Sample records for ammines

  1. Surface adsorption in strontium chloride ammines

    DEFF Research Database (Denmark)

    Ammitzbøll, Andreas L.; Lysgaard, Steen; Klukowska, Agata


    An adsorbed state and its implications on the ab- and desorption kinetics of ammonia in strontium chloride ammine is identified using a combination of ammonia absorption measurements, thermogravimetric analysis, and density functional theory calculations. During thermogravimetric analysis, ammoni...

  2. Computational screening of mixed metal halide ammines

    DEFF Research Database (Denmark)

    Jensen, Peter Bjerre; Lysgaard, Steen; Quaade, Ulrich;

    the search spaces consists of millions combinations, which makes a GA ideal, to reduce the number of necessary calculations. We are screening for a one step release from either a hexa or octa ammine, and we have found promising candidates, which will be further investigated ? both computationally...

  3. Metal ammine complexes for hydrogen storage

    DEFF Research Database (Denmark)

    Christensen, Claus H.; Sørensen, Rasmus Zink; Johannessen, Tue


    The hopes of using hydrogen as an energy carrier are severely dampened by the fact that there is still no safe, high-density method available for storing hydrogen. We investigate the possibility of using metal ammine complexes as a solid form of hydrogen storage. Using Mg(NH3)(6)Cl-2 as the example......, we show that it can store 9.1% hydrogen by weight in the form of ammonia. The storage is completely reversible, and by combining it with an ammonia decomposition catalyst, hydrogen can be delivered at temperatures below 620 K....

  4. Calcium-Amidoborane-Ammine Complexes : Thermal Decomposition of Model Systems

    NARCIS (Netherlands)

    Harder, Sjoerd; Spielmann, Jan; Tobey, Briac


    Hydrocarbon-soluble model systems for the calcium-amidoborane-ammine complex Ca(NH2BH3)2.(NH3)2 were prepared and structurally characterized. The following complexes were obtained by the reaction of RNH2BH3 (R=H, Me, iPr, DIPP; DIPP=2,6-diisopropylphenyl) with Ca(DIPP-nacnac)(NH2).(NH3)2 (DIPP-nacna

  5. Ammine Calcium and Strontium Borohydrides: Syntheses, Structures, and Properties. (United States)

    Jepsen, Lars H; Lee, Young-Su; Černý, Radovan; Sarusie, Ram S; Cho, Young Whan; Besenbacher, Flemming; Jensen, Torben R


    A new series of solvent- and halide-free ammine strontium metal borohydrides Sr(NH3 )n (BH4 )2 (n=1, 2, and 4) and further investigations of Ca(NH3 )n (BH4 )2 (n=1, 2, 4, and 6) are presented. Crystal structures have been determined by powder XRD and optimized by DFT calculations to evaluate the strength of the dihydrogen bonds. Sr(NH3 )(BH4 )2 (Pbcn) and Sr(NH3 )2 (BH4 )2 (Pnc2) are layered structures, whereas M(NH3 )4 (BH4 )2 (M=Ca and Sr; P21 /c) are molecular structures connected by dihydrogen bonds. Both series of compounds release NH3 gas upon thermal treatment if the partial pressure of ammonia is low. Therefore, the strength of the dihydrogen bonds, the structure of the compounds, and the NH3 /BH4 (-) ratio for M(NH3 )n (BH4 )m have little influence on the composition of the released gasses. The composition of the released gas depends mainly on the thermal stability of the ammine metal borohydride and the corresponding metal borohydride.

  6. Ammonia dynamics in magnesium ammine from DFT and neutron scattering

    DEFF Research Database (Denmark)

    Tekin, Adem; Hummelshøj, Jens Strabo; Jacobsen, Hjalte Sylvest;


    Energy storage in the form of ammonia bound in metal salts, so-called metal ammines, combines high energy density with the possibility of fast and reversible NH3 ab- and desorption kinetics. The mechanisms and processes involved in the NH3 kinetics are investigated by density functional theory (DFT...... structure for the uncharacterized low temperature phase of Mg(NH3)(6)Cl-2. It is found from DFT that the rotation of ammonia in the hexammine complex (n = 6) requires an activation energy of 0.09 eV in the low temperature phase of Mg(NH3)(6)Cl-2 and 0.002-0.12 eV in the high temperature phases; effectively......, 1 systems. DFT calculations involving bulk diffusion of NH3 correctly reproduces the trends observed in the experimental desorption enthalpies. In particular, for n = 6, 2, 1, there is a good agreement between activation barriers and experimental enthalpies. These results indicate...

