-ray absorption (XRF/XANES), Raman, and fluorescence spectroscopy, along with imaging of Li(x)Ni(0.5)Mn(1.5)O(4-δ) positive and graphite negative electrodes from tested Li-ion batteries, reveal the formation of a variety of Mn(II/III) and Ni(II) complexes with β-diketonate ligands. These metal complexes, which are generated upon anodic oxidation of ethyl and diethyl carbonates at Li(x)Ni(0.5)Mn(1.5)O(4-δ), form a surface film that partially dissolves in the electrolyte. The dissolved Mn(III) complexes are reduced to their Mn(II) analogues, which are incorporated into the solid electrolyte interphase surface layer at the graphite negative electrode. This work elucidates possible reaction pathways and evaluates their implications for Li(+) transport kinetics in Li-ion batteries.

  18. Five phosphonate operon gene products as components of a multi-subunit complex of the carbon-phosphorus lyase pathway

    DEFF Research Database (Denmark)

    Jochimsen, Bjarne; Lolle, Signe; McSorley, Fern R.;

    2011-01-01

    Organophosphonate utilization by Escherichia coli requires the 14 cistrons of the phnCDEFGHIJKLMNOP operon, of which the carbon-phosphorus lyase has been postulated to consist of the seven polypeptides specified by phnG to phnM. A 5,660-bp DNA fragment encompassing phnGHIJKLM is cloned, followed ...

  19. XAFS study on the sulfidation mechanisms of Co-Mo catalysts supported on activated carbon and alumina: effect of complexing agent.

    Science.gov (United States)

    Tsuji, K; Umeki, T; Yokoyama, Y; Kitada, T; Iwanami, Y; Nonaka, O; Shimada, H; Matsubayashi, N; Nishijima, A; Nomura, M

    2001-03-01

    The effect of nitrilotriacetic acid (NTA) as a complexing agent on the sulfidation mechanisms of Co-Mo catalysts supported on activated carbon and alumina was examined by the XAFS technique. The XAFS results revealed that NTA interacted with Co atoms and formed the Co-NTA interaction, while it showed almost no influence on the local structures around Mo atoms. The Co-NTA interaction suppressed the aggregation of cobalt atoms and the interaction between cobalt and alumina during sulfiding, and consequently promoted the formation of the Co-Mo-S phase.

  20. Metal Complexes of 1,3,4-Thiadiazole-2,5-Disulfonamide are Strong Dual Carbonic Anhydrase Inhibitors, although the Ligand Possesses very Weak such Properties.

    Science.gov (United States)

    Supuran, C T

    1995-01-01

    Coordination compounds of Co(II), Ni(II), Cu(II), Zn(II), and Cd(II) with 1,3,4-thiadiazole-2,5-disulfonamide as ligand were synthesized and characterized by IR and UV spectroscopy, conductimetry and thermogravimetry. The parent ligand is a very weak carbonic anhydrase (CA) inhibitor, although it constituted the lead for developing important classes of diuretics. The complex derivatives behave as much stronger CA inhibitors, with IC(50) values around 10(-8)M against isozyme CA II, and 10(-7) M against isozyme CAI.

  1. Covalent and Non-covalent Chemical Modification of Multi-walled Carbon Nanotubes with Tetra-(4-hydroxylphenyl)porphyrin and Its Complexes

    Institute of Scientific and Technical Information of China (English)

    Zhao, Hongbin; Wang, Hongke; Chang, Hui; Qiu, Shijun; Deng, Biyun; Liao, Junxu

    2011-01-01

    Multi-walled carbon nanotubes (MWNTs) were covalently and non-covalently functionalized with tetra- (4-hydroxylphenyl) porphyrin (THPPH2) and its complexes (ZnTHPP) forming dispersible nanohybrids in organic solution. The morphology of the nanohybrids was observed with transmission electron microscopy. The structure of the product was characterized by FT-IR, UV-Vis spectrophotometer, fluorescence spectroscopy and thermogravim- etric analysis. The photo-induced electron-transfer process of the nanohybrids in organic solution was also revealed.

  2. Metal Complexes of 1,3,4-Thiadiazole-2,5-Disulfonamide are Strong Dual Carbonic Anhydrase Inhibitors, although the Ligand Possesses very Weak such Properties

    Science.gov (United States)

    Supuran, Claudiu T.

    1995-01-01

    Coordination compounds of Co(II), Ni(II), Cu(II), Zn(II), and Cd(II) with 1,3,4-thiadiazole-2,5-disulfonamide as ligand were synthesized and characterized by IR and UV spectroscopy, conductimetry and thermogravimetry. The parent ligand is a very weak carbonic anhydrase (CA) inhibitor, although it constituted the lead for developing important classes of diuretics. The complex derivatives behave as much stronger CA inhibitors, with IC50 values around 10−8M against isozyme CA II, and 10−7 M against isozyme CAI. PMID:18472784

  3. Cobalt(III) complexes of [3(5)] adamanzane, 1,5,9,13-tetraazabicyclo[7.7.3]nonadecane. Report of an inert, chelate hydrogen carbonate ion.

    Science.gov (United States)

    Broge, L; Søtofte, I; Olsen, C E; Springborg, J

    2001-06-18

    Three cobalt(III) complexes of the macrocyclic tetraamine [3(5)]adamanzane (1,5,9,13-tetraazabicyclo[7.7.3]nonadecane) were isolated as salts. The X-ray crystal structures were solved for the compounds [Co([3(5)]adz)(CO(3))]AsF(6) (1b), [Co([3(5)]adz)(HCO(3))]ZnBr(4).H(2)O (2a), and [Co([3(5)]adz)(SO(4))]AsF(6).H(2)O (3a). The coordination geometry around the cobalt(III) ion is a distorted octahedron with the inorganic ligands at cis-positions. Complex 2 is the second example of a cobalt(III) complex for which the X-ray structure shows a chelate binding mode of the hydrogen carbonate entity. The pK(a) value of the [Co([3(5)]adz)(HCO(3))](2+) ion (2) was determined spectrophotometrically to be 0.27 (25 degrees C, I = 5.0 M). The protonation appears to occur at the noncoordinated carbonyl oxygen atom of the carbonate group, with hydrogen bonding to the crystal water molecule. Evidence is presented for this oxygen atom as the site of protonation in solution as well. In 5.0 M CF(3)SO(3)H a slow reaction of the carbonato complex, quantitatively yielding the [Co([3(5)]adz)(H(2)O)(2)](3+) ion, was observed. k(obs) = 7.9(1) x 10(-)(6) s(-)(1) at 25 degrees C.

  4. Actinide metals with multiple bonds to carbon: synthesis, characterization, and reactivity of U(IV) and Th(IV) bis(iminophosphorano)methandiide pincer carbene complexes.

    Science.gov (United States)

    Ma, Guibin; Ferguson, Michael J; McDonald, Robert; Cavell, Ronald G

    2011-07-18

    Treatment of ThCl(4)(DME)(2) or UCl(4) with 1 equiv of dilithiumbis(iminophosphorano) methandiide, [Li(2)C(Ph(2)P═NSiMe(3))(2)] (1), afforded the chloro actinide carbene complexes [Cl(2)M(C(Ph(2)P═NSiMe(3))(2))] (2 (M = Th) and 3 (M = U)) in situ. Stable PCP metal-carbene complexes [Cp(2)Th(C(Ph(2)P═NSiMe(3))(2))] (4), [Cp(2)U(C(Ph(2)P═NSiMe(3))(2))] (5), [TpTh(C(Ph(2)P═NSiMe(3))(2))Cl] (6), and [TpU(C(Ph(2)P═NSiMe(3))(2))Cl] (7) were generated from 2 or 3 by further reaction with 2 equiv of thallium(I) cyclopentadienide (CpTl) in THF to yield 4 or 5 or with 1 equiv of potassium hydrotris(pyrazol-1-yl) borate (TpK) also in THF to give 6 or 7, respectively. The derivative complexes were isolated, and their crystal structures were determined by X-ray diffraction. All of these U (or Th)-carbene complexes (4-7) possess a very short M (Th or U)═carbene bond with evidence for multiple bond character. Gaussian 03 DFT calculations indicate that the M═C double bond is constructed by interaction of the 5f and 6d orbitals of the actinide metal with carbene 2p orbitals of both π and σ character. Complex 3 reacted with acetonitrile or benzonitrile to cyclo-add C≡N to the U═carbon double bond, thereby forming a new C-C bond in a new chelated quadridentate ligand in the bridged dimetallic complexes (9 and 10). A single carbon-U bond is retained. The newly coordinated uranium complex dimerizes with one equivalent of unconverted 3 using two chlorides and the newly formed imine derived from the nitrile as three connecting bridges. In addition, a new crystal structure of [CpUCl(3)(THF)(2)] (8) was determined by X-ray diffraction.

  5. Synthesis of Polyketone by Copolymerization of Styrene and CO Using Carbon Nanotube-Complex Pd2+Catalyst

    Institute of Scientific and Technical Information of China (English)

    郭锦棠; 肖淼; 王海霞; 胡光

    2014-01-01

    The dipping method was devised to deposit Pd onto carbon nanotube as supported catalyst (Pd/CNT) for the copolymerization of carbon monoxide (CO) and styrene(ST) towards the formation of polyketone (PK). The Pd/CNT was characterized by X-ray photoelectron spectroscopy (XPS), X-ray diffraction (XRD) and high-resolution transmission electron microscopy (HRTEM). The construction and crystallization property of PK were evaluated by Fourier transform infrared spectroscopy (FTIR), 13C-nuclear magnetic resonance(NMR) and XRD, respectively. The catalyst showed excellent activity and reusability in promoting the fabrication of PK. It can be recycled 14 times with the highest total catalytic activity of 4 239.64 gPK/(gPd·h) at Pd content of 8.63wt%. The results indicate that the prepared catalyst is effective to catalyze the copolymerization of CO and styrene.

  6. Studies of properties of complex carbon-silica adsorbents used in sorption-desorption processes (solid-phase extraction)

    Energy Technology Data Exchange (ETDEWEB)

    Rudzinski, W. [Maria Curie-Sklodowska Univ., Lublin (Poland). Faculty of Chemistry; Gierak, A. [Maria Curie-Sklodowska Univ., Lublin (Poland). Faculty of Chemistry; Leboda, R. [Maria Curie-Sklodowska Univ., Lublin (Poland). Faculty of Chemistry; Dabrowski, A. [Maria Curie-Sklodowska Univ., Lublin (Poland). Faculty of Chemistry

    1995-08-01

    Adsorption properties of carbon and carbon-silica adsorbents, prepared by n-octanol and glucose pyrolysis and catalytic decomposition of n-butane, have been studied regarding their applicability for the extraction and concentration of phenol, its nitro- and chloro-derivatives and trihalomethanes [THM] from aqueous solutions in the concentration range of 2 to 20 mg/l. The adsorbents investigated have been subjected to various physico-chemical processes (hydrothermal treatment, oxidation, silanization) in order to improve their efficiency. The adsorption isotherms measured correspond well to the Freundlich equation. A good correlation have been observed between the values of the Freundlich constant k and the adsorbent efficiency. The investigation has been carried out using the ``off line`` method, and recovery rates for the compounds studied as high as 40-100% have been obtained. (orig.)

  7. Real-time imaging of complex nanoscale mechanical responses of carbon nanotubes in highly compressible porous monoliths

    Energy Technology Data Exchange (ETDEWEB)

    Whitby, Raymond L D; Mikhalovsky, Sergey V [Brighton Nanoscience and Nanotechnology Group, PABS, University of Brighton, Lewes Road, Brighton, BN2 4GJ (United Kingdom); Fukuda, Takahiro; Maekawa, Toru [Bio-Nano Electronics Research Centre, Toyo University, 2100 Kujirai, Kawagoe Saitama 350-8585 (Japan); Cundy, Andrew B, E-mail: r.whitby@brighton.ac.uk [School of Environment and Technology, University of Brighton, Lewes Road, Brighton, BN2 4GJ (United Kingdom)

    2010-02-19

    A facile and rapid assembly of powdered carbon nanotubes (CNTs) into compressible, porous, macroscale monoliths is reported. Despite a Poisson's ratio just above zero, we found that the sample under compression inside a scanning electron microscope (SEM) revealed CNT regions behaving in auxetic and vortex-like rotational modes as well as standard collapse responses. This method is crucial in understanding the macroscale behaviour based on the accumulation of nanoscale responses to an applied force.

  8. Real-time imaging of complex nanoscale mechanical responses of carbon nanotubes in highly compressible porous monoliths

    Science.gov (United States)

    Whitby, Raymond L. D.; Fukuda, Takahiro; Maekawa, Toru; Mikhalovsky, Sergey V.; Cundy, Andrew B.

    2010-02-01

    A facile and rapid assembly of powdered carbon nanotubes (CNTs) into compressible, porous, macroscale monoliths is reported. Despite a Poisson's ratio just above zero, we found that the sample under compression inside a scanning electron microscope (SEM) revealed CNT regions behaving in auxetic and vortex-like rotational modes as well as standard collapse responses. This method is crucial in understanding the macroscale behaviour based on the accumulation of nanoscale responses to an applied force.

  9. Effects of germanium doping on the behavior of oxygen and carbon impurities and impurity-related complexes in Si

    Energy Technology Data Exchange (ETDEWEB)

    Londos, C.A., E-mail: hlontos@phys.uoa.g [University of Athens, Solid State Physics Section, Panepistimiopolis Zografos, Athens 157 84 (Greece); Andrianakis, A. [University of Athens, Solid State Physics Section, Panepistimiopolis Zografos, Athens 157 84 (Greece); Emtsev, V.V.; Oganesyan, G.A. [Ioffe Physicotechnical Institute of the Russian Academy of Sciences, Politeknicheskaya ul. 26, 194021 St. Petersburg (Russian Federation); Ohyama, H. [Kumamoto National College of Technology, 26592, Nishigoshi, Kumamoto 861-1102 (Japan)

    2009-12-15

    The production and annealing of oxygen and carbon related defects in electron-irradiated Ge-doped Czochralski silicon have been studied by means of IR spectroscopy. The results demonstrate that the role of Ge changes with increasing Ge content. At low Ge concentrations, much less than 10{sup 20} cm{sup -3}, Ge atoms act as temporary traps for vacancies preventing their annihilation with self-interstitials. At high Ge concentrations, Ge atoms form clusters which tend to attract vacancies and self-interstitials, enhancing their mutual annihilation. As a result, for low Ge concentrations the production of oxygen-related defects (VO) and carbon-related defects (C{sub i}O{sub i}, C{sub i}O{sub i}(Si{sub I}), C{sub i}C{sub s}) tend to increase as a function of Ge content, while for high Ge concentrations tend to decrease. The annealing of the oxygen-related defects VO{sub n} (1<=n<=6) is also affected by the Ge presence. The ratio of the VO defects that convert to VO{sub 2} is reduced in Ge doped material. However, this ratio increases for the conversions VO{sub n}->VO{sub n+1} (3<=n<=5), respectively. The annealing temperature of VO defect and the growth temperature of VO{sub 2} defect decrease versus Ge content. On the other hand, the thermal stability of the carbon-related defects was found to be insensitive to the presence of Ge. It was also found that the carbon precipitation process shows some marked differences in irradiated Ge-doped Si, in comparison with the undoped material.

  10. A New Nitrogenase Mechanism Using a CFe8S9 Model: Does H2 Elimination Activate the Complex to N2 Addition to the Central Carbon Atom?

    Science.gov (United States)

    McKee, Michael L

    2016-02-11

    A truncated model of the FeMo cofactor is used to explore a new mechanism for the conversion of N2 to NH3 by the nitrogenase enzyme. After four initial protonation/reduction steps, the H4CFe8S9 cluster has two hydrogen atoms attached to sulfur, one hydrogen bridging two iron centers and one hydrogen bonded to carbon. The loss of the CH and FeHFe hydrogens as molecular hydrogen activates the cluster to addition of N2 to the carbon center. This unique step takes place at a nearly planar four-coordinate carbon center and leads to an intermediate with a significantly weakened N-N bond. A hydrogen attached to a sulfur atom is then transferred to the distal nitrogen atom. Additional prontonation/reduction steps are modeled by adding a hydrogen atom to sulfur and locating the transition states for transfer to nitrogen. The first NH3 is lost in a thermal neutral step, while the second step is endothermic. The loss of H2 activates the complex by reducing the barrier for N2 addition by 3.5 kcal/mol. Since this is the most difficult step in the mechanism, reducing the barrier for this step justifies the "extra expense" of H2 production.

  11. Complexing Agents on Carbon Content and Lithium Storage Capacity of LiFePO4/C Cathode Synthesized via Sol-Gel Approach

    Directory of Open Access Journals (Sweden)

    C. Guan

    2016-01-01

    Full Text Available Olivine-structured LiFePO4 faces its intrinsic challenges in terms of poor electrical conductivity and lithium-ion diffusion capability for application to lithium-ion batteries. Cost-effective sol-gel approach is advantageous to in situ synthesize carbon-coated LiFePO4 (LiFePO4/C which can not only improve electronic conductivity but also constrain particle size to nanometer scale. In this study, the key parameter is focused on the choice and amount of chelating agents in this synthesis route. It was found that stability of complexing compounds has significant impacts on the carbon contents and electrochemical properties of the products. At the favorable choice of precursors, composition, and synthesis conditions, nanocrystalline LiFePO4/C materials with appropriate amount of carbon coating were successfully obtained. A reversible capacity of 162 mAh/g was achieved at 0.2C rate, in addition to good discharge rate capability.

  12. Five phosphonate operon gene products as components of a multi-subunit complex of the carbon-phosphorus lyase pathway

    DEFF Research Database (Denmark)

    Jochimsen, Bjarne; Lolle, Signe; McSorley, Fern R.

    2011-01-01

    by expression in E. coli and purification of Phn-polypeptides. PhnG, PhnH, PhnI, PhnJ, and PhnK copurify as a protein complex by ion-exchange, size-exclusion, and affinity chromatography. The five polypeptides also comigrate in native-PAGE. Cross-linking of the purified protein complex reveals a close proximity...... is suggested to be PhnG4H2I2J2K. Deletion of individual phn genes reveals that a strain harboring plasmid-borne phnGHIJ produces a protein complex consisting of PhnG, PhnH, PhnI, and PhnJ, whereas a strain harboring plasmid-borne phnGIJK produces a protein complex consisting of PhnG and PhnI. We conclude...

  13. Polydopamine/polyethyleneimine complex adhered to micrometer-sized magnetic carbon fibers for high-efficiency hemoperfusion.

    Science.gov (United States)

    Liu, Rui-Lin; Wang, Yan; Ge, Xian-Li; Yu, Pei; Liu, Hui-Qin; Wang, Ming-Chan; Lu, Wen; Fu, Qiang

    2017-10-01

    Carbon-based nanomaterials have recently attracted tremendous attention in adsorption, separation and biological fields. However, such modification is not always straightforward when the surface is not chemically reactive. Given this reason, most carbon materials modification processes employ reactive linkers or coupling agents, which are complicated and time-consuming. Herein, we report on a dopamine-polyethyleneimine (PEI) coating strategy to fabricate micrometer-sized magnetic carbon fiber (MSMCF)-based extracorporeal blood-cleansing sorbent for hemoperfusion. Results showed that the dopamine/PEI-coated MSMCF had a twisted fiber shape with a size range of 80-120 μm in diameter and porous structure with a specific surface area of 146 m(2) g(-1). Adsorption behavior of dopamine/PEI-modified MSMCF was examined by using bilirubin as a toxin model compound. Equilibrium data were well fitted to the Langmuir isotherm model with a maximal adsorption capacity of 335.1 mg g(-1) at ambient temperature. The as-obtained material had relatively high bilirubin adsorption selectivity against albumin at a normal albumin concentration. In particular, the dopamine/PEI-coated MSMCF has excellent adsorption capacity and hemocompatibility compared to the MSMCF decorated only by dopamine or PEI. Therefore, this work may pave the way for enhancing the property of the extracorporeal blood-cleansing sorbent during hemoperfusion.