  7. A study on synthetic method and material characteristics of magnesium ammine chloride as ammonia transport materials for solid SCR

    Energy Technology Data Exchange (ETDEWEB)

    Shin, Jong Kook; Yoon, Cheon Seog [Dept. of Mechanical Engineering, Hannam University, Daejeon (Korea, Republic of); Kim, Hong Suk [Engine Research Center, Korea Institute of Machinery and Materials, Daejeon (Korea, Republic of)


    Among various ammonium salts and metal ammine chlorides used as solid materials for the sources of ammonia with solid SCR for lean NOx reduction, magnesium ammine chloride was taken up for study in this paper because of its ease of handling and safety. Lab-scale synthetic method of magnesium ammine chloride were studied for different durations, temperatures, and pressures with proper ammonia gas charged, as a respect of ammonia gas adsorption rate(%). To understand material characteristics for lab-made magnesium ammine chloride, DA, IC, FT-IR, XRD and SDT analyses were performed using the published data available in literature. From the analytical results, the water content in the lab-made magnesium ammine chloride can be determined. A new test procedure for water removal was proposed, by which the adsorption rate of lab-made sample was found to be approximately 100%.

  8. Designing mixed metal halide ammines for ammonia storage using density functional theory and genetic algorithms

    DEFF Research Database (Denmark)

    Jensen, Peter Bjerre; Lysgaard, Steen; Quaade, Ulrich J.


    Metal halide ammines have great potential as a future, high-density energy carrier in vehicles. So far known materials, e.g. Mg(NH3)6Cl2 and Sr(NH3)8Cl2, are not suitable for automotive, fuel cell applications, because the release of ammonia is a multi-step reaction, requiring too much heat...... to be supplied, making the total efficiency lower. Here, we apply density functional theory (DFT) calculations to predict new mixed metal halide ammines with improved storage capacities and the ability to release the stored ammonia in one step, at temperatures suitable for system integration with polymer...... electrolyte membrane fuel cells (PEMFC). We use genetic algorithms (GAs) to search for materials containing up to three different metals (alkaline-earth, 3d and 4d) and two different halides (Cl, Br and I) – almost 27000 combinations, and have identified novel mixtures, with significantly improved storage...

  9. De novo generation of singlet oxygen and ammine ligands by photoactivation of a platinum anticancer complex. (United States)

    Zhao, Yao; Farrer, Nicola J; Li, Huilin; Butler, Jennifer S; McQuitty, Ruth J; Habtemariam, Abraha; Wang, Fuyi; Sadler, Peter J


    Worth the excitement: Highly reactive oxygen and nitrogen species are generated by photoactivation of the anticancer platinum(IV) complex trans,trans,trans-[Pt(N3 )2 (OH)2 (MA)(Py)] (MA=methylamine, Py=pyridine). Singlet oxygen is formed from the hydroxido ligands and not from dissolved oxygen, and ammine ligands are products from the conversion of azido ligands to nitrenes. Both processes can induce oxidation of guanine.

  10. Designing mixed metal halide ammines for ammonia storage using density functional theory and genetic algorithms. (United States)

    Jensen, Peter Bjerre; Lysgaard, Steen; Quaade, Ulrich J; Vegge, Tejs


    Metal halide ammines have great potential as a future, high-density energy carrier in vehicles. So far known materials, e.g. Mg(NH3)6Cl2 and Sr(NH3)8Cl2, are not suitable for automotive, fuel cell applications, because the release of ammonia is a multi-step reaction, requiring too much heat to be supplied, making the total efficiency lower. Here, we apply density functional theory (DFT) calculations to predict new mixed metal halide ammines with improved storage capacities and the ability to release the stored ammonia in one step, at temperatures suitable for system integration with polymer electrolyte membrane fuel cells (PEMFC). We use genetic algorithms (GAs) to search for materials containing up to three different metals (alkaline-earth, 3d and 4d) and two different halides (Cl, Br and I) - almost 27,000 combinations, and have identified novel mixtures, with significantly improved storage capacities. The size of the search space and the chosen fitness function make it possible to verify that the found candidates are the best possible candidates in the search space, proving that the GA implementation is ideal for this kind of computational materials design, requiring calculations on less than two percent of the candidates to identify the global optimum.

  11. Tailoring the properties of ammine metal borohydrides for solid-state hydrogen storage. (United States)

    Jepsen, Lars H; Ley, Morten B; Filinchuk, Yaroslav; Besenbacher, Flemming; Jensen, Torben R


    A series of halide-free ammine manganese borohydrides, Mn(BH4 )2 ⋅nNH3 , n=1, 2, 3, and 6, a new bimetallic compound Li2 Mn(BH4 )4 ⋅6NH3 , and the first ammine metal borohydride solid solution Mg1-x Mnx (BH4 )2 ⋅6NH3 are presented. Four new crystal structures have been determined by synchrotron radiation powder X-ray diffraction and the thermal decomposition is systematically investigated for all the new compounds. The solid-gas reaction between Mn(BH4 )2 and NH3 provides Mn(BH4 )2 ⋅6NH3 . The number of NH3 per Mn has been varied by mechanochemical treatment of Mn(BH4 )2 ⋅6NH3 -Mn(BH4 )2 mixtures giving rise to increased hydrogen purity for n/m≤1 for M(BH4 )m ⋅nNH3 . The structures of Mg(BH4 )2 ⋅3NH3 and Li2 Mg(BH4 )4 ⋅6NH3 have been revisited and new structural models are presented. Finally, we demonstrate that ammonia destabilizes metal borohydrides with low electronegativity of the metal (χp ∼1.6) are generally stabilized.