  14. Tuning the activity of platinum(IV) anticancer complexes through asymmetric acylation.

    Science.gov (United States)

    Chin, Chee Fei; Tian, Quan; Setyawati, Magdiel Inggrid; Fang, Wanru; Tan, Emelyn Sue Qing; Leong, David Tai; Ang, Wee Han

    2012-09-13

    Platinum(II) anticancer drug cisplatin is one of the most important chemotherapeutic agents in clinical use but is limited by its high toxicity and severe side effects. Platinum(IV) anticancer prodrugs can overcome these limitations by resisting premature aquation and binding to essential plasma proteins. Structure-activity relationship studies revealed a link between the efficacy of platinum(IV) complexes with the nature of their axial ligands, which can be modified to enhance the properties of the prodrug. The existing paradigm of employing platinum(IV) complexes with symmetrical axial carboxylate ligands does not fully exploit their vast potential. A new approach was conceived to control properties of platinum(IV) prodrugs using contrasting axial ligands via sequential acylation. We report a novel class of asymmetric platinum(IV) carboxylates based on the cisplatin template containing both hydrophilic and lipophilic ligands on the same scaffold designed to improve their aqueous properties and enhance their efficacy against cancer cells in vitro.

  15. The loading of coordination complex modified polyoxometalate nanobelts on activated carbon fiber: a feasible strategy to obtain visible light active and highly efficient polyoxometalate based photocatalysts.

    Science.gov (United States)

    Lu, Tingting; Xu, Xinxin; Li, Huili; Li, Zhenyu; Zhang, Xia; Ou, Jinzhao; Mei, Mingliang

    2015-02-01

    To enhance the photocatalytic properties of coordination complex modified polyoxometalates (CC/POMs) in the visible light region, its nanobelts (CC/POMNBs) were loaded on activated carbon fiber (ACF) through a simple colloidal blending process. The resulting coordination complex modified polyoxometalate nanobelts loaded activated carbon fiber composite materials (CC/POMNBs/ACF) exhibited dramatic photocatalytic activity for the degradation of rhodamine B (RhB) under visible light irradiation. Optical and electrochemical methods illustrated the enhanced photocatalytic activity of CC/POMNBs/ACF, which originates from the high separation efficiency of the photogenerated electrons and holes on the interface of the CC/POMNBs and ACF, which results from the synergistic effects between them. In the composite material, the role of ACF could be described as a photosensitizer and a good electron transporter. Furthermore, the influence of the mass ratio between the CC/POMNBs and ACF on the photocatalytic performance of the resulting composite material was discussed, and an ideal value to obtain highly efficient photocatalysts was obtained. The results suggested that the loading of CC/POMNBs on the surface of ACF would be a feasible strategy to enhance their photocatalytic activity.

  16. Zn(II), Cd(II) and Cu(II) complexes of 2,5-bis{N-(2,6-diisopropylphenyl)iminomethyl}pyrrole: synthesis, structures and their high catalytic activity for efficient cyclic carbonate synthesis.

    Science.gov (United States)

    Vignesh Babu, Heeralal; Muralidharan, Krishnamurthi

    2013-01-28

    The syntheses of Zn(II), Cd(II) and Cu(II) complexes of 2,5-bis{N-(2,6-diisopropylphenyl)iminomethyl}pyrrole (DIP(2)pyr)H 1 and their catalytic activities in CO(2) fixation are reported. The structures of these complexes were characterized by IR, (1)H, (13)C NMR and single crystal X-ray diffraction techniques. The catalytic activities of these complexes for the cycloaddition of CO(2) to an epoxide under one atmosphere of pressure and mild temperature conditions to yield cyclic carbonate have been studied. Among the four complexes synthesized, the Zn(II) and Cu(II) complexes were found to be versatile whereas the Cu(II) complex was more selective in the conversion. They were highly effective for the conversion of monosubstituted terminal epoxides, disubstituted terminal and internal epoxides to their corresponding cyclic carbonates with good to high yields.

  17. Trace analysis of cefotaxime at carbon paste electrode modified with novel Schiff base Zn(II) complex.

    Science.gov (United States)

    Nigam, Preeti; Mohan, Swati; Kundu, Subir; Prakash, Rajiv

    2009-02-15

    Cefotaxime a third generation cephalosporin drug estimation in nanomolar concentration range is demonstrated for the first time in aqueous and human blood samples using novel Schiff base octahedral Zn(II) complex. The cefotaxime electrochemistry is studied over graphite paste and Zn(II) complex modified graphite paste capillary electrodes in H(2)SO(4) (pH 2.3) using cyclic voltammetry and differential pulse voltammetry. Cefotaxime enrichment is observed over Zn(II) complex modified graphite paste electrode probably due to interaction of functional groups of cefotaxime with Zn(II) complex. Possible interactions between metal complex and cefotaxime drug is examined by UV-vis and electrochemical quartz crystal microbalance (EQCM) techniques and further supported by voltammetric analysis. Differential pulse voltammetry (DPV) with modified electrode is applied for the determination of cefotaxime in acidified aqueous and blood samples. Cefotaxime estimation is successfully demonstrated in the range of 1-500 nM for aqueous samples and 0.1-100 microM in human blood samples. Reproducibility, accuracy and repeatability of the method are checked by triplicate reading for large number of samples. The variation in the measurements is obtained less than 10% without any interference of electrolyte or blood constituents.

  18. Carbon dioxide is tightly bound in the [Co(Pyridine)(CO{sub 2})]{sup −} anionic complex

    Energy Technology Data Exchange (ETDEWEB)

    Graham, Jacob D.; Buytendyk, Allyson M.; Zhang, Xinxing; Bowen, Kit H., E-mail: kbowen@jhu.edu [Department of Chemistry, Johns Hopkins University, Baltimore, Maryland 21218 (United States); Kim, Seong K. [Department of Chemistry, Seoul National University, Seoul 151-747 (Korea, Republic of)

    2015-11-14

    The [Co(Pyridine)(CO{sub 2})]{sup −} anionic complex was studied through the combination of photoelectron spectroscopy and density functional theory calculations. This complex was envisioned as a primitive model system for studying CO{sub 2} binding to negatively charged sites in metal organic frameworks. The vertical detachment energy (VDE) measured via the photoelectron spectrum is 2.7 eV. Our calculations imply a structure for [Co(Pyridine)(CO{sub 2})]{sup −} in which a central cobalt atom is bound to pyridine and CO{sub 2} moieties on either sides. This structure was validated by acceptable agreement between the calculated and measured VDE values. Based on our calculations, we found CO{sub 2} to be bound within the anionic complex by 1.4 eV.

  19. Complex Physiological Response of Norway Spruce to Atmospheric Pollution – Decreased Carbon Isotope Discrimination and Unchanged Tree Biomass Increment

    Science.gov (United States)

    Čada, Vojtěch; Šantrůčková, Hana; Šantrůček, Jiří; Kubištová, Lenka; Seedre, Meelis; Svoboda, Miroslav

    2016-01-01

    Atmospheric pollution critically affects forest ecosystems around the world by directly impacting the assimilation apparatus of trees and indirectly by altering soil conditions, which subsequently also leads to changes in carbon cycling. To evaluate the extent of the physiological effect of moderate level sulfate and reactive nitrogen acidic deposition, we performed a retrospective dendrochronological analysis of several physiological parameters derived from periodic measurements of carbon stable isotope composition (13C discrimination, intercellular CO2 concentration and intrinsic water use efficiency) and annual diameter increments (tree biomass increment, its inter-annual variability and correlation with temperature, cloud cover, precipitation and Palmer drought severity index). The analysis was performed in two mountain Norway spruce (Picea abies) stands of the Bohemian Forest (Czech Republic, central Europe), where moderate levels of pollution peaked in the 1970s and 1980s and no evident impact on tree growth or link to mortality has been reported. The significant influence of pollution on trees was expressed most sensitively by a 1.88‰ reduction of carbon isotope discrimination (Δ13C). The effects of atmospheric pollution interacted with increasing atmospheric CO2 concentration and temperature. As a result, we observed no change in intercellular CO2 concentrations (Ci), an abrupt increase in water use efficiency (iWUE) and no change in biomass increment, which could also partly result from changes in carbon partitioning (e.g., from below- to above-ground). The biomass increment was significantly related to Δ13C on an individual tree level, but the relationship was lost during the pollution period. We suggest that this was caused by a shift from the dominant influence of the photosynthetic rate to stomatal conductance on Δ13C during the pollution period. Using biomass increment-climate correlation analyses, we did not identify any clear pollution

  20. A fluorescence-Raman dual-imaging platform based on complexes of conjugated polymers and carbon nanotubes.

    Science.gov (United States)

    Liu, Yun; Huang, Jun; Sun, Min-Jie; Yu, Ji-Cheng; Chen, Yu-Lei; Zhang, Yu-Qi; Jiang, Shao-Jun; Shen, Qun-Dong

    2014-01-01

    The present study describes a flexible nanoplatform based on electrostatic assembly of conjugated polyelectrolytes (CPEs) and carboxylated multi-walled carbon nanotubes (cMWNTs). It is demonstrated that the obtained nanocomposites inherit intrinsic optical properties of CPEs and characteristic Raman vibration modes of MWNTs, providing a fluorescence-Raman dual-imaging method for intracellular tracking and locating of MWNTs. We suggest that the cellular internalization of the CPE-cMWNT nanocomposites is a surface charge-dependent process. The strengths of this nanoplatform include satisfying biocompatibility, enhanced protein-repellent property, and ease of implementation, making it available for both in vitro and in vivo applications.

  1. Efficient and high yield one-pot synthesis of cyclometalated platinum(II) β-diketonates at ambient temperature.

    Science.gov (United States)

    Hudson, Zachary M; Blight, Barry A; Wang, Suning

    2012-04-06

    Cyclometalated Pt(II) β-diketonates are widely used as efficient luminescent materials but are typically prepared at high temperatures in low yields using excess reagents. A one-pot synthesis of these complexes is described employing stoichiometric reagents and short reaction times at ambient temperature, giving yields of up to 94%. The method is applicable to a broad range of substrates including N^C, P^C, and C^C chelate Pt(II) complexes and different β-diketonate ligands.

  2. Synthesis, characterization, antibacterial activities and carbonic anhydrase enzyme inhibitor effects of new arylsulfonylhydrazone and their Ni(II), Co(II) complexes

    Science.gov (United States)

    Özdemir, Ümmühan Özmen; Arslan, Fatma; Hamurcu, Fatma

    2010-01-01

    Ethane sulfonic acide hydrazide ( esh: CH 3CH 2SO 2NHNH 2) derivatives as 5-methylsalicyl-aldehydeethanesulfonylhydrazone ( 5msalesh), 5-methyl-2-hydroxyacetophenoneethane sulfonylhydrazone ( 5mafesh) and their Ni(II), Co(II) complexes have been synthesized for the first time. The structure of these compounds has been investigated by elemental analysis, FT-IR, 1H NMR, 13C NMR, LC/MS, UV-vis spectrophotometric method, magnetic susceptibility, thermal studies and conductivity measurements. The antibacterial activities of synthesized compounds were studied against Gram positive bacteria; Staphylococcus aureus, Bacillus subtilis, Bacillus magaterium and Gram negative bacteria; Salmonella enteritidis, Escherichia coli by using the microdilution broth method. The biological activity screening showed that ligands have more activity than complexes against the tested bacteria. The inhibition activities of these compounds on carbonic anhydrase II (CA II) have been investigated by comparing IC 50 and Ki values and it has been found that 5msalesh and its complexes have more enzyme inhibition efficiency than other compounds.

  3. Reductive electropolymerization of a vinyl-containing poly-pyridyl complex on glassy carbon and fluorine-doped tin oxide electrodes.

    Science.gov (United States)

    Harrison, Daniel P; Carpenter, Logan S; Hyde, Jacob T

    2015-01-30

    Controllable electrode surface modification is important in a number of fields, especially those with solar fuels applications. Electropolymerization is one surface modification technique that electrodeposits a polymeric film at the surface of an electrode by utilizing an applied potential to initiate the polymerization of substrates in the Helmholtz layer. This useful technique was first established by a Murray-Meyer collaboration at the University of North Carolina at Chapel Hill in the early 1980s and utilized to study numerous physical phenomena of films containing inorganic complexes as the monomeric substrate. Here, we highlight a procedure for coating electrodes with an inorganic complex by performing reductive electropolymerization of the vinyl-containing poly-pyridyl complex onto glassy carbon and fluorine doped tin oxide coated electrodes. Recommendations on electrochemical cell configurations and troubleshooting procedures are included. Although not explicitly described here, oxidative electropolymerization of pyrrole-containing compounds follows similar procedures to vinyl-based reductive electropolymerization but are far less sensitive to oxygen and water.

  4. Preclinical toxicity and pharmacology of liposome-entrapped cis-bis-neodecanoato-trans-R,R-1,2-diaminocyclohexane platinum(II).

    Science.gov (United States)

    Perez-Soler, R; Lautersztain, J; Stephens, L C; Wright, K; Khokhar, A R

    1989-01-01

    Liposome-entrapped cis-bis-neodecanoate-trans-R,R-1,2-diaminocylohexane platinum(II) (L-NDDP) is a new lipophilic cisplatin derivative formulated in a liposomal carrier currently in phase I clinical trials. The preclinical toxicity and pharmacology of L-NDDP were studied in mice and dogs. At the LD50 dose (i.v. bolus) in mice (60.5 mg/kg or 181.5 mg/m2), a tenfold decrease in the granulocyte and platelet counts was observed in the absence of renal toxic effects. In dogs, the maximum tolerated dose (MTD) of L-NDDP given i.v. over a period of 45-60 min was 150 mg/m2. This dose produced significant vomiting (6-18 episodes), minimal renal dysfunction, a maximal decrease in granulocyte and platelet counts of from 30% to 70%, and acute and transient elevation of liver enzymes. Higher doses (225 and 300 mg/m2) resulted in severe gastrointestinal (GI) toxicity in one animal and the death of two others within 48 h. Autopsy results showed multifocal hemorrhages in the lungs, GI tract, kidney, and liver. Three dogs were treated monthly with the MTD up to a cumulative dose of 637.5-712.5 mg/m2 with excellent tolerance. No cumulative myelosuppression or liver dysfunction was observed, whereas a slight increase in the creatinine baseline level was detected in all three animals. Autopsy results at the end of the study showed mild changes limited to the liver, kidney, and GI tract. Pharmacologic studies showed that the drug was cleared, fitting a two-compartment model with a mean t1/2 alpha of 7.1 min and a t1/2 beta of 87.8 h. These studies show that L-NDDP can safely be given at therapeutic doses to animals and that the dose-limiting toxic effects consists of myelosuppression in mice and a multiorgan hemorrhagic syndrome related to vascular injury in dogs.

  5. Platinum(II/IV) complexes containing ethylenediamine-N,N'-di-2/3-propionate ester ligands induced caspase-dependent apoptosis in cisplatin-resistant colon cancer cells.

    Science.gov (United States)

    Kaluđerović, Goran N; Mijatović, Sanja A; Zmejkovski, Bojana B; Bulatović, Mirna Z; Gómez-Ruiz, Santiago; Mojić, Marija K; Steinborn, Dirk; Miljković, Djordje M; Schmidt, Harry; Stošić-Grujičić, Stanislava D; Sabo, Tibor J; Maksimović-Ivanić, Danijela D

    2012-08-01

    Several new R(2)eddp (R = i-Pr, i-Bu; eddp = ethylenediamine-N,N'-di-3-propionate) esters and corresponding platinum(ii) and platinum(iv) complexes of the general formula [PtCl(n)(R(2)edda-type)] (n = 2, 4) were synthesized and characterized by spectroscopic methods (IR, (1)H and (13)C NMR) and elemental analysis. The crystal structure of platinum(iv) complex [PtCl(4){(c-Pe)(2)eddip}] (3a) was resolved and is given herein. Ligand precursors, platinum(ii), and platinum(iv) complexes were tested against eight tumor cell lines (CT26CL25, HTC116, SW620, PC3, LNCaP, U251, A375, and B16). Selectivity in the action of those compounds between tumor and two normal primary cells (fibroblasts and keratinocytes) are discussed. A structure-activity relationship of these compounds is discussed. Furthermore, cell cycle distribution, induction of necrosis, apoptosis, autophagy, anoikis, caspase activation, ROS, and RNS are presented on the cisplatin-resistant colon carcinoma HCT116 cell line.

  6. Development and evaluation of pH-responsive single-walled carbon nanotube-doxorubicin complexes in cancer cells

    Directory of Open Access Journals (Sweden)

    Gu YJ

    2011-11-01

    Full Text Available Yan-Juan Gu1,2,*, Jinping Cheng2,*, Jiefu Jin3, Shuk Han Cheng2, Wing-Tak Wong11Department of Applied Biology and Chemical Technology, The Hong Kong Polytechnic University, 2Department of Biology and Chemistry, The City University of Hong Kong, 3Department of Chemistry, The University of Hong Kong, Hong Kong, China*These authors contributed equally to this workAbstract: Single-walled carbon nanotubes (SWNTs have been identified as an efficient drug carrier. Here a controlled drug-delivery system based on SWNTs coated with doxorubicin (DOX through hydrazone bonds was developed, because the hydrazone bond is more sensitive to tumor microenvironments than other covalent linkers. The SWNTs were firstly stabilized with polyethylene glycol (H2N-PEG-NH2. Hydrazinobenzoic acid (HBA was then covalently attached on SWNTs via carbodiimide-activated coupling reaction to form hydrazine-modified SWNTs. The anticancer drug DOX was conjugated to the HBA segments of SWNT using hydrazine as the linker. The resulting hydrazone bonds formed between the DOX molecules and the HBA segments of SWNTs are acid cleavable, thereby providing a strong pH-responsive drug release, which may facilitate effective DOX release near the acidic tumor microenvironment and thus reduce its overall systemic toxicity. The DOX-loaded SWNTs were efficiently taken up by HepG2 tumor cells, and DOX was released intracellularly, as revealed by MTT assay and confocal microscope observations. Compared with SWNT-DOX conjugate formed by supramolecular interaction, the SWNT-HBA-DOX featured high weight loading and prolonged release of DOX, and thus improved its cytotoxicity against cancer cells. This study suggests that while SWNTs have great potential as a drug carrier, the efficient formulation strategy requires further study.Keywords: carbon nanotubes, drug delivery, controlled release, SWNTs

  7. Extraction of superoxide dismutase, catalase, and carbonic anhydrase from stroma-free red blood cell hemolysate for the preparation of the nanobiotechnological complex of polyhemoglobin-superoxide dismutase-catalase-carbonic anhydrase.