  12. Hydrometallurgical process for the recycling of copper using anodic oxidation of cuprous ammine complexes and flow-through electrolysis

    Energy Technology Data Exchange (ETDEWEB)

    Oishi, T.; Yaguchi, M.; Koyama, K.; Tanaka, M. [Metals Recycling Group, Research Institute for Environmental Management Technology, National Institute of Advanced Industrial Science and Technology (AIST), 16-1 Onogawa, Tsukuba, Ibaraki 305-8569 (Japan); Lee, J.-C. [Minerals and Materials Processing Division, Korea Institute of Geoscience and Mineral Resources (KIGAM), 30 Gajeong-dong, Yuseong-ku, Daejeon 305-350 (Korea)


    Flow-through electrolysis for copper electrowinning from cuprous ammine complex was studied in order to develop a hydrometallurgical copper recycling process using an ammoniacal chloride solution, focusing on the anodic oxidation of cuprous to cupric ammine complexes. The current efficiency of this anodic oxidation was 96% at a current density of 200 A m{sup -2} under a batch condition. In a flow-through electrolysis using a sub-liter cell and a carbon felt anode, the anodic current efficiency increased with the flow rate and was typically higher than 97%. This tendency was explained by the backward flow of the cupric ammine complex, which was formed on the anode, through the diaphragm. The anodic overpotential was lower than 0.3 V even at an apparent current density of 1500 A m{sup -2}. A similar current efficiency and overpotential were also achieved in a liter scale cell, which indicates the scale flexibility of this electrolysis. The power consumption requirements for copper electrowinning in this cell were 460 and 770 kWh t{sup -1} at the current densities of 250 and 500 A m{sup -2}, respectively, which were much lower than that of the conventional copper electrowinning despite the longer interpolar distance. (author)

  13. Nanocrystalline lanthanide nitride materials synthesised by thermal treatment of amido and ammine metallocenes: X-ray studies and DFT calculations. (United States)

    Baisch, Ulrich; Pagano, Sandro; Zeuner, Martin; Barros, Noémi; Maron, Laurent; Schnick, Wolfgang


    The decomposition process of ammine lanthanide metallocenes was studied by X-ray diffractometry, spectroscopy and theoretical investigations. A series of ammine-tris(eta(5)-cyclopentadienyl)lanthanide(III) complexes 1-Ln (Lanthanide (Ln)=Sm, Gd, Dy, Ho, Er, Yb) was synthesised by the reaction of [Cp(3)Ln] complexes (Cp=cyclopentadienyl) with liquid ammonia at -78 degrees C and structurally characterised by X-ray diffraction methods, mass spectrometry and vibrational (IR, Raman) spectroscopy. Furthermore, amido-bis(eta(5)-cyclopentadienyl)lanthanide(III) complexes 2-Ln (Ln=Dy, Ho, Er, Yb) were synthesised by heating the respective ammine adduct 1-Ln in an inert gas atmosphere at temperatures of between 240 and 290 degrees C. X-ray diffraction studies, mass spectrometry and vibrational (IR, Raman) spectroscopy were carried out for several 2-Ln species and proved the formation of dimeric mu(2)-bridged compounds. Species 1-Ln are highly reactive coordination compounds and showed different behaviour regarding the decomposition to 2-Ln. The reaction of 1-Ln and 2-Ln with inorganic bases yielded lanthanide nitride LnN powders with an estimated crystallite size of between 40 and 90 nm at unprecedented low temperatures of 240 to 300 degrees C. Temperature-dependent X-ray powder diffraction and transmission electron microscopy (TEM) investigations were performed and showed that the decomposition reaction yielded nanocrystalline material. Structural optimisations were carried out for 1-Ln and 2-Ln by employing density functional (DFT) calculations. A good agreement was found between the observed and calculated structural parameters. Also, Gibbs free energies were calculated for 1-Ln, 2-Ln and the pyrolysis reaction to the nitride material, and were found to fit well with the expected ranges.

  14. Improved Automotive NO (x) Aftertreatment System: Metal Ammine Complexes as NH3 Source for SCR Using Fe-Containing Zeolite Catalysts

    DEFF Research Database (Denmark)

    Johannessen, Tue; Schmidt, Henning; Frey, Anne Mette


    Ammonia storage is a challenge in the selective catalytic reduction of NO (x) in vehicles. We propose a new system, based on metal ammines as the ammonia source. In combination with iron containing zeolites as the SCR catalyst it should be possible to obtain a low temperature system for NO (x...

  15. Assessment of the. pi. -acceptor capability of selected ligands based on the photoelectron spectra of ruthenium ammine complexes

    Energy Technology Data Exchange (ETDEWEB)

    Shepherd, R. E.; Proctor, A.; Henderson, W.W.; Myser, T.K.


    ESCA spectra have been recorded for a series of Ru/sup II/ and Ru/sup III/ ammine complexes of general formula ((NH/sub 3/)/sub 5/RuL)X/sub n/ (X/sup -/ = PF/sub 6//sup -/, Cl/sup -/). Binding energy regions of the C/sub 1s/, Ru/sub 3d3/s/, and Ru/sub 3d5/s/, and Ru/sub 3p3/2/ photopeaks were studied. Binding energies were determined by using nonlinear-least-squares curve fitting. equal to the binding energy difference for (C/sub 1s/ - Ru/sub 3d5/2/) has been used to assign a fractional increase in charge at the Ru/sup II/ center when L = a series of ..pi..-acceptor ligands: N-methylpyrazinium (CH/sub 3/pz/sup +/), CO dimethyl acetylenedicarboxylate ester (dmad), CO, pyrazine (pz), pyridine (py), and CH/sub 3/CN. Authentic Ru/sup II/ and Ru/sup III/ oxidation states were assumed for (Ru(en)/sub 3/)ZnCl/sub 4/, = 5.1 eV, and (Ru(NH/sub 3/)/sub 6/)Cl/sub 3/, = 2.5 eV, respectively. The ..pi..-acceptor order and effective Ru oxidation state were determined to be as follows: CH/sub 3/pz/sup +/, 3.01 > CO, 2.88 > dmad, 2.73 > pz, 2.51 > CH/sub 3/CN, 2.31 > py, 2.20. was also found to be linear in the value of E/sub 1/2/ for the (NH/sub 3/)/sub 5/RuL/sup 3+/2+/ couple. ..pi..-Donor ligands exhibit little influence on for Ru/sup III/ derivatives; = 2.4 +/- 0.1 eV for 3,5-dimethylpyrazole, 4-(dimethylamino)pyridine, and 4-aminopyridine.

  16. Synthesis and Characterization of 2-imino-3–(2-Hydroxylphenyl-1-Thiazolidin-4-one Substituted Ammine Complexes of Cr(III, Co(III, Ni(II and Cu(II

    Directory of Open Access Journals (Sweden)

    Abadi Hadush


    Full Text Available Mixed ligand complexes of Cr(III, Co(III, Ni(II and Cu(II synthesized by partial substitution of 2-imino-3–(2-hydroxylphenyl-1-thiazolidin-4-one in respective ammine complexes were characterized by elemental analysis, conductance and magnetic measurements, infrared and uv-visible spectroscopy. Cr(III, Co(III and Ni(II complexes were octahedral whereas Cu(II complex was square planar.

  17. High-Pressure Synthesis of Cd(NH₃)₂[B₃O₅(NH₃)]₂: Pioneering the Way to the Substance Class of Ammine Borates. (United States)

    Sohr, Gerhard; Ciaghi, Nina; Schauperl, Michael; Wurst, Klaus; Liedl, Klaus R; Huppertz, Hubert


    To date, the access to the substance class of borates containing nitrogen, for example, nitridoborates, oxonitridoborates, or amine borates, was an extreme effort owing to the difficult starting materials and reaction conditions. Although a number of compounds containing boron and nitrogen are known, no adduct of ammonia to an inorganic borate has been observed so far. A new synthetic approach starting from the simple educts CdO, B2O3, and aqueous ammonia under conditions of 4.7 GPa and 800 °C led to the synthesis of Cd(NH3)2[B3O5(NH3)]2 as the first ammine borate. We thoroughly characterized this compound on the basis of low-temperature single-crystal and powder X-ray diffraction data, IR and Raman spectroscopy, and by quantum theoretical calculations. This contribution shows that the adduct of NH3 to the BO3 group of a complex B-O network can be stabilized, opening up a fundamentally new synthetic route to nitrogen-containing borates.

  18. Trends in Syntheses, Structures, and Properties for Three Series of Ammine Rare-Earth Metal Borohydrides, M(BH4)3·nNH3 (M = Y, Gd, and Dy). (United States)

    Jepsen, Lars H; Ley, Morten B; Černý, Radovan; Lee, Young-Su; Cho, Young Whan; Ravnsbæk, Dorthe; Besenbacher, Flemming; Skibsted, Jørgen; Jensen, Torben R