    Science.gov (United States)

    Guo, C; Gynn, M; Chang, T M S

    2015-06-01

    We report a novel method to simultaneously extract superoxide dismutase (SOD), catalase (CAT), and carbonic anhydrase (CA) from the same sample of red blood cells (RBCs). This avoids the need to use expensive commercial enzymes, thus enabling a cost-effective process for large-scale production of a nanobiotechnological polyHb-SOD-CAT-CA complex, with enhancement of all three red blood cell functions. An optimal concentration of phosphate buffer for ethanol-chloroform treatment results in good recovery of CAT, SOD, and CA after extraction. Different concentrations of the enzymes can be used to enhance the activity of polyHb-SOD-CAT-CA to 2, 4, or 6 times that of RBC.

  8. Enhanced Conversion Efficiencies in Dye-Sensitized Solar Cells Achieved through Self-Assembled Platinum(II) Metallacages

    Science.gov (United States)

    He, Zuoli; Hou, Zhiqiang; Xing, Yonglei; Liu, Xiaobin; Yin, Xingtian; Que, Meidan; Shao, Jinyou; Que, Wenxiu; Stang, Peter J.

    2016-07-01

    Two-component self-assembly supramolecular coordination complexes with particular photo-physical property, wherein unique donors are combined with a single metal acceptor, can be utilized for many applications including in photo-devices. In this communication, we described the synthesis and characterization of two-component self-assembly supramolecular coordination complexes (SCCs) bearing triazine and porphyrin faces with promising light-harvesting properties. These complexes were obtained from the self-assembly of a 90° Pt(II) acceptor with 2,4,6-tris(4-pyridyl)-1,3,5-triazine (TPyT) or 5,10,15,20-Tetra(4-pyridyl)-21H,23H-porphine (TPyP). The greatly improved conversion efficiencies of the dye-sensitized TiO2 solar cells were 6.79 and 6.08 respectively, while these SCCs were introduced into the TiO2 nanoparticle film photoanodes. In addition, the open circuit voltage (Voc) of dye-sensitized solar cells was also increased to 0.769 and 0.768 V, which could be ascribed to the inhibited interfacial charge recombination due to the addition of SCCs.

  9. Improving the Spatial Prediction of Soil Organic Carbon Stocks in a Complex Tropical Mountain Landscape by Methodological Specifications in Machine Learning Approaches.

    Science.gov (United States)

    Ließ, Mareike; Schmidt, Johannes; Glaser, Bruno

    2016-01-01

    Tropical forests are significant carbon sinks and their soils' carbon storage potential is immense. However, little is known about the soil organic carbon (SOC) stocks of tropical mountain areas whose complex soil-landscape and difficult accessibility pose a challenge to spatial analysis. The choice of methodology for spatial prediction is of high importance to improve the expected poor model results in case of low predictor-response correlations. Four aspects were considered to improve model performance in predicting SOC stocks of the organic layer of a tropical mountain forest landscape: Different spatial predictor settings, predictor selection strategies, various machine learning algorithms and model tuning. Five machine learning algorithms: random forests, artificial neural networks, multivariate adaptive regression splines, boosted regression trees and support vector machines were trained and tuned to predict SOC stocks from predictors derived from a digital elevation model and satellite image. Topographical predictors were calculated with a GIS search radius of 45 to 615 m. Finally, three predictor selection strategies were applied to the total set of 236 predictors. All machine learning algorithms-including the model tuning and predictor selection-were compared via five repetitions of a tenfold cross-validation. The boosted regression tree algorithm resulted in the overall best model. SOC stocks ranged between 0.2 to 17.7 kg m-2, displaying a huge variability with diffuse insolation and curvatures of different scale guiding the spatial pattern. Predictor selection and model tuning improved the models' predictive performance in all five machine learning algorithms. The rather low number of selected predictors favours forward compared to backward selection procedures. Choosing predictors due to their indiviual performance was vanquished by the two procedures which accounted for predictor interaction.

  10. Lithium insertion into boron containing carbons prepared by co-pyrolysis of coal-tar pitch and borane-pyridine complex

    Energy Technology Data Exchange (ETDEWEB)

    Machnikowski, J.; Frackowiak, E.; Kierzek, K.; Waszak, D.; Benoit, R.; Beguin, F. [Wroclaw University of Technology, Wroclaw (Poland)

    2004-03-01

    Carbon materials of boron content ranging from 0.6 to 4 wt.% were synthesized by co-pyrolysis of QI-free coal-tar pitch with the borane-pyridine complex. The growing amount of boron introduced into the carbonaceous material is associated with an increase in nitrogen content and a progressive degradation of structural and textural ordering. The structural variations of the boron-doped materials on heat treatment up to 2500{sup o}C were monitored using X-ray diffraction and X-ray photoelectron spectroscopy. The intrinsic boron acts effectively as a catalyst of graphitization above 2100{sup o}C. The carbonaceous material with boron content of about 1.5 wt% shows the highest degree of structural ordering after thermal treatment. A high amount of oxygen was found in the graphitized boronated carbons, proving that the incorporated boron induces a strong chemisorption activity of the material when exposed to air. For a series of cokes calcined at 1000 {sup o}C, the most striking effect of increasing the boron content is an increase of irreversible capacity X-irr from 0.2 to 0.7. The reversible capacity (X-rev) amounts to about 1, with a slight tendency to decrease with the boron content. Upon increasing the temperature up to 2500{sup o}C, X-irr decreases to about 0.1 in the graphitic carbons, while X-rev reaches a minimum of 0.4-0.5 at 1700{sup o}C and next increases to a value close to 1 at 2500{sup o}C. In the boron doped graphite, X-irr has a slight tendency to increase with the boron content, due to the simultaneous presence of nitrogen in these materials and their strong affinity for oxygen from the atmosphere.

  11. Fabrication of TiO{sub 2} nanoparticles/surfactant polymer complex film on glassy carbon electrode and its application to sensing trace dopamine

    Energy Technology Data Exchange (ETDEWEB)

    Yuan Shuai [Department of Chemistry, Wuhan University, Wuhan 430072 (China); Chen Wanhua [Department of Chemistry, Wuhan University, Wuhan 430072 (China); Hu Shengshui [Department of Chemistry, Wuhan University, Wuhan 430072 (China)]. E-mail: sshu@whu.edu.cn

    2005-06-15

    A novel method for the fabrication of a TiO{sub 2}/Nafion nano-film on glassy carbon electrode (NTGCE) is described. In the presence of dispersant, TiO{sub 2} nanoparticles were dispersed into water to give a homogeneous and stable suspension. After the solvent evaporation, a porous and uniform TiO{sub 2} nano-film was obtained on the GCE surface. Further coated with Nafion, the complex film possesses remarkable stability in aqueous solution. This nano-film was characterized by scanning electron microscopy (SEM) and atomic force microscopy (AFM). The prepared electrode showed excellent electrocatalytic behavior of dopamine and high concentration of ascorbic acid does not interfere with the dopamine detection. Based on this, an electrochemical method is developed for the determination of dopamine with simplicity and high sensitivity.

  12. Fabrication of electrochemical sensor for paracetamol based on multi-walled carbon nanotubes and chitosan-copper complex by self-assembly technique.

    Science.gov (United States)

    Mao, Airong; Li, Hongbo; Jin, Dangqin; Yu, Liangyun; Hu, Xiaoya

    2015-11-01

    An electrochemical sensor for paracetamol based on multi-walled carbon nanotubes and chitosan-copper complex (MWCNTs/CTS-Cu) was fabricated by self-assembly technique. The MWCNTs/CTS-Cu modified GCE showed an excellent electrocatalytic activity for the oxidation of paracetamol, and accelerated electron transfer between the electrode and paracetamol. Under optimal experimental conditions, the differential pulse peak current was linear with the concentration of paracetamol in the range of 0.1-200 μmol L(-1) with a detection limit of 0.024 μmol L(-1). The sensitivity was found to be 0.603 A/mol L(-1). The proposed sensor also showed a high selectivity for paracetamol in the presence of ascorbic acid and dopamine. Moreover, the proposed electrode revealed good reproducibility and stability. The proposed method was successfully applied for the determination of paracetamol in tablet and human serum samples.

  13. Organometallic ruthenium(II) complexes: synthesis, structure and influence of substitution at azomethine carbon towards DNA/BSA binding, radical scavenging and cytotoxicity.

    Science.gov (United States)

    Sathyadevi, Palanisamy; Krishnamoorthy, Paramasivam; Bhuvanesh, Nattamai S P; Kalaiselvi, Palaniswamy; Vijaya Padma, Viswanadha; Dharmaraj, Nallasamy

    2012-09-01

    Bivalent, ruthenium organometallics containing hydrazone ligands with the composition [RuH(CO)(PPh(3))(2)(L(1-3))] (4-6) have been synthesised from the reactions of [RuH(2)(CO)(PPh(3))(3)] and benzoic acid pyridine-2-ylmethylene-hydrazide (HL(1)) (1) /benzoic acid (1-pyridin-2-yl-ethylidene)-hydrazide (HL(2)) (2)/benzoic acid (phenyl-pyridin-2-yl-methylene)-hydrazide (HL(3)) (3) and characterised by various physico-chemical techniques. The X-ray crystal structure of one of the above complexes, [RuH(CO)(PPh(3))(2)(L(3))] (6) demonstrated a distorted octahedral coordination geometry around the metal centre. Results of our investigation on the effect of substitution (H or CH(3) or C(6)H(5)) at the azomethine carbon of coordinated hydrazone in these ruthenium chelates on the potential binding with DNA/BSA, free radical scavenging and cytotoxicity is presented.

  14. Nickel-phendione complex covalently attached onto carbon nanotube/cross linked glucose dehydrogenase as bioanode for glucose/oxygen compartment-less biofuel cell

    Science.gov (United States)

    Korani, Aazam; Salimi, Abdollah; Hadadzadeh, Hasan

    2015-05-01

    Here, [Ni(phendion) (phen)]Cl2 complex, (phendion and phen are 1,10-phenanthroline-5,6-dione and 5-amino-1, 10-phenanthrolin) covalently attached onto carboxyl functionalized multi walls carbon nanotube modified glassy carbon electrode (GCE/MWCNTs-COOH) using solid phase interactions and combinatorial approaches.The attached [Ni(phendion) (phen)]Cl2 complex displays a surface controlled electrode process and it acts as an effective redox mediator for electrocatalytic oxidation of dihydronicotinamide adenine dinucleotide (NADH) at reduced overpotentials. With co-immobilization of glucose dehydrogenase enzyme (GDH) by crosslinking an effective biocatalyst for glucose oxidation designed. The onset potential and current density are -0.1 V versus Ag/AgCl electrode and 0.550 mA cm-2, which indicate the applicability of the proposed system as an efficient bioanode for biofuel cell (BFC) design. A GCE/MWCNTs modified with electrodeposited gold nanoparticles (AuNPs) as a platform for immobilization of bilirubin oxidase (BOD) and the prepared GCE/MWCNTs/AuNPs/BOD biocathode exhibits an onset potential of 0.56 V versus Ag/AgCl. The performance of the fabricated bioanode and biocathode in a membraneless enzyme based glucose/O2 biofuel cell is evaluated. The open circuit voltage of the cell and maximum current density are 520 mV and 0.233 mA cm-2, respectively, while maximum power density of 40 μWcm-2 achieves at voltage of 280 mV with stable output power after 24 h continues operation.

  15. The properties of the Lewis acid-base complexes of boron trifluoride with some carbon dioxide analogues. An ab initio study

    Science.gov (United States)

    Ford, Thomas A.

    2017-07-01

    The properties of nine binary Lewis acid-base complexes, formed between boron trifluoride, on the one hand, and the carbon dioxide analogues XCY (X, Y = O, S, Se) on the other, have been investigated by means of ab initio calculations. The properties of most interest are the structures, the interaction energies, the vibrational spectra and the natural orbital population changes. The structures of the complexes bound through either a sulphur or a selenium atom are remarkably similar, and feature a FB … XC fragment in a trans arrangement, with FB … X and B … XC angles close to 90°. The adducts bound through oxygen have quite different structures, with a B … OC angle close to 150° in the case of BF3·OCO and with linear B … OCS and B … OCSe moieties in the other two cases. The binding energies of all nine complexes span a very narrow range, and are all less than 10 kJ mol-1. The changes of the intramolecular BF, XC and CY bond lengths are small, but they vary in a systematic way with the strength of interaction. The wavenumber shifts of the modes of the BF3 and XCY fragments are also fairly insignificant, except for the symmetric bending mode of the BF3 molecule, where the shifts are found to be in the range from -20 to -40 cm-1. The similarities and differences in the properties of the three families of adducts have been rationalized by reference to the redistribution of the natural orbital populations resulting from complex formation.

  16. Evidence of different stoichiometries for the limiting carbonate complexes across the lanthanide(III) series: A capillary electrophoresis-mass spectrometry study

    Energy Technology Data Exchange (ETDEWEB)

    Philippini, V.; Vercouter, T.; Vitorge, P. [CEA, Dept Physicochem, Lab Speciat Radionucleides et Mol, F-91191 Gif Sur Yvette, (France); Aupiais, J.; Topin, S.; Ambard, C. [CEA, Serv Radioanalyse Chim et Environm, Bruyeres Le Chatel, (France); Chausse, A.; Vitorge, P. [Lab Analyse et Modelisat Biol et Environm, Evry, (France)

    2008-07-01

    The electrophoretic mobilities ({mu}{sub ep,Ln}) of twelve lanthanides (not Ce, Pr and Yb) were measured by CE-ICP-MS in 0.15 and 0.5 mol L{sup -1} Alk{sub 2}CO{sub 3} aqueous solutions for Alk{sup +} = Li{sup +}, Na{sup +}, K{sup +} and Cs{sup +}. In 0.5 mol L{sup -1} solutions, two different {mu}{sub ep,Ln} values were found for the light (La to Nd) and the heavy (Dy to Tm) lanthanides, which suggests two different stoichiometries for the carbonate limiting complexes. These results are consistent with a solubility study that attests the Ln(CO{sub 3}){sub 3}{sup 3-} and Ln(CO{sub 3}){sub 4}{sup 5-} stoichiometries for the heavy (small) and the light (big) lanthanides, respectively. The Alk{sup +} counter-ions influence the {mu}{sub ep,Ln}{sup Alk2CO3} values, but not the overall shape of the {mu}{sub ep,Ln}{sup Alk2CO3} plots as a function of the lanthanide atomic numbers: the counter-ions do not modify the stoichiometries of the inner sphere complexes. The influence of the Alk{sup +} counter-ions decreases in the Li{sup +} {>=} Na{sup +} {>=}{>=} K{sup +} {>=} Cs{sup +} series. The K{sub 3,Ln} stepwise formation constants of the Ln(CO{sub 3}){sub 3}{sup 3-} complexes slightly increase with the atomic numbers of the lanthanides while K{sub 4,Ln}, the stepwise formation constants of Ln(CO{sub 3}){sub 4}{sup 5-} complexes, slightly decrease from La to Th, and is no longer measurable for heavier lanthanides. (authors)

  17. Activation of SO{sub 2} and CO{sub 2} by trivalent uranium leading to sulfite/dithionite and carbonate/oxalate complexes

    Energy Technology Data Exchange (ETDEWEB)

    Schmidt, Anna-Corina; Heinemann, Frank W.; Meyer, Karsten [Friedrich-Alexander University Erlangen-Nuernberg (FAU), Department of Chemistry and Pharmacy, Inorganic Chemistry, Erlangen (Germany); Kefalidis, Christos E.; Maron, Laurent [LPCNO, Universite de Toulouse, INSA Toulouse (France); Roesky, Peter W. [Karlsruhe Institute of Technology (KIT), Institute of Inorganic Chemistry, Karlsruhe (Germany)

    2014-10-13

    The first sulfite [{(("n"P","M"eArO)_3tacn)U"I"V}{sub 2}(μ-κ{sup 1}:κ{sup 2}-SO{sub 3})] (tacn=triazacyclononane) and dithionite [{(("n"P","M"eArO)_3tacn)U"I"V}{sub 2}(μ-κ{sup 2}:κ{sup 2}-S{sub 2}O{sub 4})] complexes of uranium from reaction with gaseous SO{sub 2} have been prepared. Additionally, the reductive activation of CO{sub 2} was investigated with respect to the rare oxalate [{(("n"P","M"eArO)_3tacn)U"I"V}{sub 2}(μ-κ{sup 2}:κ{sup 2}-C{sub 2}O{sub 4})] formation. This ultimately provides the unique S{sub 2}O{sub 4}{sup 2-}/C{sub 2}O{sub 4}{sup 2-} and SO{sub 3}{sup 2-}/CO{sub 3}{sup 2-} complex pairs. All new complexes were characterized by a combination of single-crystal X-ray diffraction, elemental analysis, UV/Vis/NIR electronic absorption, IR vibrational, and {sup 1}H NMR spectroscopy, as well as magnetization (VT SQUID) studies. Moreover, density functional theory (DFT) calculations were carried out to gain further insight into the reaction mechanisms. All observations, together with DFT, support the assumption that SO{sub 2} and CO{sub 2} show similar (dithionite/oxalate) to analogous (sulfite/carbonate) activation behavior with uranium complexes. (copyright 2014 WILEY-VCH Verlag GmbH and Co. KGaA, Weinheim)

  18. Highly active and selective catalysis of copper diphosphine complexes for the transformation of carbon dioxide into silyl formate.

    Science.gov (United States)

    Motokura, Ken; Kashiwame, Daiki; Takahashi, Naoki; Miyaji, Akimitsu; Baba, Toshihide

    2013-07-22

    Copper diphosphine complexes have been found to be highly active and selective homogeneous catalysts for the hydrosilylation of CO2. The structure of the phosphine ligands strongly affects their catalytic activity. Turnover number (TON) reaches 70,000 after 24 hours with 1,2-bis(diisopropylphosphino)benzene as a ligand under 1 atmosphere of CO2. (1)H and (13)C NMR spectra, carried out under the reaction conditions, showed the reaction mechanism through insertion of CO2 into Cu-H to afford Cu/formate species.

  19. C-H Bond Activation of Bisimines by Palladium (Ⅱ) and Platinum (Ⅱ).Synthesis,Characterization of Bis (imino) aryl-palladium (Ⅱ) Pincer Complexes and Their Application in Carbon-Carbon Cross Coupling Reactions%C-H Bond Activation of Bisimines by Palladium (Ⅱ) and Platinum (Ⅱ).Synthesis, Characterization of Bis (imino) aryl-palladium (Ⅱ) Pincer Complexes and Their Application in Carbon-Carbon Cross Coupling Reactions

    Institute of Scientific and Technical Information of China (English)

    CHEN Rong; CHEN Ying; LIU Fang; LI Ping; HU Zhao-xia; WANG Hong-xing

    2013-01-01

    Abstract:The reactions of a variety of 4,6-dimethyl-1,3-bis (imino) benzenes 2a-g derived from 4,6-dimethylisophthalaldehyde and anilines or benzylamine with palladium (Ⅱ) acetate in anhydrous acetic acid under nitrogen were investigated.Experiment results demonstrate that cyclopalladations in such condition are applicable not only to the present system under study but also to the 5-substituted bis(imino)benzenes 6,7.The molecular structure of 3 b was further confirmed by X-Ray single-crystal diffraction.3b Crystallizes in orthorhombic,space groupP2 (1) 2 (1) 2 (1) with a =0.734 53 (8),b =1.683 8 (3),c =1.691 7(2) nm,α =β =γ =90°.Treatment of 2b with K2PtCl4 in anhydrous acetic acid affords the corresponding NCN-platinum pincer.Carbon-carbon cross coupling reactions catalyzed with 3b were investigated.These palladium complexes have been proved to be high effective catalysts for Suzuki coupling reaction.

  20. Quantitative electrochemical detection of cathepsin B activity in complex tissue lysates using enhanced AC voltammetry at carbon nanofiber nanoelectrode arrays.

    Science.gov (United States)

    Swisher, Luxi Z; Prior, Allan M; Shishido, Stephanie; Nguyen, Thu A; Hua, Duy H; Li, Jun

    2014-06-15

    The proteolytic activity of a cancer-related enzyme cathepsin B is measured with alternating current voltammetry (ACV) using ferrocene (Fc) labeled tetrapeptides attached to nanoelectrode arrays (NEAs) fabricated with vertically aligned carbon nanofibers (VACNFs). This combination enables the use of high AC frequencies (~1kHz) with enhanced electrochemical signals. The specific proteolysis of the Fc-peptide by cathepsin B produces decay in the ACV peak current versus the reaction time. The exponential component of the raw data can be extracted and defined as the "extracted proteolytic signal" which allows consistent quantitative analyses using a heterogeneous Michaelis-Menten model. A "specificity constant" kcat/KM = (3.68 ± 0.50) × 10(4)M(-1)s(-1) for purified cathepsin B was obtained. The detections of cathepsin B activity in different concentrations of whole lysate of human breast tissue, tissue lysate spiked with varied concentrations of cathepsin B, and the tissue lysate after immunoprecipitation showed that there is ~13.4 nM higher cathepsin B concentration in 29.1 µg mL(-1) of whole tissue lysate than the immunoprecipitated sample. The well-defined regular VACNF NEAs by e-beam lithography show a much faster kinetics for cathepsin B proteolysis with kcat/KM = 9.2 × 10(4)M(-1)s(-1). These results illustrate the potential of this technique as a portable multiplex electronic system for cancer diagnosis by rapid protease profiling of serum or blood samples.

  1. An Endohyphal Bacterium (Chitinophaga, Bacteroidetes) Alters Carbon Source Use by Fusarium keratoplasticum (F. solani Species Complex, Nectriaceae)

    Science.gov (United States)

    Shaffer, Justin P.; U'Ren, Jana M.; Gallery, Rachel E.; Baltrus, David A.; Arnold, A. Elizabeth

    2017-01-01

    Bacterial endosymbionts occur in diverse fungi, including members of many lineages of Ascomycota that inhabit living plants. These endosymbiotic bacteria (endohyphal bacteria, EHB) often can be removed from living fungi by antibiotic treatment, providing an opportunity to assess their effects on functional traits of their fungal hosts. We examined the effects of an endohyphal bacterium (Chitinophaga sp., Bacteroidetes) on substrate use by its host, a seed-associated strain of the fungus Fusarium keratoplasticum, by comparing growth between naturally infected and cured fungal strains across 95 carbon sources with a Biolog® phenotypic microarray. Across the majority of substrates (62%), the strain harboring the bacterium significantly outperformed the cured strain as measured by respiration and hyphal density. These substrates included many that are important for plant- and seed-fungus interactions, such as D-trehalose, myo-inositol, and sucrose, highlighting the potential influence of EHB on the breadth and efficiency of substrate use by an important Fusarium species. Cases in which the cured strain outperformed the strain harboring the bacterium were observed in only 5% of substrates. We propose that additive or synergistic substrate use by the fungus-bacterium pair enhances fungal growth in this association. More generally, alteration of the breadth or efficiency of substrate use by dispensable EHB may change fungal niches in short timeframes, potentially shaping fungal ecology and the outcomes of fungal-host interactions. PMID:28382021

  2. Exploring molecular complexity with ALMA (EMoCA): Simulations of branched carbon-chain chemistry in Sgr B2(N)

    Science.gov (United States)

    Garrod, R. T.; Belloche, A.; Müller, H. S. P.; Menten, K. M.

    2017-05-01

    Context. Using millimeter wavelength data from the Atacama Large Millimeter/submillimeter Array (ALMA), the EMoCA spectral line survey recently revealed the presence of both the straight-chain (normal) and branched (iso) forms of propyl cyanide (C3H7CN) toward the Galactic Center star-forming source Sgr B2(N2). This was the first interstellar detection of a branched aliphatic molecule. Aims: Through computational methods, we seek to explain the observed i:n ratio for propyl cyanide, and to predict the abundances of the four different forms of the homologous nitrile, butyl cyanide (C4H9CN). We also investigate whether other molecules will show a similar degree of branching, by modeling the chemistry of alkanes up to pentane (C5H12). Methods: We use the coupled three-phase chemical kinetics model, MAGICKAL, to simulate the chemistry of the hot-core source Sgr B2(N2), using an updated chemical network that includes grain-surface/ice-mantle formation routes for branched nitriles and alkanes. The network explicitly considers radical species with an unpaired electron on either the primary or secondary carbon in a chain. We also include mechanisms for the addition of the cyanide radical, CN, to hydrocarbons with multiple bonds between carbon atoms, using activation energy barriers from the literature. We use the EMoCA survey data to search for the straight-chain form of butyl cyanide toward Sgr B2(N2). Results: The observed i:n ratio for propyl cyanide is reproduced by the models, with intermediate to fast warm-up timescales providing the most accurate result. Butyl cyanide is predicted to show similar abundances to propyl cyanide, and to exhibit strong branching, with the sec form clearly dominant over all others. Normal and iso-butyl cyanide are expected to have similar abundances to each other, while the tert form is significantly less abundant. The addition of CN to acetylene and ethene is found to be important to the production of vinyl, ethyl, propyl, and butyl

  3. Study of Copper and Purine-Copper Complexes on Modified Carbon Electrodes by Cyclic and Elimination Voltammetry

    Science.gov (United States)

    Trnkova, Libuse; Zerzankova, Lenka; Dycka, Filip; Mikelova, Radka; Jelen, Frantisek

    2008-01-01

    Using a paraffin impregnated graphite electrode (PIGE) and mercury-modified pyrolytic graphite electrode with basal orientation (Hg-PGEb) copper(II) and Cu(II)-DNA purine base solutions have been studied by cyclic (CV) and linear sweep voltammetry (LSV) in connection with elimination voltammetry with linear scan (EVLS). In chloride and bromide solutions (pH 6), the redox process of Cu(II) proceeded on PIGE with two cathodic and two anodic potentially separated signals. According to the elimination function E4, the first cathodic peak corresponds to the reduction Cu(II) + e- → Cu(I) with the possibility of fast disproportionation 2Cu(I) → Cu(II)+ Cu(0). The E4 of the second cathodic peak signalized an electrode process controlled by a surface reaction. The electrode system of Cu(II) on Hg-PGEb in borate buffer (pH 9.2) was characterized by one cathodic and one anodic peak. Anodic stripping voltammetry (ASV) on PIGE and cathodic stripping voltammetry (CSV) on Hg-PGEb were carried out at potentials where the reduction of copper ions took place and Cu(I)-purine complexes were formed. By using ASV and CSV in combination with EVLS, the sensitivity of Cu(I)-purine complex detection was enhanced relative to either ASV or CSV alone, resulting in higher peak currents of more than one order of magnitude. The statistical treatment of CE data was used to determine the reproducibility of measurements. Our results show that EVLS in connection with the stripping procedure is useful for both qualitative and quantitative microanalysis of purine derivatives and can also reveal details of studied electrode processes. PMID:27879715

  4. Robust binding between carbon nitride nanosheets and a binuclear ruthenium(II) complex enabling durable, selective CO{sub 2} reduction under visible light in aqueous solution

    Energy Technology Data Exchange (ETDEWEB)

    Kuriki, Ryo; Ishitani, Osamu; Maeda, Kazuhiko [Department of Chemistry, School of Science, Tokyo Institute of Technology (Japan); Yamamoto, Muneaki; Yoshida, Tomoko [Advanced Research Institute for Natural Science and Technology, Osaka City University (Japan); Higuchi, Kimitaka; Yamamoto, Yuta; Akatsuka, Masato; Yagi, Shinya [Institute of Materials and Systems for Sustainability, Nagoya University (Japan); Lu, Daling [Suzukakedai Materials Analysis Division, Technical Department, Tokyo Institute of Technology, Yokohama (Japan)

    2017-04-18

    Carbon nitride nanosheets (NS-C{sub 3}N{sub 4}) were found to undergo robust binding with a binuclear ruthenium(II) complex (RuRu') even in basic aqueous solution. A hybrid material consisting of NS-C{sub 3}N{sub 4} (further modified with nanoparticulate Ag) and RuRu' promoted the photocatalytic reduction of CO{sub 2} to formate in aqueous media, in conjunction with high selectivity (approximately 98 %) and a good turnover number (>2000 with respect to the loaded Ru complex). These represent the highest values yet reported for a powder-based photocatalytic system during CO{sub 2} reduction under visible light in an aqueous environment. We also assessed the desorption of RuRu' from the Ag/C{sub 3}N{sub 4} surface, a factor that can contribute to a loss of activity. It was determined that desorption is not induced by salt additives, pH changes, or photoirradiation, which partly explains the high photocatalytic performance of this material. (copyright 2017 Wiley-VCH Verlag GmbH and Co. KGaA, Weinheim)

  5. BaFe12O19-chitosan Schiff-base Ag (I) complexes embedded in carbon nanotube networks for high-performance electromagnetic materials.

    Science.gov (United States)

    Zhao, Jie; Xie, Yu; Guan, Dongsheng; Hua, Helin; Zhong, Rong; Qin, Yuancheng; Fang, Jing; Liu, Huilong; Chen, Junhong

    2015-07-28

    The multiwalled carbon nanotubes/BaFe12O19-chitosan (MCNTs/BF-CS) Schiff base Ag (I) complex composites were synthesized successfully by a chemical bonding method. The morphology and structures of the composites were characterized with electron microscopy, Fourier transform infrared spectroscopy and X-ray diffraction techniques. Their conductive properties were measured using a four-probe conductivity tester at room temperature, and their magnetic properties were tested by a vibrating sample magnetometer. The results show that the BF-CS Schiff base Ag (I) complexes are embedded into MCNT networks. When the mass ratio of MCNTs and BF-CS Schiff base is 0.95:1, the conductivity, Ms (saturation magnetization), Mr (residual magnetization), and Hc (coercivity) of the BF-CS Schiff base composites reach 1.908 S cm(-1), 28.20 emu g(-1), 16.66 emu g(-1) and 3604.79 Oe, respectively. Finally, a possible magnetic mechanism of the composites has also been proposed.

  6. CAl2Be3(2-) and its salt complex LiCAl2Be3-: anionic global minima with planar pentacoordinate carbon.

    Science.gov (United States)

    Wu, Yan-Bo; Duan, Yan; Lu, Hai-Gang; Li, Si-Dian

    2012-03-29

    Following the isoelectronic relationship in global minima planar pentacoordinate carbon (ppC) species (cationic CAl(5)(+), neutral CAl(4)Be, and monoanionic CAl(3)Be(2)(-)), we designed a dianionic ppC species C(2v) CAl(2)Be(3)(2-) (1a) and its salt complex C(2v) LiCAl(2)Be(3)(-) (2a) in this work. In combination with DFT and high-level ab initio calculations (CCSD(T)), the extensive exploration on their potential energy surfaces indicates that they are the global minima. Their kinetic stability was proved by two sets of 100 ps ab initio Born-Oppenheimer molecular dynamic simulations at the B3LYP/6-31+G(d) level. The detailed analyses indicate that the introduction of Li(+) into 1a only influences the electrovalent bonding (through changing of the charge distribution) and the σ aromaticity (through changing of the in-plane ring current), while the structures, the bonding properties, the π aromaticity, and so forth are almost unchanged. Nevertheless, the MO energy levels, the HOMO-LUMO gaps, and the values of vertical detachment energies (VDEs) all verify that the lithiation significantly improves the stability. We think the ppC dianion 1a is possible to detect directly in the gas-phase experiments, but it can be detected as its salt complex 2a more easily.

  7. Formation of molecular complexes of salicylic acid, acetylsalicylic acid, and methyl salicylate in a mixture of supercritical carbon dioxide with a polar cosolvent

    Science.gov (United States)

    Petrenko, V. E.; Antipova, M. L.; Gurina, D. L.; Odintsova, E. G.

    2015-08-01

    The solvate structures formed by salicylic acid, acetylsalicylic acid, and methyl salicylate in supercritical (SC) carbon dioxide with a polar cosolvent (methanol, 0.03 mole fractions) at a density of 0.7 g/cm3 and a temperature of 318 K were studied by the molecular dynamics method. Salicylic and acetylsalicylic acids were found to form highly stable hydrogen-bonded complexes with methanol via the hydrogen atom of the carboxyl group. For methyl salicylate in which the carboxyl hydrogen is substituted by a methyl radical, the formation of stable hydrogen bonds with methanol was not revealed. The contribution of other functional groups of the solute to the interactions with the cosolvent was much smaller. An analysis of correlations between the obtained data and the literature data on the cosolvent effect on the solubility of the compounds in SC CO2 showed that the dissolving ability of SC CO2 with respect to a polar organic substance in the presence of a cosolvent increased only when stable hydrogen-bonded complexes are formed between this substance and the cosolvent.

  8. Five Coordinate Platinum(II in [Pt(bpy(cod(Me][SbF6]: A Structural and Spectroscopic Study

    Directory of Open Access Journals (Sweden)

    Axel Klein

    2015-05-01

    Full Text Available The five coordinate organoplatinum complex [Pt(bpy(cod(Me][SbF6] (cod = 1,5-cyclooctadiene, bpy = 2,2’-bipyridine was obtained reacting [Pt(cod(MeCl] with Ag[SbF6] and bpy and characterized by multiple spectroscopy (IR and NMR and single crystal XRD. Although the application of the τ values for the discrimination between trigonal bipyramidal vs. square pyramidal coordination fails, the molecular structure can be unequivocally described as basally-distorted trigonal bipyramidal. Detailed multinuclear NMR spectroscopy in solution at ambient temperature gives strong evidence for the same structure; corresponding low-temperature measurements down to −70 °C revealed no marked dynamic processes.

  9. Thermodynamic and kinetic studies of the equilibration reaction between the sulfur and carbon bonded forms of a cobalt(III) complex with the ligands 1,4,7-triazycyclononane and 1,4-diaza-7-thiacyclodecane

    DEFF Research Database (Denmark)

    Song, Y.S.; Becker, J.; Kofod, Pauli

    1996-01-01

    -sulfur complex to form the alkyl complex gave 100% loss of deuterium. It is concluded that the labile methylene proton is bound to the carbon atom which in the alkyl complex is bound to cobalt(III). From the kinetic data it is estd. that the carbanion reacts with water 270 times faster than it is captured......The new cyclic thioether 1,4-diaza-7-thiacyclodecane, dathicd, has been synthesized and used for the prepn. of the sulfur- and carbon-bonded cobalt(III) complexes: [Co(tacn)(S-dathicd)]Cl3.5H2O and [Co(tacn)(C-dathicd)](ClO4)2 (tacn, 1,4,7-triazacyclononane; C-dathicd, 1,4-diamino-7-thiacyclodecan...

  10. Development of quercetin-phospholipid complex to improve the bioavailability and protection effects against carbon tetrachloride-induced hepatotoxicity in SD rats.

    Science.gov (United States)

    Zhang, Kexia; Zhang, Meiyu; Liu, Ziying; Zhang, Yuanyuan; Gu, Liqiang; Hu, Gaosheng; Chen, Xiaohui; Jia, Jingming

    2016-09-01

    Quercetin (QT) is a natural flavonoid with various biological activities and pharmacological actions. However, the bioavailability of QT is relatively low due to its low solubility which severely limits its use. In this study, we intended to improve the bioavailability of QT by preparing quercetin-phospholipid complex (QT-PC) and investigate the protective effect of QT-PC against carbon tetrachloride (CCl4) induced acute liver damage in Sprague-Dawley (SD) rats. The physicochemical properties of QT-PC were characterized in terms of infrared spectroscopy (FTIR), differential scanning calorimetry (DSC), powder X-ray diffraction (XRPD) and water/n-octanol solubility. FTIR, DSC and XRPD data confirmed the formation of QT-PC. The water solubility of QT was improved significantly in the prepared complex, indicating its increased hydrophilicity. Oral bioavailability of QT and QT-PC was evaluated in SD rats, and the plasma QT was estimated by HPLC-MS. QT-PC exhibited higher Cmax (1.58±0.11 vs. 0.67±0.08μg/mL), increased AUC0-∞ (8.60±1.25 vs. 2.41±0.51mg/Lh) and t1/2z (7.76±1.09 vs. 4.81±0.87h) when compared to free QT. The greater absorption of QT-PC group suggested the improved bioavailability. Moreover, biochemical changes and histopathological observations revealed that QT-PC provided better protection to rat liver than free QT at the same dose. Thus, phospholipid complexation might be one of the suitable approaches to improve the oral bioavailability of QT and obtain better protective effects against CCl4 induced acute liver damage in SD rats than free QT at the same dose level.

  11. Planting increases the abundance and structure complexity of soil core functional genes relevant to carbon and nitrogen cycling.

    Science.gov (United States)

    Wang, Feng; Liang, Yuting; Jiang, Yuji; Yang, Yunfeng; Xue, Kai; Xiong, Jinbo; Zhou, Jizhong; Sun, Bo

    2015-09-23

    Plants have an important impact on soil microbial communities and their functions. However, how plants determine the microbial composition and network interactions is still poorly understood. During a four-year field experiment, we investigated the functional gene composition of three types of soils (Phaeozem, Cambisols and Acrisol) under maize planting and bare fallow regimes located in cold temperate, warm temperate and subtropical regions, respectively. The core genes were identified using high-throughput functional gene microarray (GeoChip 3.0), and functional molecular ecological networks (fMENs) were subsequently developed with the random matrix theory (RMT)-based conceptual framework. Our results demonstrated that planting significantly (P soils and 83.5% of microbial alpha-diversity can be explained by the plant factor. Moreover, planting had significant impacts on the microbial community structure and the network interactions of the microbial communities. The calculated network complexity was higher under maize planting than under bare fallow regimes. The increase of the functional genes led to an increase in both soil respiration and nitrification potential with maize planting, indicating that changes in the soil microbial communities and network interactions influenced ecological functioning.

  12. Pyrazine-based organometallic complex: synthesis, characterization, and supramolecular chemistry.

    Science.gov (United States)

    Bhowmick, Sourav; Chakraborty, Sourav; Das, Atanu; Rajamohanan, P R; Das, Neeladri

    2015-03-16

    The design, synthesis, and characterization of a new pyrazine-based ditopic platinum(II) organometallic complex are reported. The molecular structure of the organoplatinum pyrazine dipod was determined by single-crystal X-ray crystallography. The potential utility of this organometallic ditopic acceptor as a building block in the construction of neutral metallasupramolecular macrocycles containing the pyrazine motif was explored. Pyrazine motifs containing supramolecules were characterized by multinuclear NMR (including (1)H DOSY), mass spectrometry, and elemental analysis. The geometry of each supramolecular framework was optimized by employing the PM6 semiempirical molecular orbital method to predict its shape and size. The ability of the pyrazine-based organoplatinum complex to act as a host for nitroaromatic guest (2,4-dinitrotoluene and PA) molecules was explored by isothermal titration calorimetry (ITC). The binding stoichiometry and thermodynamic parameters of these host-guest complexation reactions were evaluated using ITC. Theoretical calculations were performed to obtain insight into the binding pattern between the organometallic host and nitroaromatic guests. The preferable binding propensity of the binding sites of complex 1 for both nitroaromatics (PA and 2,4-dinitrotoluene) determined by molecular simulation studies corroborates well with the experimental results as obtained by ITC experiments.