    Fourteen solvent- and halide-free ammine rare-earth metal borohydrides M(BH4)3·nNH3, M = Y, Gd, Dy, n = 7, 6, 5, 4, 2, and 1, have been synthesized by a new approach, and their structures as well as chemical and physical properties are characterized. Extensive series of coordination complexes with systematic variation in the number of ligands are presented, as prepared by combined mechanochemistry, solvent-based methods, solid-gas reactions, and thermal treatment. This new synthesis approach may have a significant impact within inorganic coordination chemistry. Halide-free metal borohydrides have been synthesized by solvent-based metathesis reactions of LiBH4 and MCl3 (3:1), followed by reactions of M(BH4)3 with an excess of NH3 gas, yielding M(BH4)3·7NH3 (M = Y, Gd, and Dy). Crystal structure models for M(BH4)3·nNH3 are derived from a combination of powder X-ray diffraction (PXD), (11)B magic-angle spinning NMR, and density functional theory (DFT) calculations. The structures vary from two-dimensional layers (n = 1), one-dimensional chains (n = 2), molecular compounds (n = 4 and 5), to contain complex ions (n = 6 and 7). NH3 coordinates to the metal in all compounds, while BH4(-) has a flexible coordination, i.e., either as a terminal or bridging ligand or as a counterion. M(BH4)3·7NH3 releases ammonia stepwise by thermal treatment producing M(BH4)3·nNH3 (6, 5, and 4), whereas hydrogen is released for n ≤ 4. Detailed analysis of the dihydrogen bonds reveals new insight about the hydrogen elimination mechanism, which contradicts current hypotheses. Overall, the present work provides new general knowledge toward rational materials design and preparation along with limitations of PXD and DFT for analysis of structures with a significant degree of dynamics in the structures.

  19. Indirect, reversible high-density hydrogen storage in compact metal ammine salts

    DEFF Research Database (Denmark)

    Sørensen, Rasmus Zink; Hummelshøj, Jens Strabo; Klerke, Asbjørn;


    densities both gravimetrically and volumetrically. Upon heating, NH3 is released from the salts, and by employing an appropriate catalyst, H-2 can be released corresponding to up to 9.78 wt % H and 0.116 kg H/L for the Ca(NH3)(8)Cl-2 salt. The NH3 release from all four salts is investigated using...

  20. The Synthesis and Analysis of Ammine Complexes of Copper and Silver Sulfate: An Undergraduate Laboratory Project (United States)

    Clareen, Steven S.; Marshall, Shireen R.; Price, Kristin E.; Royall, Margaret B.; Yoder, Claude H.; Schaeffer, Richard W.


    An undergraduate chemistry laboratory project involving the synthesis of [Ag(NH3)2]2SO4 and Cu(NH3)4SO4 from the simple sulfate salts is described. Characterization of the stoichiometry of the complexes is accomplished by gravimetric and volumetric analysis. Silver is precipitated as the chloride and copper is precipitated as the hydroxide and converted to the oxide before weighing. The ammonia content of each complex is determined with a back titration using dilute nitric acid and sodium hydroxide. Typical student work gives results for the stoichiometry of the complexes within 1-5% of the theoretical values. The project provides a convenient preparation of two compounds whose identity and formula will not be obvious to the student. The analytical procedures illustrate the fundamentals of gravimetric and volumetric analysis and some basic characteristics of simple coordination complexes. The analytical data allow the student to determine the identity of each product by determining its empirical formula.


    Directory of Open Access Journals (Sweden)

    P. Bavazzano


    Full Text Available Pecorino cheese is one of the “D.O.P.” products made in Tuscany. There are two types of pecorino cheese one of which undergoes a curing time period which is not less than four months. Considering this curing time period, processes are conceivable that could lead to the formation of amines such as free amino acids. The biogenic amines have unquestionable effects on health in particular histamine and tyramine, they are also important indicators of hygienic quality of the profile of the movement shortly after the curing time period and included in the shelf life period which the product is commercialized.

  2. Ammine-Stabilized Transition-Metal Borohydrides of Iron, Cobalt, and Chromium: Synthesis and Characterization. (United States)

    Roedern, Elsa; Jensen, Torben R


    Iron and cobalt borohydrides stabilized by ammonia (NH3), [Fe(NH3)6](BH4)2 and [Co(NH3)6](BH4)2, were synthesized along with a solid solution, [Co(NH3)6](BH4)(2-x)Cl(x) (x ∼ 1), and a bimetallic compound, [Fe(NH3)6](Li2(BH4)4). The compounds were prepared by new low-temperature, solvent-based synthesis methods, using dimethyl sulfide or liquid NH3, which allow for the removal of inert metal halides. The crystal structures were determined from synchrotron radiation powder X-ray diffraction (SR-PXD) data. [M(NH3)6](BH4)2 (M = Fe, Co) and [Co(NH3)6](BH4)(2-x)Cl(x) crystallize in the cubic crystal system, where the transition metals are octahedrally coordinated by NH3. Polymeric chains of lithium coordinated by four bridging BH4(-) anions are found in [Fe(NH3)6](Li2(BH4)4). The new compounds have high hydrogen densities of ∼14 wt % H2 and ∼140 g H2/L and release a mixture of hydrogen and NH3 gas at low temperatures, T < 80 °C. The decomposition mechanisms of the prepared compounds along with the composites [Fe(NH3)6](BH4)2·nNH3BH3 (n = 2, 4, 6) were studied by thermal analysis and in situ SR-PXD.