  13. Study of Copper and Purine-Copper Complexes on Modified Carbon Electrodes by Cyclic and Elimination Voltammetry

    Directory of Open Access Journals (Sweden)

    Frantisek Jelen

    2008-01-01

    Full Text Available Using a paraffin impregnated graphite electrode (PIGE and mercury-modifiedpyrolytic graphite electrode with basal orientation (Hg-PGEb copper(II and Cu(II-DNApurine base solutions have been studied by cyclic (CV and linear sweep voltammetry(LSV in connection with elimination voltammetry with linear scan (EVLS. In chlorideand bromide solutions (pH 6, the redox process of Cu(II proceeded on PIGE with twocathodic and two anodic potentially separated signals. According to the eliminationfunction E4, the first cathodic peak corresponds to the reduction Cu(II e- → Cu(I withthe possibility of fast disproportionation 2Cu(I → Cu(II Cu(0. The E4 of the secondcathodic peak signalized an electrode process controlled by a surface reaction. Theelectrode system of Cu(II on Hg-PGEb in borate buffer (pH 9.2 was characterized by onecathodic and one anodic peak. Anodic stripping voltammetry (ASV on PIGE and cathodicstripping voltammetry (CSV on Hg-PGEb were carried out at potentials where thereduction of copper ions took place and Cu(I-purine complexes were formed. By usingASV and CSV in combination with EVLS, the sensitivity of Cu(I-purine complexdetection was enhanced relative to either ASV or CSV alone, resulting in higher peakcurrents of more than one order of magnitude. The statistical treatment of CE data wasused to determine the reproducibility of measurements. Our results show that EVLS inconnection with the stripping procedure is useful for both qualitative and quantitativemicroanalysis of purine derivatives and can also reveal details of studied electrodeprocesses.

  14. Study of Copper and Purine-Copper Complexes on Modified Carbon Electrodes by Cyclic and Elimination Voltammetry.

    Science.gov (United States)

    Trnkova, Libuse; Zerzankova, Lenka; Dycka, Filip; Mikelova, Radka; Jelen, Frantisek

    2008-01-24

    Using a paraffin impregnated graphite electrode (PIGE) and mercury-modifiedpyrolytic graphite electrode with basal orientation (Hg-PGEb) copper(II) and Cu(II)-DNApurine base solutions have been studied by cyclic (CV) and linear sweep voltammetry(LSV) in connection with elimination voltammetry with linear scan (EVLS). In chlorideand bromide solutions (pH 6), the redox process of Cu(II) proceeded on PIGE with twocathodic and two anodic potentially separated signals. According to the eliminationfunction E4, the first cathodic peak corresponds to the reduction Cu(II) e⁻ → Cu(I) withthe possibility of fast disproportionation 2Cu(I) → Cu(II) Cu(0). The E4 of the secondcathodic peak signalized an electrode process controlled by a surface reaction. Theelectrode system of Cu(II) on Hg-PGEb in borate buffer (pH 9.2) was characterized by onecathodic and one anodic peak. Anodic stripping voltammetry (ASV) on PIGE and cathodicstripping voltammetry (CSV) on Hg-PGEb were carried out at potentials where thereduction of copper ions took place and Cu(I)-purine complexes were formed. By usingASV and CSV in combination with EVLS, the sensitivity of Cu(I)-purine complexdetection was enhanced relative to either ASV or CSV alone, resulting in higher peakcurrents of more than one order of magnitude. The statistical treatment of CE data wasused to determine the reproducibility of measurements. Our results show that EVLS inconnection with the stripping procedure is useful for both qualitative and quantitativemicroanalysis of purine derivatives and can also reveal details of studied electrodeprocesses.

  15. 碳纳米管-苯胺电荷转移复合物中的胺荧光淬灭效应%Quenching Effects of Amine on Fluorescence of Carbon Nanotube-Aniline Charge Transfer Complex

    Institute of Scientific and Technical Information of China (English)

    SUN Xu-feng; WANG Yu; JIN Wei-jun

    2005-01-01

    Under refluxing, carbon nanotube (CNT) and aniline (An) can form the charge transfer complex (CTC) of CNT-An.The corresponding fluorescence emission peaks lied at 564nm and 606nm, respectively, with the excitation wavelength of 516nm in the acetone solution. The quenching effects of various amines on CNT- An CTC fluorescence were investigated in detail.

  16. Toxicity of cobalt-complexed cyanide to Oncorhynchus mykiss, Daphnia magna, and Ceriodaphnia dubia: Potentiation by ultraviolet radiation and attenuation by dissolved organic carbon and adaptive UV tolerance

    Science.gov (United States)

    Little, Edward E.; Calfee, Robin D.; Theodorakos, Peter M.; Brown, Zoe Ann; Johnson, Craig A.

    2007-01-01

    BackgroundCobalt cyanide complexes often result when ore is treated with cyanide solutions to extract gold and other metals. These have recently been discovered in low but significant concentrations in effluents from gold leach operations. This study was conducted to determine the potential toxicity of cobalt-cyanide complexes to freshwater organisms and the extent to which ultraviolet radiation (UV) potentiates this toxicity. Tests were also conducted to determine if humic acids or if adaptation to UV influenced sensitivity to the cyanide complexes.MethodsRainbow trout (Oncorhynchus mykiss), Daphnia magna, and Ceriodaphnia dubia were exposed to potassium hexacyanocobaltate in the presence and absence of UV radiation, in the presence and absence of humic acids. Cyano-cobalt exposures were also conducted with C. dubia from cultures adapted to elevated UV.ResultsWith an LC50 concentration of 0.38 mg/L, cyanocobalt was over a 1000 times more toxic to rainbow trout in the presence of UV at a low, environmentally relevant irradiance level (4 μW/cm2 as UVB) than exposure to this compound in the absence of UV with an LC50 of 112.9 mg/L. Toxicity was immediately apparent, with mortality occurring within an hour of the onset of exposure at the highest concentration. Fish were unaffected by exposure to UV alone. Weak-acid dissociable cyanide concentrations were observed in irradiated aqueous solutions of cyanocobaltate within hours of UV exposure and persisted in the presence of UV for at least 96 hours, whereas negligible concentrations were observed in the absence of UV. The presence of humic acids significantly diminished cyanocobalt toxicity to D. magna and reduced mortality from UV exposure. Humic acids did not significantly influence survival among C. dubia. C. dubia from UV-adapted populations were less sensitive to metallocyanide compounds than organisms from unadapted populations.ConclusionsThe results indicate that metallocyanide complexes may pose a hazard to

  17. REE: Alkaline intensive and carbonates complexes at Fuerteventura (Canary Islands). Mineralizaciones de tierras raras: los complejos de rocas plutonicas alcalinas y carbonatitas del complejo basal de Fuerteventura (Islas Canarias)

    Energy Technology Data Exchange (ETDEWEB)

    Mangas Viuela, J.; Perez Torrado, F.J.

    1993-01-01

    Alkaline intrusive complexes at Fuerteventura have been explored as potential source of REE. Two main complexes constituted by ultramafic to salic rocks and carbonatitas are present in the island: the Puerto de la Pea-Cueva de Lobos (= 60 Ma) in the western centerpoint and the Esquinzo (=30 Ma) in the northern zone. The calciocarbonatites (sovites and alwikites), formed in the last crystallization phases of these complexes, show the highest values of REE (511-7,372 ppm) and these elements mainly are associated with carbonates (synchysite), phosphates (REE apatite), silicates (allanite). (Author) 17 refs.

  18. Alkali-metal ion coordination in uranyl(VI) poly-peroxo complexes in solution, inorganic analogues to crown-ethers. Part 2. Complex formation in the tetramethyl ammonium-, Li(+)-, Na(+)- and K(+)-uranyl(VI)-peroxide-carbonate systems.

    Science.gov (United States)

    Zanonato, Pier Luigi; Szabó, Zoltán; Vallet, Valerie; Di Bernardo, Plinio; Grenthe, Ingmar

    2015-10-01

    The constitution and equilibrium constants of ternary uranyl(vi) peroxide carbonate complexes [(UO2)p(O2)q(CO3)r](2(p-q-r)) have been determined at 0 °C in 0.50 M MNO3, M = Li, K, and TMA (tetramethyl ammonium), ionic media using potentiometric and spectrophotometric data; (17)O NMR data were used to determine the number of complexes present. The formation of cyclic oligomers, "[(UO2)(O2)(CO3)]n", n = 4, 5, 6, with different stoichiometries depending on the ionic medium used, suggests that Li(+), Na(+), K(+) and TMA ions act as templates for the formation of uranyl peroxide rings where the uranyl-units are linked by μ-η(2)-η(2) bridged peroxide-ions. The templating effect is due to the coordination of the M(+)-ions to the uranyl oxygen atoms, where the coordination of Li(+) results in the formation of Li[(UO2)(O2)(CO3)]4(7-), Na(+) and K(+) in the formation of Na/K[(UO2)(O2)(CO3)]5(9-) complexes, while the large tetramethyl ammonium ion promotes the formation of two oligomers, TMA[(UO2)(O2)(CO3)]5(9-) and TMA[(UO2)(O2)(CO3)]6(11-). The NMR spectra demonstrate that the coordination of Na(+) in the five- and six-membered oligomers is significantly stronger than that of TMA(+); these observations suggest that the templating effect is similar to the one observed in the synthesis of crown-ethers. The NMR experiments also demonstrate that the exchange between TMA[(UO2)(O2)(CO3)]5(9-) and TMA[(UO2)(O2)(CO3)]6(11-) is slow on the (17)O chemical shift time-scale, while the exchange between TMA[(UO2)(O2)(CO3)]6(11-) and Na[(UO2)(O2)(CO3)]6(11-) is fast. There was no indication of the presence of large clusters of the type identified by Burns and Nyman (M. Nyman and P. C. Burns, Chem. Soc. Rev., 2012, 41, 7314-7367) and possible reasons for this and the implications for the synthesis of large clusters are briefly discussed.

  19. Immobilized organoruthenium(II) complexes onto polyethyleneimine-wrapped carbon nanotubes/in situ formed gold nanoparticles as a novel electrochemical sensing platform

    Energy Technology Data Exchange (ETDEWEB)

    Azadbakht, Azadeh, E-mail: Azadbakht.a@gmail.com; Abbasi, Amir Reza; Derikvand, Zohreh; Amraei, Shiba

    2015-03-01

    The polyethyleneimine (PEI) wrapped multi-walled carbon nanotubes functionalized with a carboxylic acid group (CNTs–COOH) gold nanoparticle (AuNP)-modified gold (Au) electrode has been utilized as a platform to immobilize organoruthenium(II) complexes (ORC). The surface structure and composition of the sensor were characterized by scanning electron microscopy (SEM). Electrocatalytic reduction of iodate and nitrite on the surface of modified electrode was investigated with cyclic voltammetry, electrochemical impedance spectroscopy (EIS) and hydrodynamic voltammetry methods. The cyclic voltammetric results indicated the ability of AuNPs/PEI/CNT–COOH/ORC modified Au electrode to catalyze the reduction of this compound. AuNPs/PEI/CNTs–COOH nanocomposite combined the advantages of PEI-well dispersed CNTs–COOH and in situ formed AuNPs. - Highlights: • We prepared composite containing polyethyleneimine (PEI), CNTs and AuNPs. • AuNPs were in situ formed on the surface of CNTs–PEI. • When the AuNPs were in situ formed the stability would be improved. • Nanocomposite combined the advantages of PEI–CNTs and in situ formed AuNPs. • Modified nanocomposite Au electrode catalyzes the reduction of iodate and nitrite.

  20. RING-OPENING POLYMERIZAION OF 2,2-DIMETHYLTRIMETHYLENE CARBONATE INITIATED BY IN SITU GENERATED, TETRAHYDROSALEN STABLIZED YTTRIUM BOROHYDRIDE COMPLEX AND RANDOM COPOLYMERIZATION WITH ε-CAPROLACTONE

    Institute of Scientific and Technical Information of China (English)

    Jing Huang; Jian-fang Yu; Han-jian Yu; Wei-lin Sun; Zhi-quan Shen

    2011-01-01

    The poly(2,2-dimethyltrimethylene carbonate) (PDTC) with one hydroxyl and one formate tenninal fimctions was synthesized by in situ generated, tetrahydrosalen stabilized yttrium borohydride complex. The influences of monomer/initiator molar ratio, temperature and reaction time on polymerization of DTC were investigated. Under the condition: [DTC]/[I] = 500, 55℃, toluene: 0.5 mL, DTC: 0.6 g, PDTC with Mn = 15600 and PDI = 2.15 was obtained.Through 1H-NMR and 13C-NMR analyses, the structure of PDTC was characterized and a coordination-insertion mechanism was proposed. In addition, the random copolymerization of DTC and caprolactone (CL) initiated by rare-earth borohydride compound was studied. The microstructure of PDTC-co-PCL includes four diads: DTC-CL, CL-CL, DTC-DTC and CLDTC, which were determined by the specific signals in 1H-NMR spectra. Based on the typical signals of the formate (δ=8.08) and hydroxyl (δ = 3.34) end groups of PDTC-co-PCL, a mechanism involving DTC monomer inserts before CL during the initiation process was presumed. Furthermore, the thermal properties of amorphous copolymer were characterized by differential scanning calorimetry (DSC). The results support the random structure of PDTC-co-PCL.

  1. Determination of total selenium content in sediments and natural water by graphite furnace-atomic absorption spectroscopy after collection as a selenium(IV) complex on activated carbon.

    Science.gov (United States)

    Kubota, T; Suzuki, K; Okutani, T

    1995-07-01

    A trace level of Se was collected on activated carbon (AC) as the Se(IV)-3-phenyl-5-mercapto-1,3,4-thiadiazole-2(3H)-thione (Bismuthiol II) complex. The AC was directly introduced as an AC-suspension into the graphite tube atomizer and the Se concentration was determined by atomic absorption spectroscopy (T. Okutani, T. Kubota, N. Sugiyama and Y. Turuta, Nippon Kagaku Kaishi, (1991) 375). The amount of Se in heavily contaminated samples including sediment, lake water and seawater was determined using this method. The sediments were digested with HNO(3)HClO(4)HF and the interference from AlF(3) was removed using H(3)BO(3)HClO(4). Lake water and seawater were acidified with H(2)SO(4) and digested with KMnO(4). The Se concentrations of these samples were determined by this method with satisfactory results. The above method is simple, rapid and applicable to heavily contaminated samples.

  2. Controlled synthesis, formation mechanism, and carbon oxidation properties of Ho2Cu2O5 nanoplates prepared with a coordination-complex method

    Science.gov (United States)

    Guo, Rui; You, Junhua; Han, Fei; Li, Chaoyang; Zheng, Guiyuan; Xiao, Weicheng; Liu, Xuanwen

    2017-02-01

    Ho2Cu2O5 nanoplates with perovskite structures were synthesized via a simple solution method (SSM) and a coordination-complex method (CCM) using [HoCu(3,4-pdc)2(OAc)(H2O)3]·8H2O (L = 3,4-pyridinedicarboxylic acid) as a precursor. The CCM was also performed in an N2 environment (CCMN) under various calcination conditions. The crystallization processes were characterized using X-ray diffraction, scanning electron microscopy, and high-resolution transmission electron microscopy. Ho2Cu2O5 formed through the diffusion of CuO into Ho2O3 particles. Cu2+ diffused faster than Ho3+ during this process. The initial products of CCMN (along with the thermal decomposition products) were initially laminarized in the N2 atmosphere, which prevented the growth of CuO particles and decreased the size of the Ho2Cu2O5 particles. The final Ho2Cu2O5 particles from CCMN had a nanoplate morphology with an average thickness of 75 nm. The decomposition of organic molecules and protection from N2 played important roles in determining the morphology of the resulting Ho2Cu2O5. The catalytic oxidation activity of Ho2Cu2O5 samples for carbon was characterized using a specific surface area measurement and thermogravimetric analysis, which revealed that the samples produced by CCMN had the highest catalytic activity.

  3. Warm ISM in the Sagittarius A Complex. I. Mid-J CO, atomic carbon, ionized atomic carbon, and ionized nitrogen sub-mm/FIR line observations with the Herschel-HIFI and NANTEN2/SMART telescopes

    Science.gov (United States)

    García, P.; Simon, R.; Stutzki, J.; Güsten, R.; Requena-Torres, M. A.; Higgins, R.

    2016-04-01

    Aims: We investigate the spatial and spectral distribution of the local standard of rest (LSR) velocity resolved submillimetre emission from the warm (25-90 K) gas in the Sgr A Complex, located in the Galactic centre. Methods: We present large-scale submillimetre heterodyne observations towards the Sgr A Complex covering ~300 arcmin2. These data were obtained in the frame of the Herschel EXtraGALactic guaranteed time key program (HEXGAL) with the Herschel-HIFI satellite and are complemented with submillimetre observations obtained with the NANTEN2/SMART telescope as part of the NANTEN2/SMART Central Nuclear Zone Survey. The observed species are CO(J = 4-3) at 461.0 GHz observed with the NANTEN2/SMART telescope, and [CI] 3P1-3P0 at 492.2 GHz, [CI] 3P2-3P1 at 809.3 GHz, [NII] 3P1-3P0 at 1461.1 GHz, and [CII] 2P3/2-2P1/2 at 1900.5 GHz observed with the Herschel-HIFI satellite. The observations are presented in a 1 km s-1 spectral resolution and a spatial resolution ranging from 46 arcsec to 28 arcsec. The spectral coverage of the three lower frequency lines is ±200 km s-1, while in the two high frequency lines, the upper LSR velocity limit is +94 km s-1 and +145 km s-1 for the [NII] and [CII] lines, respectively. Results: The spatial distribution of the emission in all lines is very widespread. The bulk of the carbon monoxide emission is found towards Galactic latitudes below the Galactic plane, and all the known molecular clouds are identified. Both neutral atomic carbon lines have their brightest emission associated with the +50 km s-1 cloud. Their spatial distribution at this LSR velocity describes a crescent-shape structure, which is probably the result of interaction with the energetic event (one or several supernovae explosions) that gave origin to the non-thermal Sgr A-East source. The [CII] and [NII] emissions have most of their flux associated with the thermal arched-filaments and the H region and bright spots in [CII] emission towards the central nuclear

  4. Synthesis, structure, and reactivity of iridium perfluorocarbene complexes: regio- and stereo-specific addition of HCl across a metal carbon double bond.

    Science.gov (United States)

    Yuan, Jian; Bourgeois, Cheryl J; Rheingold, Arnold L; Hughes, Russell P

    2015-12-07

    Reductive activation of an α-fluorine in the perfluoroalkyl complexes Cp*(L)(i)Ir-CF2RF using Mg/graphite leads to perfluorocarbene complexes Cp*(L)Ir[double bond, length as m-dash]CFRF (L = CO, PMe3; RF = CF3, C2F5, C6F5). New complexes E-Cp*(PMe3)Ir[double bond, length as m-dash]CFC2F5 and E-Cp*(CO)Ir[double bond, length as m-dash]CFC6F5 have been characterized by single crystal X-ray diffraction studies, and a comparison of metric parameters with previously reported analogues is reported. Experimental NMR and computational DFT (B3LYP/LACV3P**++) studies agree that for Ir[double bond, length as m-dash]CFRF complexes (RF = CF3, CF2CF3) the thermodynamic preference for the E or Z isomer depends on the steric requirements of ligand L; when L = CO the Z-isomer (F cis to Cp*) is preferred and for L = PMe3 the E-isomer is preferred. When reduction of the precursors is carried out in the dark the reaction is completely selective to produce E- or Z-isomers. Exposure of solutions of these compounds to ambient light results in slow conversion to a photostationary non-equilibrium mixture of E and Z isomers. In the dark, these E/Z mixtures convert thermally to their preferred E or Z equilibrium geometries in an even slower reaction. A study of the temperature dependent kinetics of this dark transformation allows ΔG(‡)298 for rotation about the Ir[double bond, length as m-dash]CFCF3 double bond to be experimentally determined as 25 kcal mol(-1); a DFT/B3LYP/LACV3P**++ calculation of this rotation barrier is in excellent agreement (27 kcal mol(-1)) with the experimental value. Reaction of HCl with toluene solutions of Cp*(L)Ir[double bond, length as m-dash]CFRF (L = CO, PMe3) or Cp*(CO)Ir[double bond, length as m-dash]C(CF3)2 at low temperature resulted in regiospecific addition of HCl across the metal carbon double bond, ultimately yielding Cp*(L)Ir(CHFRF)Cl and Cp*(CO)Ir[CH(CF3)2]Cl. Reaction of HCl with single E or Z diastereomers of Cp*(L)Ir[double bond, length as m

  5. Sintesi, reattività, chiralità in complessi di Pt(II)

    OpenAIRE

    Sini, Alessandro

    2010-01-01

    My PhD thesis concerns basically the synthesis and reactivity of organometallic platinum(II) complexes with pyridine and bipyridine ligands. These complexes are very interesting due to their applications in many fields: catalysis, biology and farmacology, photophysic and photochemistry. Chirality of several complexes with 2-R-pyridines, S-(-)-nicotine and 1,2-bis(2-pyridil)benzene has been carefully taken into account. Concerning bipyridine complexes, reactivity with carbon monoxide and phosp...

  6. Changes of soil organic carbon and complex iron in Momoge Wetland%莫莫格湿地土壤有机碳与络合态铁的动态变化

    Institute of Scientific and Technical Information of China (English)

    于秀丽; 许林书

    2012-01-01

    The temporal changes of soil organic carbon and complex iron content were studied in three types wetland soil of Momoge Wetlands, which include Phragmites marsh and Leymus chinensis meadow and Phragmites-Leymus chinensis meadow. The result showed that the highest content of soil total organic carbon is in Phragmites marsh,followed by Leymus chinensis meadow and the lowest is in Phragmites-Leymus chinensis meadow. The content of soil complex iron has the same variation as soil total organic carbon. However, the highest content of soil dissolved organic carbon is in Leymus chinensis meadow,followed by Phragmites-Leymus chinensis meadow and the lowest is in Phragmites marsh. With the soil depth increases,the content of soil total organic carbon,dissolved organic carbon and complex iron decreased gradually. Correlation analysis showed that in the vertical change soil total organic carbon and dissolved organic carbon were positively correlated with soil complex iron. And in the seasonal variation,soil complex iron was negatively correlated with total organic carbon;Between soil dissolved organic carbon with complex iron there were significantly negative correlations in Phragmites marsh and Leymus chinensis meadow soil, but there were significantly negative correlations in Phragmites-Leymus chinensis meadow.%以莫莫格芦苇沼泽、芦苇-羊草草甸和羊草草甸3种类型湿地土壤为对象,研究了土壤总有机碳(TOC)、溶解有机碳(DOC)和络合态铁的动态变化情况.结果表明:3种类型湿地土壤TOC含量芦苇沼泽最高,羊草草旬次之,芦苇-羊草草甸最低;土壤络合态铁含量变化规律与TOC变化相同;土壤DOC含量则表现为羊草草甸最高,芦苇-羊草草甸次之,芦苇沼泽最低.随着土层深度的增加,湿地土壤TOC、DOC以及络合态铁含量都表现为自表层向深层递减的规律.相关性分析表明:从垂直动态变化看,土壤络合态铁与土壤TOC、DOC含量均有正相关关系

  7. σ-Aromatic cyclic M3(+) (M = Cu, Ag, Au) clusters and their complexation with dimethyl imidazol-2-ylidene, pyridine, isoxazole, furan, noble gases and carbon monoxide.

    Science.gov (United States)

    Pan, Sudip; Saha, Ranajit; Mandal, Subhajit; Chattaraj, Pratim K

    2016-04-28

    The σ-aromaticity of M3(+) (M = Cu, Ag, Au) is analyzed and compared with that of Li3(+) and a prototype σ-aromatic system, H3(+). Ligands (L) like dimethyl imidazol-2-ylidene, pyridine, isoxazole and furan are employed to stabilize these monocationic M3(+) clusters. They all bind M3(+) with favorable interaction energy. Dimethyl imidazol-2-ylidene forms the strongest bond with M3(+) followed by pyridine, isoxazole and furan. Electrostatic contribution is considerably more than that of orbital contribution in these M-L bonds. The orbital interaction arises from both L → M σ donation and L ← M back donation. M3(+) clusters also bind noble gas atoms and carbon monoxide effectively. In general, among the studied systems Au3(+) binds a given L most strongly followed by Cu3(+) and Ag3(+). Computation of the nucleus-independent chemical shift (NICS) and its different extensions like the NICS-rate and NICS in-plane component vs. NICS out-of-plane component shows that the σ-aromaticity in L bound M3(+) increases compared to that of bare clusters. The aromaticity in pyridine, isoxazole and furan bound Au3(+) complexes is quite comparable with that in the recently synthesized Zn3(C5(CH3)5)3(+). The energy gap between the highest occupied molecular orbital and the lowest unoccupied molecular orbital also increases upon binding with L. The blue-shift and red-shift in the C-O stretching frequency of M3(CO)3(+) and M3(OC)3(+), respectively, are analyzed through reverse polarization of the σ- and π-orbitals of CO as well as the relative amount of OC → M σ donation and M → CO π back donation. The electron density analysis is also performed to gain further insight into the nature of interaction.

  8. Neutron structure of human carbonic anhydrase II in complex with methazolamide: mapping the solvent and hydrogen-bonding patterns of an effective clinical drug

    Directory of Open Access Journals (Sweden)

    Mayank Aggarwal

    2016-09-01

    Full Text Available Carbonic anhydrases (CAs; EC 4.2.1.1 catalyze the interconversion of CO2 and HCO3−, and their inhibitors have long been used as diuretics and as a therapeutic treatment for many disorders such as glaucoma and epilepsy. Acetazolamide (AZM and methazolamide (MZM, a methyl derivative of AZM are two of the classical CA inhibitory drugs that have been used clinically for decades. The jointly refined X-ray/neutron structure of MZM in complex with human CA isoform II (hCA II has been determined to a resolution of 2.2 Å with an Rcryst of ∼16.0%. Presented in this article, along with only the second neutron structure of a clinical drug-bound hCA, is an in-depth structural comparison and analyses of differences in hydrogen-bonding network, water-molecule orientation and solvent displacement that take place upon the binding of AZM and MZM in the active site of hCA II. Even though MZM is slightly more hydrophobic and displaces more waters than AZM, the overall binding affinity (Ki for both of the drugs against hCA II is similar (∼10 nM. The plausible reasons behind this finding have also been discussed using molecular dynamics and X-ray crystal structures of hCA II–MZM determined at cryotemperature and room temperature. This study not only allows a direct comparison of the hydrogen bonding, protonation states and solvent orientation/displacement of AZM and MZM, but also shows the significant effect that the methyl derivative has on the solvent organization in the hCA II active site.

  9. EGFR-targeting peptide-coupled platinum(IV) complexes.

    Science.gov (United States)

    Mayr, Josef; Hager, Sonja; Koblmüller, Bettina; Klose, Matthias H M; Holste, Katharina; Fischer, Britta; Pelivan, Karla; Berger, Walter; Heffeter, Petra; Kowol, Christian R; Keppler, Bernhard K

    2017-06-01

    The high mortality rate of lung cancer patients and the frequent occurrence of side effects during cancer therapy demonstrate the need for more selective and targeted drugs. An important and well-established target for lung cancer treatment is the occasionally mutated epidermal growth factor receptor (EGFR). As platinum(II) drugs are still the most important therapeutics against lung cancer, we synthesized in this study the first platinum(IV) complexes coupled to the EGFR-targeting peptide LARLLT (and the shuffled RTALLL as reference). Notably, HPLC-MS measurements revealed two different peaks with the same molecular mass, which turned out to be a transcyclization reaction in the linker between maleimide and the coupled cysteine moiety. With regard to the EGFR specificity, subsequent biological investigations (3-day viability, 14-day clonogenic assays and platinum uptake) on four different cell lines with different verified EGFR expression levels were performed. Unexpectedly, the results showed neither an enhanced activity nor an EGFR expression-dependent uptake of our new compounds. Consequently, fluorophore-coupled peptides were synthesized to re-evaluate the targeting ability of LARLLT itself. However, also with these molecules, flow cytometry measurements showed no correlation of drug uptake with the EGFR expression levels. Taken together, we successfully synthesized the first platinum(IV) complexes coupled to an EGFR-targeting peptide; however, the biological investigations revealed that LARLLT is not an appropriate peptide for enhancing the specific uptake of small-molecule drugs into EGFR-overexpressing cancer cells.

  10. Metal-mediated controllable creation of secondary, tertiary, and quaternary carbon centers: a powerful strategy for the synthesis of iron, cobalt, and copper complexes with in situ generated substituted 1-pyridineimidazo[1,5-a]pyridine ligands.

    Science.gov (United States)

    Chen, Yanmei; Li, Lei; Chen, Zhou; Liu, Yonglu; Hu, Hailiang; Chen, Wenqian; Liu, Wei; Li, Yahong; Lei, Tao; Cao, Yanyuan; Kang, Zhenghui; Lin, Miaoshui; Li, Wu

    2012-09-17

    An efficient strategy for the synthesis of a wide variety of coordination complexes has been developed. The synthetic protocol involves a solvothermal in situ metal-ligand reaction of picolinaldehyde, ammonium acetate, and transition-metal ions, leading to the generation of 12 coordination complexes supported by a novel class of substituted 1-pyridineimidazo[1,5-a]pyridine ligands (L1-L5). The ligands L1-L5 were afforded by metal-mediated controllable conversion of the aldehyde group of picolialdehyde into a ketone and secondary, tertiary, and quaternary carbon centers, respectively. Complexes of various nuclearities were obtained: from mono-, di-, and tetranuclear to 1D chain polymers. The structures of the in situ formed complexes could be controlled rationally via the choice of appropriate starting materials and tuning of the ratio of the starting materials. The plausible mechanisms for the formation of the ligands L1-L5 were proposed.

  11. Mammary excretion and placental transfer of cis-malonato[(4R,5R)-4,5-bis(aminomethyl)-2-isopropyl-1,3-dioxolane] platinum(II) in rats.

    Science.gov (United States)

    Cho, Y B; Kim, K H; Kim, D K; Miyamoto, G

    1996-09-01

    The mammary excretion and placental transfer of cis-malonato[(4R,5R)-4,5-bis(aminomethyl)-2-isopropyl-1,3-dioxolan e] platinum(II) (CAS 146665-77-2, SKI 2053R), a new potential anticancer agent, were investigated in the lactating or pregnant rats after a single intravenous administration of 14C-SKI 2053R (20 mg/kg, 100 microCi/kg). The radioactivity of the milk declined in a biexponential fashion with an initial half-life of 0.39 h and with a terminal half-life of 14.05 h in the lactating rats. The radioactivity of the milk was lower than that of plasma until 1 h after dosing, but was higher than that of plasma from 4 h after dosing. 14C-SKI 2053R was well distributed to most tissues including uterus and placenta in the pregnant rats, but the levels of radioactivity in the amniotic fluid and fetuses were markedly lower than that in the maternal plasma. Therefore, it is concluded that SKI 2053R scarcely passes the blood-placenta barrier, which was confirmed by the whole-body autoradiography study.

  12. Fixation of carbon dioxide by macrocyclic lanthanide(III) complexes under neutral conditions producing self-assembled trimeric carbonato-bridged compounds with μ3-η2:η2:η2 bonding.

    Science.gov (United States)

    Bag, Pradip; Dutta, Supriya; Biswas, Papu; Maji, Swarup Kumar; Flörke, Ulrich; Nag, Kamalaksha

    2012-03-28

    A series of mononuclear lanthanide(III) complexes [Ln(LH(2))(H(2)O)(3)Cl](ClO(4))(2) (Ln = La, Nd, Sm, Eu, Gd, Tb, Lu) of the tetraiminodiphenolate macrocyclic ligand (LH(2)) in 95 : 5 (v/v) methanol-water solution fix atmospheric carbon dioxide to produce the carbonato-bridged trinuclear complexes [{Ln(LH(2))(H(2)O)Cl}(3)(μ(3)-CO(3))](ClO(4))(4)·nH(2)O. Under similar conditions, the mononuclear Y(III) complex forms the dimeric compound [{Y(LH(2))(H(2)O)Cl}(μ(2)-CO(3)){Y(LH(2))(H(2)O)(2)}](ClO(4))(3)·4H(2)O. These complexes have been characterized by their IR and NMR ((1)H, (13)C) spectra. The X-ray crystal structures have been determined for the trinuclear carbonato-bridged compounds of Nd(III), Gd(III) and Tb(III) and the dinuclear compound of Y(III). In all cases, each of the metal centers are 8-coordinate involving two imine nitrogens and two phenolate oxygens of the macrocyclic ligand (LH(2)) whose two other imines are protonated and intramolecularly hydrogen-bonded with the phenolate oxygens. The oxygen atoms of the carbonate anion in the trinuclear complexes are bonded to the metal ions in tris-bidentate μ(3)-η(2):η(2):η(2) fashion, while they are in bis-bidentate μ(2)-η(2):η(2) mode in the Y(III) complex. The magnetic properties of the Gd(III) complex have been studied over the temperature range 2 to 300 K and the magnetic susceptibility data indicate a very weak antiferromagnetic exchange interaction (J = -0.042 cm(-1)) between the Gd(III) centers (S = 7/2) in the metal triangle through the carbonate bridge. The luminescence spectral behaviors of the complexes of Sm(III), Eu(III), and Tb(III) have been studied. The ligand LH(2) acts as a sensitizer for the metal ions in an acetonitrile-toluene glassy matrix (at 77 K) and luminescence intensities of the complexes decrease in the order Eu(3+) > Sm(3+) > Tb(3+).

  13. Carbon quantum dots and a method of making the same

    Energy Technology Data Exchange (ETDEWEB)

    Zidan, Ragaiy; Teprovich, Joseph A.; Washington, Aaron L.

    2017-08-22

    The present invention is directed to a method of preparing a carbon quantum dot. The carbon quantum dot can be prepared from a carbon precursor, such as a fullerene, and a complex metal hydride. The present invention also discloses a carbon quantum dot made by reacting a carbon precursor with a complex metal hydride and a polymer containing a carbon quantum dot made by reacting a carbon precursor with a complex metal hydride.

  14. Catalytic applications of mono- and dinuclear complexes containing metal-carbon sigma bonds. Final report, November 1, 1993--October 31, 1996

    Energy Technology Data Exchange (ETDEWEB)

    Norton, J.R.

    1996-12-31

    This report discusses results from several studies involved in the project. Investigations include: vibrational models for surface olefins and alkylidenes; mechanism of the formation and fragmentation of diosmacyclobutanes; reaction of dienes and allenes with diosmacyclobutanes; determination by nematic phase NMR of the structure of mononuclear and dinuclear ethylene complexes of osmium; and generation of ``coordinatively unsaturated`` complexes by protonation of methyl osmium complexes.

  15. Organo-platinum complexes as antitumor agents (review).

    Science.gov (United States)

    Hill, J M; Speer, R J

    1982-01-01

    Rosenberg et al discovered in the coordination complexes of platinum a new, novel type of potential antitumor agent. Cisplatin [cis-dichlorodiammine platinum (II)4 proved active against a variety of rodent tumors and acted synergistically when combined with other chemotherapeutic agents. Initial clinical tests by Hill et al in 1971, showed cisplatin to be active against malignant lymphoma, Hodgkin's disease, and certain other malignancies. Significant nephrotoxicity, nausea, and vomiting were noted. Since then, cisplatin has been tested alone and in combination chemotherapy and has proven an efficacious anticancer agent in squamous cell carcinoma of head and neck, ovarian carcinoma, disseminated testicular cancer, and others. Its therapeutic value was acknowledged when approved in 1978 by the U.S. FDA for treatment of the latter cancer. The current clinical literature indicates clearly that the full potential of this drug has not yet been realized. Hydration and diuresis have served to mitigate much of the nephrotoxicity, while significant strides toward amelioration of the nausea and vomiting have also been achieved. Literally, thousands of chemically-related congeners have been synthesized, and many have shown marked potency against rodent tumors. Very few, however, have been evaluated clinically, vis-a-vis malonato trans(-)-1,2-diaminocyclohexane platinum(II); this appears a most promising and fertile area of future investigation.

  16. Simultaneous determination of hydrazine and phenyl hydrazine using 4′-(4-carboxyphenyl)-2,2′:6′,2″ terpyridine diacetonitrile triphenylphosphine ruthenium(II) tetrafluoroborate complex functionalized multiwalled carbon nanotubes modified electrode

    Energy Technology Data Exchange (ETDEWEB)

    Tiwari, Ida, E-mail: idatiwari_2001@rediffmail.com [Department of Chemistry (Center of Advanced Study), Faculty of Science, Banaras Hindu University, Varanasi (India); Gupta, Mandakini; Sinha, Preeti [Department of Chemistry (Center of Advanced Study), Faculty of Science, Banaras Hindu University, Varanasi (India); Banks, Craig E. [Faculty of Science and Engineering, School of Science and the Environment, Division of Chemistry and Environmental Science, Manchester Metropolitan University, Chester Street, Manchester M1 5GD (United Kingdom)

    2014-12-15

    Highlights: • A nanocomposite of ruthenium(II) terpyridine, triphenylphosphine based complex and multiwalled carbon nanotubes have been used first time for simultaneous detection of hydrazine and phenyl hydrazine. • The detection limit reported is lower as compared to other reported works. • The paper also focuses towards effect of ligand variation attached to ruthenium(II) terpyridine based complexes complex for the hydrazine and phenyl hydrazine detection. • Nanocomposite does not involve any biological entity hence high stability. - Abstract: A nanocomposite based on the incorporation of the complex 4′-(4-carboxyphenyl)-2,2′:6′,2″ terpyridine triphenylphosphine diacetonitrile ruthenium(II) tetrafluoroborate with multiwalled carbon nanotubes and ionomer supported upon a glassy carbon electrode substrate is reported and characterized with scanning electron microscopy, transmission electron microscopy and infrared spectroscopy. The electrochemical behavior and stability of the composite electrode was investigated via cyclic voltammetry. The modified electrode exhibits an electro-catalytic activity towards the oxidation of both hydrazine and phenyl hydrazine in 0.1 M phosphate buffer solution (PBS, pH 7.4). The oxidation of hydrazine and phenyl hydrazine occurs at 0.81 V and 0.32 V with limit of detection found to be 3.7 × 10{sup −7} M and 1.15 × 10{sup −7} M and having a linear range from 5 × 10{sup −6} M to 6.5 × 10{sup −3} M, and 5 × 10{sup −6} M to 0.2 × 10{sup −3} M, respectively.