  3. Synthesis, Characterization and Cytotoxicity of Ammine/Methylamine Platinum(Ⅱ) Complexes with Carboxylates

    Institute of Scientific and Technical Information of China (English)


    Seven novel platinum (Ⅱ) complexes [Pt (Ⅱ) (NH3) (CH3NH2) X2] (Ⅰ -Ⅶ) (X: CH3COO- ,CH2 ClCOO - , CHCl2COO -, C6H5-COO - , p-CH3O-C6H4 -COO - , p-NH2-C6 H4 -COO - , p-NO2 -C6 H4 -COO-) were prepared and characterized by means of elemental analysis, molar conductivity, thermal analysis,IR, UV, and 1 H NMR spectrometries. The cytotoxicity against HCT-8, BGC-823, MCF-7, EJ, and HL-60 cell lines increases in the following sequence: cisplatin >Ⅳ>Ⅴ>Ⅵ>Ⅶ>Ⅰ>Ⅱ>Ⅲ. Moreover, the complexes(Ⅰ -Ⅶ) display substantially greater activities against EJ and HL-60 cell lines than those against the cell lines from other carcinomas. They can induce a concentration-dependent accumulation of HL-60 cells in the G2/M phase of the cell cycle as cisplatin. There is no significant correlation between total DNA platination levels and cytotoxicity of the complexes.

  4. The physical chemistry of coordinated aqua-, ammine-, and mixed-ligand Co2+ complexes: DFT studies on the structure, energetics, and topological properties of the electron density. (United States)

    Varadwaj, Pradeep R; Marques, Helder M


    Spin-unrestricted DFT-X3LYP/6-311++G(d,p) calculations have been performed on a series of complexes of the form [Co(H(2)O)(6-n)(NH(3))(n)](2+) (n = 0-6) to examine their equilibrium gas-phase structures, energetics, and electronic properties in their quartet electronic ground states. In all cases Co(2+) in the energy-minimised structures is in a pseudo-octahedral environment. The calculations overestimate the Co-O and Co-N bond lengths by 0.04 and 0.08 A, respectively, compared to the crystallographically observed mean values. There is a very small Jahn-Teller distortion in the structure of [Co(H(2)O)(6)](2+) which is in contrast to the very marked distortions observed in most (but not all) structures of this cation that have been observed experimentally. The successive replacement of ligated H(2)O by NH(3) leads to an increase in complex stability by 6 +/- 1 kcal mol(-1) per additional NH(3) ligand. Calculations using UB3LYP give stabilisation energies of the complexes about 5 kcal mol(-1) smaller and metal-ligand bond lengths about 0.005 A longer than the X3LYP values since the X3LYP level accounts for the London dispersion energy contribution to the overall stabilisation energy whilst it is largely missing at the B3LYP level. From a natural population analysis (NPA) it is shown that the formation of these complexes is accompanied by ligand-to-metal charge transfer the extent of which increases with the number of NH(3) ligands in the coordination sphere of Co(2+). From an examination of the topological properties of the electron charge density using Bader's quantum theory of atoms in molecules it is shown that the electron density rho(c) at the Co-O bond critical points is generally smaller than that at the Co-N bond critical points. Hence Co-O bonds are weaker than Co-N bonds in these complexes and the stability increases as NH(3) replaces H(2)O in the metal's coordination sphere. Several indicators, including the sign and magnitude of the Laplacian of the charge density nabla(2)rho(c), the ratio of the local potential and kinetic energy densities, |V(c)|/G(c), the sign of the total energy density H(c), and the delocalisation index delta(Co,X), X = O, N, are used to show that whilst the metal-ligand bonds are predominantly ionic in nature, they gain covalent character as NH(3) replaces H(2)O, and the Co-N bond is significantly more covalent than the Co-O bond. We have shown that the delocalisation index delta(Co,X), X = O, N, is strongly correlated with the zero-point corrected stabilisation energy E demonstrating that delta can be used as a measure of the bond stability in these complexes.