  17. Synthesis, characterization and multi-spectroscopic DNA interaction studies of a new platinum complex containing the drug metformin

    Science.gov (United States)

    Shahabadi, Nahid; Heidari, Leila

    2014-07-01

    A new platinum(II) complex; [Pt(Met)(DMSO)Cl]Cl in which Met = metformin and DMSO: dimethylsulfoxide, was synthesized and characterized by 1H NMR, IR, UV-Vis spectra, molar conductivity and computational methods. Binding interaction of this complex with calf thymus (CT) DNA has been investigated by using absorption, emission, circular dichroism, viscosity measurements, differential pulse voltammetry and cleavage studies by agarose gel electrophoresis. UV-Vis absorption studies showed hyperchromism. CD studies showed less perturbation on the base stacking and helicity bands in the CD spectrum of CT-DNA (B → C structural transition). In fluorimeteric studies, the Pt(II) complex can bind with DNA-NR complex and forms a new non-fluorescence adduct. The anodic peak current in the differential pulse voltammogram of the Pt(II) complex decreased gradually with the addition of DNA. Cleavage experiments showed that the Pt(II) complex does not induce any cleavage under the experimental setup. Finally all results indicated that Pt(II) complex interact with DNA via groove binding mode.

  18. Synthesis, characterization and multi-spectroscopic DNA interaction studies of a new platinum complex containing the drug metformin.

    Science.gov (United States)

    Shahabadi, Nahid; Heidari, Leila

    2014-07-15

    A new platinum(II) complex; [Pt(Met)(DMSO)Cl]Cl in which Met = metformin and DMSO: dimethylsulfoxide, was synthesized and characterized by (1)H NMR, IR, UV-Vis spectra, molar conductivity and computational methods. Binding interaction of this complex with calf thymus (CT) DNA has been investigated by using absorption, emission, circular dichroism, viscosity measurements, differential pulse voltammetry and cleavage studies by agarose gel electrophoresis. UV-Vis absorption studies showed hyperchromism. CD studies showed less perturbation on the base stacking and helicity bands in the CD spectrum of CT-DNA (B→C structural transition). In fluorimeteric studies, the Pt(II) complex can bind with DNA-NR complex and forms a new non-fluorescence adduct. The anodic peak current in the differential pulse voltammogram of the Pt(II) complex decreased gradually with the addition of DNA. Cleavage experiments showed that the Pt(II) complex does not induce any cleavage under the experimental setup. Finally all results indicated that Pt(II) complex interact with DNA via groove binding mode.

  19. Immobilization of [Cu(bpy){sub 2}]Br{sub 2} complex onto a glassy carbon electrode modified with {alpha}-SiMo{sub 12}O{sub 40}{sup 4-} and single walled carbon nanotubes: Application to nanomolar detection of hydrogen peroxide and bromate

    Energy Technology Data Exchange (ETDEWEB)

    Salimi, Abdollah [Department of Chemistry, University of Kurdistan, P.O. Box 416, Sanandaj (Iran, Islamic Republic of); Research Center for Nanotechnology, University of Kurdistan, P.O. Box 416, Sanandaj (Iran, Islamic Republic of)], E-mail: absalimi@uok.ac.ir; Korani, Aazam; Hallaj, Rahman; Khoshnavazi, Roshan [Department of Chemistry, University of Kurdistan, P.O. Box 416, Sanandaj (Iran, Islamic Republic of); Hadadzadeh, Hasan [Department of Chemistry, Isfahan University of Technology, Isfahan 84156-83111 (Iran, Islamic Republic of)

    2009-03-02

    A simple procedure has been used for preparation of modified glassy carbon electrode with carbon nanotubes and copper complex. Copper complex [Cu(bpy){sub 2}]Br{sub 2} was immobilized onto glassy carbon (GC) electrode modified with silicomolybdate, {alpha}-SiMo{sub 12}O{sub 40}{sup 4-} and single walled carbon nanotubes (SWCNTs){sub .} Copper complex and silicomolybdate irreversibly and strongly adsorbed onto GC electrode modified with CNTs. Electrostatic interactions between polyoxometalates (POMs) anions and Cu-complex, cations mentioned as an effective method for fabrication of three-dimensional structures. The modified electrode shows three reversible redox couples for polyoxometalate and one redox couple for Cu-complex at wide range of pH values. The electrochemical behavior, stability and electron transfer kinetics of the adsorbed redox couples were investigated using cyclic voltammetry. Due to electrostatic interaction, copper complex immobilized onto GC/CNTs/{alpha}-SiMo{sub 12}O{sub 40}{sup 4-} electrode shows more stable voltammetric response compared to GC/CNTs/Cu-complex modified electrode. In comparison to GC/CNTs/Cu-complex the GC/CNTs/{alpha}-SiMo{sub 12}O{sub 40}{sup 4-} modified electrodes shows excellent electrocatalytic activity toward reduction H{sub 2}O{sub 2} and BrO{sub 3}{sup -} at more reduced overpotential. The catalytic rate constants for catalytic reduction hydrogen peroxide and bromate were 4.5({+-}0.2) x 10{sup 3} M{sup -1} s{sup -1} and 3.0({+-}0.10) x 10{sup 3} M{sup -1} s{sup -1}, respectively. The hydrodynamic amperommetry technique at 0.08 V was used for detection of nanomolar concentration of hydrogen peroxide and bromate. Detection limit, sensitivity and linear concentration range proposed sensor for bromate and hydrogen peroxide detection were 1.1 nM and 6.7 nA nM{sup -1}, 10 nM-20 {mu}M, 1 nM, 5.5 nA nM{sup -1} and 10 nM-18 {mu}M, respectively.

  20. Mechanistic studies of the copolymerization reaction of oxetane and carbon dioxide to provide aliphatic polycarbonates catalyzed by (Salen)CrX complexes.

    Science.gov (United States)

    Darensbourg, Donald J; Moncada, Adriana I; Choi, Wonsook; Reibenspies, Joseph H

    2008-05-21

    Chromium salen derivatives in the presence of anionic initiators have been shown to be very effective catalytic systems for the selective coupling of oxetane and carbon dioxide to provide the corresponding polycarbonate with a minimal amount of ether linkages. Optimization of the chromium(III) system was achieved utilizing a salen ligand with tert-butyl groups in the 3,5-positions of the phenolate rings and a cyclohexylene backbone for the diimine along with an azide ion initiator. The mechanism for the coupling reaction of oxetane and carbon dioxide has been studied. Based on binding studies done by infrared spectroscopy, X-ray crystallography, kinetic data, end group analysis done by (1)H NMR, and infrared spectroscopy, a mechanism of the copolymerization reaction is proposed. The formation of the copolymer is shown to proceed in part by way of the intermediacy of trimethylene carbonate, which was observed as a minor product of the coupling reaction, and by the direct enchainment of oxetane and CO 2. The parity of the determined free energies of activation for these two processes, namely 101.9 kJ x mol (-1) for ring-opening polymerization of trimethylene carbonate and 107.6 kJ x mol (-1) for copolymerization of oxetane and carbon dioxide supports this conclusion.

  1. On the electronic structure of nitro-substituted bipyridines and their platinum complexes.

    Science.gov (United States)

    Murray, Paul R; Crawford, Stephen; Dawson, Alice; Delf, Alexander; Findlay, Calum; Jack, Lorna; McInnes, Eric J L; Al-Musharafi, Salma; Nichol, Gary S; Oswald, Iain; Yellowlees, Lesley J

    2012-01-07

    We report the preparation and electrochemical studies of a systematic series of mono- and di-nitro-substituted 2,2'-bipyridine (bipy) compounds [x-NO(2)-bipy (x = 3,4) and x,x'-(NO(2))(2)-bipy (x,x' = 3, 4, 5)] and their complexes with platinum(II), [Pt(x-NO(2)-bipy)Cl(2)] and [Pt(x,x'-(NO(2))(2)-bipy)Cl(2)]. The effect of the number and substitution pattern of the nitro groups on the low-lying acceptor molecular orbitals (involved in charge transfer transitions) is probed by in situ UV/Vis/NIR and EPR spectroelectrochemical methods, supported by DFT calculations. The LUMOs of x-NO(2)-bipy (x = 3-5) are largely localised on the NO(2)-pyridyl moiety; this is also true of their {PtCl(2)} complexes but with a small but significant shift of electron density from the nitro groups. The LUMOs of x,x'-(NO(2))(2)-bipy with x = 3 and 5 are delocalised over both NO(2)-pyridyl rings, but for 4,4'-(NO(2))(2)-bipy is localised on a single NO(2)-pyridyl ring. In all cases the LUMO of the [Pt(x,x'-(NO(2))(2)-bipy)Cl(2)] complexes is delocalised over both nitro-pyridyl rings. For all complexes, the 4(4') derivatives allows greatest overlap with metal valence orbitals in the LUMO.

  2. Preparation and electrochemical properties of core-shell carbon coated Mn–Sn complex metal oxide as anode materials for lithium-ion batteries

    Energy Technology Data Exchange (ETDEWEB)

    Zhang, Ruixue [Key Laboratory of Lithium Battery Materials of Jiangsu Province, Institute of chemical power sources, Soochow University, Suzhou 215006 (China); Fang, Guoqing; Liu, Weiwei [Key Laboratory of Lithium Battery Materials of Jiangsu Province, Institute of chemical power sources, Soochow University, Suzhou 215006 (China); Changzhou Institute of Energy Storage Materials and Devices, Changzhou 213000 (China); Xia, Bingbo; Sun, Hongdan; Zheng, Junwei [Key Laboratory of Lithium Battery Materials of Jiangsu Province, Institute of chemical power sources, Soochow University, Suzhou 215006 (China); Li, Decheng, E-mail: lidecheng@suda.edu.cn [Key Laboratory of Lithium Battery Materials of Jiangsu Province, Institute of chemical power sources, Soochow University, Suzhou 215006 (China)

    2014-02-15

    In this study, we synthesized a carbon coated Mn–Sn metal oxide composite with core-shell structure (MTO@C) via a simple glucose hydrothermal reaction and subsequent carbonization approach. When the MTO@C composite was applied as an anode material for lithium-ion batteries, it maintained a reversible capacity of 409 mA h g{sup −1} after 200 cycles at a current density of 100 mA g{sup −1}. The uniformed and continuous carbon layer formed on the MTO nanoparticles, effectively buffered the volumetric change of the active material and increased electronic conductivity, which thus prolonged the cycling performance of the MTO@C electrode.

  3. The Formation Mechanism of Fluorescent Metal Complexes at the LixNi0.5Mn1.5O4-δ/Carbonate Ester Electrolyte Interface

    Energy Technology Data Exchange (ETDEWEB)

    Jarry, Angelique [Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States); Gottis, Sebastien [Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States); Yu, Young-Sang [Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States); Univ. of Illinois, Chicago, IL (United States); Roque-Rosell, Josep [Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States); Kim, Chunjoong [Univ. of Illinois, Chicago, IL (United States); Cabana, Jordi [Univ. of Illinois, Chicago, IL (United States); Kerr, John B [Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States); Kostecki, Robert [Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States)

    2015-03-18

    Electrochemical oxidation of carbonate esters at the LixNi0.5Mn1.5O4-δ/electrolyte interface results in Ni/Mn dissolution and surface film formation, which negatively affect the electrochemical performance of Li-ion batteries. Ex situ X-ray absorption (XRF/XANES), Raman, and fluorescence spectroscopy, along with imaging of LixNi0.5Mn1.5O4-δ positive and graphite negative electrodes from tested Li-ion batteries, reveal the formation of a variety of MnII/III and NiII complexes with β-diketonate ligands. These metal complexes, which are generated upon anodic oxidation of ethyl and diethyl carbonates at LixNi0.5Mn1.5O4-δ, form a surface film that partially dissolves in the electrolyte. The dissolved MnIII complexes are reduced to their MnII analogues, which are incorporated into the solid electrolyte interphase surface layer at the graphite negative electrode. This work elucidates possible reaction pathways and evaluates their implications for Li+ transport kinetics in Li-ion batteries.

  4. Efficient biological conversion of carbon monoxide (CO) to carbon dioxide (CO2) and for utilization in bioplastic production by Ralstonia eutropha through the display of an enzyme complex on the cell surface.

    Science.gov (United States)

    Hyeon, Jeong Eun; Kim, Seung Wook; Park, Chulhwan; Han, Sung Ok

    2015-06-25

    An enzyme complex for biological conversion of CO to CO2 was anchored on the cell surface of the CO2-utilizing Ralstonia eutropha and successfully resulted in a 3.3-fold increase in conversion efficiency. These results suggest that this complexed system may be a promising strategy for CO2 utilization as a biological tool for the production of bioplastics.

  5. Electronic Structures of Uranyl(VI) Carbonate Complexes in the Aqueous Phase%水溶液中碳酸铀酰化合物的电子结构

    Institute of Scientific and Technical Information of China (English)

    辜家芳; 陆春海; 陈文凯; 陈勇; 许可; 黄昕; 章永凡

    2012-01-01

    A systematic study of series of non-hydrated and hydrated Cnlm uranyl carbonate complexes (n is number of carbonate ligands, and m is number of water molecules) in the aqueous phase was carried out using relativistic density functional theory. The conductor-like screening model was used to calculate solvent effects. The zeroth-order regular approximation was used to account for scalar relativistic effects and spin-orbit coupling relativistic effects. Time-dependent density functional theory with the inclusion of spin-orbit coupling relativistic effects was used to calculate electronic transitions using the statistically averaged orbital potentials. The results indicate that carbonate ligands play an important role in the geometric and electronic transition properties of the complex. The stability of the C3/0 carbonate complex in the aqueous phase may be attributed to the involvement of 5f components in the highest occupied bonding orbital. The addition of carbonate ligands caused a blue shift in the maximum wavelength and high intensity absorptions in the near visible region.%应用相对论密度泛函理论系统研究了水溶液中非水合化和水合化碳酸铀酰化合物Cnlm(其中仃和m分别为结构中碳酸配体和水配体的个数)的结构.溶剂效应采用类导体屏蔽模型(COSMO),并采用零级规整近似(ZORA)方法考虑标量相对论效应和旋-轨耦合相对论效应,电子跃迁采用包含旋-轨耦合相对论效应的含时密度泛函理论并在相关交换势中采用轨道势能统计平均(SAOP)做近似计算,结果表明碳酸配体对配合物结构和电子跃迁有很大的影响.C3/0配合物的稳定性可归于5f轨道参与了高占据轨道的成键作用.增加碳酸盐配体导致最大波长的蓝移,并在近町见光区域出现高强度的吸收.

  6. Self-assembly of a chiral carbonate- and cytidine-containing dodecanuclear copper(II) complex: a multiarm-supplied globular capsule.

    Science.gov (United States)

    Armentano, Donatella; Marino, Nadia; Mastropietro, Teresa F; Martínez-Lillo, José; Cano, Joan; Julve, Miguel; Lloret, Francesc; De Munno, Giovanni

    2008-11-17

    A dodecanuclear copper(II) globular-shaped structure has been obtained with the cytidine nucleoside and the templating carbonate anion. It shows receptor properties through anion-cation and multiple anion-pi interactions toward ClO 4 (-) as well as an overall antiferromagnetic coupling.

  7. Polyionic complex of single-walled carbon nanotubes and PEG-grafted-hyperbranched polyethyleneimine (PEG-PEI-SWNT) for an improved doxorubicin loading and delivery: development and in vitro characterization.

    Science.gov (United States)

    Farvadi, Fakhrossadat; Tamaddon, AliMohammad; Sobhani, Zahra; Abolmaali, Samira Sadat

    2016-05-13

    To take advantages of single-walled carbon nanotubes (SWNTs) for cellular delivery of chemotherapeutic agents (e.g. doxorubicin) in order to decrease general toxicities of doxorubicin (DOX) and to promote the efficacy, we aimed to develop a novel approach to stabilize SWNTs through consequent steps of oxidation and PEG-g-PEI polyionic complexation (PEG-PEI-SWNT). The DOX loading capacity of modified SWNTs was about 900%. Moreover, it showed an enhanced dispersibility in physiologic-stimulated medium. DOX release was prolonged, independent of dilution, and exhibited an acidic pH-stimulated release. Therefore, PEG-PEI-SWNT could be used for cancer chemotherapy in vivo.

  8. Effect the conditions of the acid-thermal modification of clinoptilolite have on the catalytic properties of palladium-copper complexes anchored on it in the reaction of carbon monoxide oxidation

    Science.gov (United States)

    Rakitskaya, T. L.; Kiose, T. A.; Ennan, A. A.; Golubchik, K. O.; Oleksenko, L. P.; Gerasiova, V. G.

    2016-06-01

    The dependence of the physicochemical and structural-adsorption properties of natural and acid-thermal modified clinoptilolite, and of Pd(II)-Cu(II) catalysts based on them, on the duration of acid-thermal modification is investigated. The samples under study are described via XRD and thermal gravimetric (DTG and DTA) analysis, IR, DR UV-Vis, EPR spectroscopy, and water vapor adsorption. Values of both the specific surface area ( S sp) and pH of aqueous suspensions are determined. The resulting catalysts are tested in the reaction of low-temperature carbon monoxide oxidation with air oxygen. A conclusion is drawn about the nature of surface bimetallic Pd(II)-Cu(II) complexes. The greatest catalytic activity is shown by complexes based on clinoptilolite and modified with 3 M HNO3 for 0.5 and 1 h.

  9. Synthesis and antitumor activity of iodo-bridged-binuclear platinum complex

    Institute of Scientific and Technical Information of China (English)

    2006-01-01

    Iodo-bridged binuclear platinum(II) com- plex[Pt((◇)-NH2)I2]2(BPA) has been synthesized and characterized by elemental analysis, conductivity, differential thermal analysis, IR, UV and 1HNMR spectra techniques. The cytotoxicity of the complex was tested by MTT and SRB assays. The results show that complex BPA demonstrates better cytotoxicity than that of the clinically established cisplatin against EJ, HCT-8, BGC-823, HL-60 and MCF-7 cell lines. The complex BPA at concentrations of 1.00 and 2.00 μmol/L induces G1 cell cycle arrest in HL-60 cells. The level of total platinum bound to DNA in HL-60 cells is significantly higher than that of cisplatin under the same experimental conditions. Acute toxicity experimental results indiacte that LD50 of BPA is 815.3 mg/kg by intraperitoneal administration. BPA at dose of 12 mg/kg significantly inhibits the growth of nude mice implanted by human A2780 and HCT-116 carcinomas, and inhibition rate is similar to that of cisplatin at dose of 4 mg/kg by intraperitoneal administration. BPA at dose of 20 mg/kg inhibits the growth of nude mice implanted by human A549 carcinomas, but there was no significant statistical difference.

  10. Carbon Carbon Composites: An Overview .

    Directory of Open Access Journals (Sweden)

    G. Rohini Devi

    1993-10-01

    Full Text Available Carbon carbon composites are a new class of engineering materials that are ceramic in nature but exhibit brittle to pseudoplastic behaviour. Carbon-carbon is a unique all-carbon composite with carbon fibre embeded in carbon matrix and is known as an inverse composite. Due to their excellent thermo-structural properties, carbon-carbon composites are used in specialised application like re-entry nose-tips, leading edges, rocket nozzles, and aircraft brake discs apart from several industrial and biomedical applications. The multidirectional carbon-carbon product technology is versatile and offers design flexibility. This paper describes the multidirectional preform and carbon-carbon process technology and research and development activities within the country. Carbon-carbon product experience at DRDL has also been discussed. Development of carbon-carbon brake discs process technology using the liquid impregnation process is described. Further the test results on material characterisation, thermal, mechanical and tribological properties are presented.

  11. Textural analyses of carbon fiber materials by 2D-FFT of complex images obtained by high frequency eddy current imaging (HF-ECI)

    Science.gov (United States)

    Schulze, Martin H.; Heuer, Henning

    2012-04-01

    Carbon fiber based materials are used in many lightweight applications in aeronautical, automotive, machine and civil engineering application. By the increasing automation in the production process of CFRP laminates a manual optical inspection of each resin transfer molding (RTM) layer is not practicable. Due to the limitation to surface inspection, the quality parameters of multilayer 3 dimensional materials cannot be observed by optical systems. The Imaging Eddy- Current (EC) NDT is the only suitable inspection method for non-resin materials in the textile state that allows an inspection of surface and hidden layers in parallel. The HF-ECI method has the capability to measure layer displacements (misaligned angle orientations) and gap sizes in a multilayer carbon fiber structure. EC technique uses the variation of the electrical conductivity of carbon based materials to obtain material properties. Beside the determination of textural parameters like layer orientation and gap sizes between rovings, the detection of foreign polymer particles, fuzzy balls or visualization of undulations can be done by the method. For all of these typical parameters an imaging classification process chain based on a high resolving directional ECimaging device named EddyCus® MPECS and a 2D-FFT with adapted preprocessing algorithms are developed.

  12. Silica-grafted diethylzinc and a silsesquioxane-based zinc alkyl complex as catalysts for the alternating oxirane-carbon dioxide copolymerization

    NARCIS (Netherlands)

    Duchateau, Robbert; van Meerendonkt, Wouter J.; Huijser, Saskia; Staal, Bastiaan B. P.; van Schilt, Marcus A.; Gerritsen, Gijsbert; Meetsma, Auke; Koning, Cor E.; Kemmere, Maartje F.; Keurentjes, Jos T. F.

    2007-01-01

    A novel zinc silsesquioxane complex ([(c-C5H9)(7)Si7O11(OSiMePh2)](2)Zn4Me4 (1)) has been used as a model compound for silica-grafted zinc catalysts in the copolymerization of cyclohexene oxide and CO2. Complex 1 exists as a dimer in the solid state and is moderately active in the copolymerization,

  13. Carbonyl Activation by Borane Lewis Acid Complexation: Transition States of H2 Splitting at the Activated Carbonyl Carbon Atom in a Lewis Basic Solvent and the Proton-Transfer Dynamics of the Boroalkoxide Intermediate.

    Science.gov (United States)

    Heshmat, Mojgan; Privalov, Timofei

    2017-07-06

    By using transition-state (TS) calculations, we examined how Lewis acid (LA) complexation activates carbonyl compounds in the context of hydrogenation of carbonyl compounds by H2 in Lewis basic (ethereal) solvents containing borane LAs of the type (C6 F5 )3 B. According to our calculations, LA complexation does not activate a ketone sufficiently enough for the direct addition of H2 to the O=C unsaturated bond; but, calculations indicate a possibly facile heterolytic cleavage of H2 at the activated and thus sufficiently Lewis acidic carbonyl carbon atom with the assistance of the Lewis basic solvent (i.e., 1,4-dioxane or THF). For the solvent-assisted H2 splitting at the carbonyl carbon atom of (C6 F5 )3 B adducts with different ketones, a number of TSs are computed and the obtained results are related to insights from experiment. By using the Born-Oppenheimer molecular dynamics with the DFT for electronic structure calculations, the evolution of the (C6 F5 )3 B-alkoxide ionic intermediate and the proton transfer to the alkoxide oxygen atom were investigated. The results indicate a plausible hydrogenation mechanism with a LA, that is, (C6 F5 )3 B, as a catalyst, namely, 1) the step of H2 cleavage that involves a Lewis basic solvent molecule plus the carbonyl carbon atom of thermodynamically stable and experimentally identifiable (C6 F5 )3 B-ketone adducts in which (C6 F5 )3 B is the "Lewis acid promoter", 2) the transfer of the solvent-bound proton to the oxygen atom of the (C6 F5 )3 B-alkoxide intermediate giving the (C6 F5 )3 B-alcohol adduct, and 3) the SN 2-style displacement of the alcohol by a ketone or a Lewis basic solvent molecule. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  14. Synthesis and reactivity of iron complexes with a new pyrazine-based pincer ligand, and application in catalytic low-pressure hydrogenation of carbon dioxide.

    Science.gov (United States)

    Rivada-Wheelaghan, Orestes; Dauth, Alexander; Leitus, Gregory; Diskin-Posner, Yael; Milstein, David

    2015-05-04

    A novel pincer ligand based on the pyrazine backbone (PNzP) has been synthesized, (2,6-bis(di(tert-butyl)phosphinomethyl)pyrazine), tBu-PNzP. It reacts with FeBr2 to yield [Fe(Br)2(tBu-PNzP)], 1. Treatment of 1 with NaBH4 in MeCN/MeOH gives the hydride complex [Fe(H)(MeCN)2(tBu-PNzP)][X] (X = Br, BH4), 2·X. Counterion exchange and exposure to CO atmosphere yields the complex cis-[Fe(H)(CO)(MeCN)(tBu-PNzP)][BPh4] 4·BPh4, which upon addition of Bu4NCl forms [Fe(H)(Cl)(CO)(tBu-PNzP)] 5. Complex 5, under basic conditions, catalyzes the hydrogenation of CO2 to formate salts at low H2 pressure. Treatment of complex 5 with a base leads to aggregates, presumably of dearomatized species B, stabilized by bridging to another metal center by coordination of the nitrogen at the backbone of the pyrazine pincer ligand. Upon dissolution of compound B in EtOH the crystallographically characterized complex 7 is formed, comprised of six iron units forming a 6-membered ring. The dearomatized species can activate CO2 and H2 by metal-ligand cooperation (MLC), leading to complex 8, trans-[Fe(PNzPtBu-COO)(H)(CO)], and complex 9, trans-[Fe(H)2(CO)(tBu-PNzP)], respectively. Our results point at a very likely mechanism for CO2 hydrogenation involving MLC.

  15. Novel metals and metal complexes as platforms for cancer therapy.

    Science.gov (United States)

    Frezza, Michael; Hindo, Sarmad; Chen, Di; Davenport, Andrew; Schmitt, Sara; Tomco, Dajena; Dou, Q Ping

    2010-06-01

    Metals are essential cellular components selected by nature to function in several indispensable biochemical processes for living organisms. Metals are endowed with unique characteristics that include redox activity, variable coordination modes, and reactivity towards organic substrates. Due to their reactivity, metals are tightly regulated under normal conditions and aberrant metal ion concentrations are associated with various pathological disorders, including cancer. For these reasons, coordination complexes, either as drugs or prodrugs, become very attractive probes as potential anticancer agents. The use of metals and their salts for medicinal purposes, from iatrochemistry to modern day, has been present throughout human history. The discovery of cisplatin, cis-[Pt(II) (NH(3))(2)Cl(2)], was a defining moment which triggered the interest in platinum(II)- and other metal-containing complexes as potential novel anticancer drugs. Other interests in this field address concerns for uptake, toxicity, and resistance to metallodrugs. This review article highlights selected metals that have gained considerable interest in both the development and the treatment of cancer. For example, copper is enriched in various human cancer tissues and is a co-factor essential for tumor angiogenesis processes. However the use of copper-binding ligands to target tumor copper could provide a novel strategy for cancer selective treatment. The use of nonessential metals as probes to target molecular pathways as anticancer agents is also emphasized. Finally, based on the interface between molecular biology and bioinorganic chemistry the design of coordination complexes for cancer treatment is reviewed and design strategies and mechanisms of action are discussed.

  16. Development of an electrochemical DNA biosensor for the detection of vitamin B12 (cyanocobalamin at a carbon paste modified electrode with a manganese(II complex

    Directory of Open Access Journals (Sweden)

    Georgia Dimitropoulou

    2017-06-01

    Full Text Available A simple, fast, sensitive and selective electrochemical detection of vitamin B12 (cyanocobalamin has been developed using a DNA electrochemical biosensor and a modified carbon paste electrode. Carbon paste electrode was modified with electrochemically produced polymer of [Mn(thiophenyl-2-carboxylic acid2(triethylonamine] using cyclic voltammetry with a scan rate of 0.01 V/s and three number of scans. Vitamin B12 was immobilized onto the modified electrode. Measurements were carried out using adsorptive transfer square wave voltammetry. Detection was achieved from 3.667 μg/L to 236.0 μg/L, presenting sufficiently low detection (i.e. 1.210 μg/L and quantification (i.e. 3.667 μg/L limits. The precision was tested showing excellent results (i.e. from 5.50 % and 5.35 %. The selectivity towards certain interferences was also investigated and revealed that none of them had significant effect on the detection of vitamin B12. The electrode has been applied in the determination of Vitamin B12 in human urine sample.

  17. Facile preparation of mono-, di- and mixed-carboxylato platinum(IV) complexes for versatile anticancer prodrug design.

    Science.gov (United States)

    Zhang, Jenny Z; Bonnitcha, Paul; Wexselblatt, Ezequiel; Klein, Alice V; Najajreh, Yousef; Gibson, Dan; Hambley, Trevor W

    2013-01-28

    Facile strategies were developed for the versatile functionalization of platinum(IV) axial sites, allowing for easy accessibility to unsymmetric mono- and mixed-carboxylato, as well as symmetric di-substituted platinum(IV) complexes. The first method involves the direct oxidation and carboxylation of the platinum(II) center using an appropriate peroxide and the carboxylate of choice to firstly yield a monocarboxylato monohydroxido platinum(IV) complex. This platinum(IV) intermediate can undergo further carboxylation to give rise to a mixed-carboxylato platinum(IV) complex. The second method involves the activation of the carboxylate of choice by a common carbodiimide coupling reagent, and its reaction with a dihydroxido platinum(IV) precursor to give the monocarboxylato platinum(IV) complex. Uronium salts can be employed to promote efficient dicarboxylation of the dihydroxido platinum(IV) precursor. Lastly, an axial azide pendant group was demonstrated to be suitable for orthogonal "click" conjugation reactions. Copyright © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  18. Calculation of lipophilicity of a large, diverse dataset of anticancer platinum complexes and the relation to cellular uptake.

    Science.gov (United States)

    Oldfield, Steven P; Hall, Matthew D; Platts, James A

    2007-10-18

    A quantitative structure--property relationship (QPSR) for the octanol--water partition of platinum complexes was constructed using molecular descriptors derived from density functional (DFT) calculations. A dataset of partition data for 64 complexes, consisting of 43 square-planar platinum(II) and 21 octahedral platinum(IV) complexes, was drawn from literature sources. Not only does this dataset include considerable structural diversity of complexes considered but also a variety of techniques for the measurement of partition coefficients. These data were modeled using descriptors drawn from electrostatic potentials and hardness/softness indices projected onto molecular surfaces. This required initial descriptor selection using a genetic algorithm approach, followed by partial least-squares regression against log Po/w data. In this way, a statistically robust model was constructed, with errors of similar size to the variation in log Po/w from multiple experimental measurements. Implications of lipophilicity for cellular accumulation of Pt-based drugs, and hence for design of new drugs, are discussed, as is the uptake of metabolites of cisplatin.

  19. Cytotoxicity of cis-platinum(II) cycloaliphatic amidine complexes: Ring size and solvent effects on the biological activity.

    Science.gov (United States)

    Marzano, Cristina; Sbovata, Silvia Mazzega; Gandin, Valentina; Michelin, Rino A; Venzo, Alfonso; Bertani, Roberta; Seraglia, Roberta

    2009-08-01

    A series of new platinum(II) amidine derivatives of the type cis-[PtCl(2){Z-NHC(NHR)Me}(2)] (R=cyclopropyl, 1; cyclopentyl, 2; cyclohexyl, 3) were prepared in high yield by addition of the corresponding cyclic aliphatic amine RNH(2) to the coordinated acetonitrile ligands in cis-[PtCl(2)(NCMe)(2)]. The solution behaviour of 1-3 has been studied in DMSO, PEG 400 (polyethylene glycol) and PEG-DME 500 (polyethylene glycol dimethylether). The amidine complexes 1-3 were evaluated for their cytotoxic properties against a panel of human tumor cell lines containing examples of cervix (HeLa), breast (MCF7), lung (A549) and colon (HCT-15) cancer. Moreover, the amidine complexes were tested for their cytotoxicity against normal human fibroblasts (HFF-1). For comparison purposes, the cytotoxicity of cisplatin was examined under the same experimental conditions. The results obtained showed that PEG and PEG-DME behave as good solvents to carry out biological assays with platinum complexes which are water-insoluble and unstable in DMSO. Complexes 2 and 3 exhibited a biological activity comparable to that of cisplatin.

  20. A Photoactivatable Platinum(IV) Anticancer Complex Conjugated to the RNA Ligand Guanidinoneomycin.

    Science.gov (United States)

    Shaili, Evyenia; Fernández-Giménez, Marta; Rodríguez-Astor, Savina; Gandioso, Albert; Sandín, Lluís; García-Vélez, Carlos; Massaguer, Anna; Clarkson, Guy J; Woods, Julie A; Sadler, Peter J; Marchán, Vicente

    2015-12-07

    A photoactivatable platinum(IV) complex, trans,trans,trans-[Pt(N3 )2 (OH)(succ)(py)2 ] (succ=succinylate, py=pyridine), has been conjugated to guanidinoneomycin to study the effect of this guanidinum-rich compound on the photoactivation, intracellular accumulation and phototoxicity of the pro-drug. Surprisingly, trifluoroacetic acid treatment causes the replacement of an azido ligand and the axial hydroxide ligand by trifluoroacetate, as shown by NMR spectroscopy, MS and X-ray crystallography. Photoactivation of the platinum-guanidinoneomycin conjugate in the presence of 5'-guanosine monophosphate (5'-GMP) led to the formation of trans-[Pt(N3 )(py)2 (5'-GMP)](+) , as does the parent platinum(IV) complex. Binding of the platinum(II) photoproduct {PtN3 (py)2 }(+) to guanine nucleobases in a short single-stranded oligonucleotide was also observed. Finally, cellular uptake studies showed that guanidinoneomycin conjugation improved the intracellular accumulation of the platinum(IV) pro-drug in two cancer cell lines, particularly in SK-MEL-28 cells. Notably, the higher phototoxicity of the conjugate in SK-MEL-28 cells than in DU-145 cells suggests a degree of selectivity towards the malignant melanoma cell line.

  1. Method for the preparation of carbon fiber from polyolefin fiber precursor, and carbon fibers made thereby

    Energy Technology Data Exchange (ETDEWEB)

    Naskar, Amit Kumar; Hunt, Marcus Andrew; Saito, Tomonori

    2015-08-04

    Methods for the preparation of carbon fiber from polyolefin fiber precursor, wherein the polyolefin fiber precursor is partially sulfonated and then carbonized to produce carbon fiber. Methods for producing hollow carbon fibers, wherein the hollow core is circular- or complex-shaped, are also described. Methods for producing carbon fibers possessing a circular- or complex-shaped outer surface, which may be solid or hollow, are also described.

  2. Asymmetric carbon-carbon bond forming reactions catalyzed by chiral titanium complexes. Efficient synthesis of optically active secondary alcohols; Kiraru na chitan shokubai ni yoru fuseitanso-tanso ketsugo keisei. Kogaku kassei dainikyu arukoru no gosei

    Energy Technology Data Exchange (ETDEWEB)

    Hayashi, M. [Yamaguchi Univ., Yamaguchi (Japan). Faculty of Science

    1996-02-01

    For asymmetric metal complex catalysts with high catalytic activity and ability for recognizing asymmetry, it is most important to choose center metals and design asymmetric organic ligands. When the authors began to study on the title reactions, combination of titanium alkoxides as center metals and chiral Schiff bases as organic ligands was unknown, although two moieties had been used independently for asymmetric reactions with excellent results. Asymmetric silylcyanation of aldehydes and enantio-selective addition of diketone to aldehydes are introduced, that have been achieved by authors using titanium complexes of the above combination. In the silylcyanation, reactivity is remarkably improved, compared with a single catalyst of titanium isopropoxide. Cyanohydrin of R from was obtained preferentially with salicyladehyde, particularly having 3-tert butyl group, in an asymmetric yield of 85 % ee. In the latter addition reaction, 5-hydroxy-3-ketoesters were obtained from benzaldehyde in an asymmetric yield as high as 91 % ee. 9 refs., 2 figs.

  3. Synthesis, characterization, computational studies, antimicrobial activities and carbonic anhydrase inhibitor effects of 2-hydroxy acetophenone-N-methyl p-toluenesulfonylhydrazone and its Co(II), Pd(II), Pt(II) complexes

    Science.gov (United States)

    Özbek, Neslihan; Alyar, Saliha; Memmi, Burcu Koçak; Gündüzalp, Ayla Balaban; Bahçeci, Zafer; Alyar, Hamit

    2017-01-01

    2-Hydroxyacetophenone-N-methyl p-toluenesulfonylhydrazone (afptsmh) derived from p-toluenesulfonicacid-1-methylhydrazide (ptsmh) and its Co(II), Pd(II), Pt(II) complexes were synthesized for the first time. Synthesized compounds were characterized by spectroscopic methods (FT-IR, 1Hsbnd 13C NMR, LC-MS, UV-vis), magnetic susceptibility and conductivity measurements. 1H and 13C shielding tensors for crystal structure of ligand were calculated with GIAO/DFT/B3LYP/6-311++G(d,p) methods in CDCl3. The vibrational band assignments were performed at B3LYP/6-311++G(d,p) theory level combined with scaled quantum mechanics force field (SQMFF) methodology. The antibacterial activities of synthesized compounds were studied against some Gram positive and Gram negative bacteria by using microdilution and disc diffusion methods. In vitro enzyme inhibitory effects of the compounds were measured by UV-vis spectrophotometer. The enzyme activities against human carbonic anhydrase II (hCA II) were evaluated as IC50 (the half maximal inhibitory concentration) values. It was found that afptsmh and its metal complexes have inhibitory effects on hCA II isoenzyme. General esterase activities were determined using alpha and beta naphtyl acetate substrates (α- and β-NAs) of Drosophila melanogaster (D. melanogaster). Activity results show that afptsmh does not strongly affect the bacteria strains and also shows poor inhibitory activity against hCAII isoenzyme whereas all complexes posses higher biological activities.