  5. Chemical and cellular investigations of trans-ammine-pyridine-dichlorido-platinum(II), the likely metabolite of the antitumor active cis-diammine-pyridine-chorido-platinum(II). (United States)

    Xu, Dechen; Min, Yuanzeng; Cheng, Qinqin; Shi, Hongdong; Wei, Kaiju; Arnesano, Fabio; Natile, Giovanni; Liu, Yangzhong


    It has been proposed that the well-studied monofunctional platinum complex cis-[PtCl(NH3)2(py)](+) (cDPCP) forms DNA adducts similar to those of the trans platinum complex trans-[PtCl2(NH3)(py)] (ampyplatin, py=pyridine). Thus this latter could be the active form of cDPCP. Detailed studies on the mechanism of ampyplatin action were performed in this work. Results indicate that ampyplatin has significantly higher antiproliferative activity than cDPCP and is comparable to cisplatin. Cellular uptake experiments indicate that ampyplatin can be efficiently accumulated in A549 cancer cells. Binding of ampyplatin to DNA mainly produces monofunctional adducts; remarkably, these adducts can be recognized by the HMGB1 protein. Kinetic studies on the reaction with GMP indicate that the reactivity of ampyplatin is much lower than that of transplatin and is more similar to that of trans-[PtCl2{E-HN=C(Me)OMe}2] (trans-EE), a widely investigated antitumor active trans-oriented platinum complex. In addition, the hydrolysis of ampyplatin is significantly suppressed, whereas the hydrolysis of the mono-GMP adduct is highly enhanced. These results indicate that the mechanism of ampyplatin differs not only from that of antitumor inactive transplatin but also from that of antitumor active trans-EE and this could account for the remarkable activity of parent cDPCP.

  6. A novel three-dimensional CdII metal-organic framework based on [Cd6(malonate)6] metallomacrocycles with zeolite SOD (sodalite) topology: poly[ammine-μ3-malonato-cadmium(II)]. (United States)

    Yuan, Shuai; Liu, Mei-Jiao; Xie, Han-Yi; Xu, Meng-Zhen; Sun, Di


    A novel Cd(II) metal-organic framework, [Cd(C(3)H(2)O(4))(NH(3))](n), was synthesized by liquid diffusion conducted in the presence of ammonia. The Cd(II) atom has seven-coordinate O(6)N pentagonal-bipyramidal geometry. Six Cd(II) centers are joined by six malonate ligands to form an S(6)-symmetric [Cd(6)(malonate)(6)] metallomacrocycle, which is further extended through a side-on chelating malonate ligand to form a three-dimensional network. Topologically, each Cd(II) center is connected to four others to yield an infinite three-periodic four-coordinated SOD (sodalite) network with point symbol {4(2)·6(4)}. The overall network structure in the crystal is maintained and stabilized by the presence of N-H...O hydrogen bonds.

  7. Visualization of Metal-to-Ligand and Ligand-to-Ligand Charge Transfer in Metal-Ligand Complexes

    Institute of Scientific and Technical Information of China (English)

    Yong Ding; Jian-xiu Guo; Xiang-si Wang; Sha-sha Liu; Feng-cai Ma


    Three methods including the atomic resolved density of state, charge difference density, and the transition density matrix are used to visualize metal to ligand charge transfer (MLCT) in ruthenium(Ⅱ) ammine complex. The atomic resolved density of state shows that there is density of Ru on the HOMOs. All the density is localized on the ammine, which reveals that the excited electrons in the Ru complex are delocalized over the ammine ligand. The charge difference density shows that all the holes are localized on the Ru and the electrons on the ammine. The localization explains the MLCT on excitation. The transition density matrix shows that there is electron-hole coherence between Ru and ammine. These methods are also used to examine the MLCT in Os(bpy)(p0p)Cl ("Osp0p"; bpy=2,2'-bipyridyl; p0p=4,4'-bipyridyl) and the ligand-to-ligand charge transfer (LLCT) in Alq3. The calculated results show that these methods are powerful to examine MLCT and LLCT in the metal-ligand system.

  8. Ammonia/Hydrogen Mixtures in an SI-Engine

    DEFF Research Database (Denmark)

    Mørch, Christian Sandersen; Bjerre, Andreas; Gøttrup, Morten Piil


    In recent years there has been increasing focus on using metal ammine complexes for ammonia storage. In this paper a fuel system for ammonia fuelled internal combustion engines using metal ammine complexes as ammonia storage is analyzed. The use of ammonia/hydrogen mixtures as an SI-engine fuel...... is investigated in the same context. Ammonia and hydrogen were introduced into the intake manifold of a CFR-engine. Series of experiments with varying excess air ratio and different ammonia to hydrogen ratios was conducted. This showed that a fuel mixture with 10 vol.% hydrogen performs best with respect...

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


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


    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 ...

  10. Computational Search for Improved Ammonia Storage Materials

    DEFF Research Database (Denmark)

    Jensen, Peter Bjerre; Lysgaard, Steen; Vegge, Tejs

    Metal halide ammines, e.g. Mg(NH3)6Cl2 and Sr(NH3)8Cl2, can reversibly store ammonia, with high volumetric hydrogen storage capacities. The storage in the halide ammines is very safe, and the salts are therefore highly relevant as a carbon-free energy carrier in future transportation infrastructure....... In this project we are searching for improved mixed materials with optimal desorption temperatures and kinetics, optimally releasing all ammonia in one step. We apply Density Functional Theory, DFT, calculations on mixed compounds selected by a Genetic Algorithm (GA), relying on biological principles of natural...

  11. Role of NH3 in the Electron-Induced Reactions of Adsorbed and Solid Cisplatin

    NARCIS (Netherlands)

    Warneke, Jonas; Rohdenburg, Markus; Zhang, Yucheng; Orzagh, Juraj; Vaz, Alfredo; Utke, Ivo; De Hosson, Jeff Th M.; van Dorp, Willem F.; Swiderek, Petra


    The electron-induced decomposition of cisplatin (cis-Pt(NH3)(2)Cl-2) was investigated to reveal if ammine (NH3) ligands have a favorable effect on the purity of deposits produced from metal-containing precursor molecules by focused electron beam induced deposition (FEBID). Scanning electron microsco

  12. Ir Spectroscopy and Nickel (II) Hexammines (United States)

    Reedijk, J.; And Others


    Describes an experiment, for the general chemistry laboratory, intended to introduce the student to infrared spectroscopy. After being introduced to the theory of molecular vibrations on an elementary level, each student receives a list of 5-7 nickel (II) ammines to be prepared, analyzed and characterized by infrared spectoscopy. (MLH)

  13. Decomposition of the Precursor [Pt(NH3)4](OH)2, Genesis and Structure of the Metal-Support Interface of Alumina Supported Platinum Particles: A Structural Study Using TPR, MS and XAFS Spectroscopy.

    NARCIS (Netherlands)

    Koningsberger, D.C.; Muñoz-Paez, A.


    During the preparation of alumina supported platinum catalysts, the precursor [Pt(NH3)4](OH)2 decomposes to a neutral Pt(NH3)zO species during the drying process at 120 'C. Treatment in flowing hydrogen at 180 'C leads to partial reduction of the platinum ammine complex and formation of platinum met

  14. Nonenzymic spectrophotometric determination of potential poison ivy cross-reactors. (United States)

    Quattrone, A J


    I describe an inexpensive, nonenzymic analytical system for prescreening substances that might cross-react as Rhus toxing (e.g., poison ivy, poison oak, and sumac allergens) on human skin. By spectrophotometric assay after incubation with an oxidizing mixture of Cu(II)ammine complex and ammonium persulfate, I could accurately and reproducibly determine o-quinoidal products of several potential synthetic cross-reactors and native poison ivy allergen, and could distinguish these from catecholamines, resorcinol, p-hydroquinone, and a closely related phenol. A good correlation was obtained between this nonenzymic technique and an enzymic assay. This Cu(II)ammine/persulfate oxidative assay, however, is inexpensive and obviates any spectral interference from enzymic proteins.

  15. Sintesis Basa Schiff Dari Hasil Kondensasi Sinamaldehida Dengan Etilendiamin dan Fenilhidrazin Serta Pemanfaatannya Sebagai Inhibitor Korosi Pada Logam Seng



    It had been synthesis of Base Schiff by condensation reaction cinnamaldehide with two primery ammine sources were ethylenediamine (Base Schiff I) and phenylhydrazine (Schiff Base II). Cinnamaldehyde condensation with ethylenediamine was done by reflux into ethanol solvent in 5 hours and with phenylhydrazine was done by reflux into ethanol solvent in 1 hour. 13,2 g cinnamaldehyde that condensated with 2,4 g ethylenediamine was resulted 8,40 g Schiff Base then analysed by FT-IR Spectroscop...

  16. Handheld hydrogen - a new concept for hydrogen storage

    DEFF Research Database (Denmark)

    Johannessen, Tue; Sørensen, Rasmus Zink


    A method of hydrogen storage using metal ammine complexes in combination with an ammonia decomposition catalyst is presented. This dense hydrogen storage material has high degree of safety compared to all the other available alternatives. This technology reduces the safety hazards of using liquid...... ammonia and benefits from the properties of ammonia as a fuel. The system can be used as a safe, reversible, low-cost hydrogen carrier....

  17. In vitro platinum drug chemosensitivity of human cervical squamous cell carcinoma cell lines with intrinsic and acquired resistance to cisplatin.


    Mellish, K. J.; Kelland, L R; Harrap, K. R.


    The platinum drug chemosensitivity of five human cervical squamous cell carcinoma cell lines (HX/151, HX/155, HX/156, HX/160 and HX/171) derived from previously untreated patients has been determined. Compared to our data obtained previously using human ovarian carcinoma cell lines, all five lines were relatively resistant to cisplatin, carboplatin, iproplatin and tetraplatin. One of the lines (HX/156) was exceptionally sensitive to the novel platinum (IV) ammine/amine dicarboxylates JM216 [b...

  18. Accelerated DFT-Based Design of Materials for Ammonia Storage

    DEFF Research Database (Denmark)

    Jensen, Peter Bjerre; Bialy, Agata; Blanchard, Didier


    Future energy carriers are needed in order to lower the CO2 emissions resulting from the burning of fossil fuels. One possible energy carrier is ammonia, which can be stored safely and reversibly in metal halide ammines; however, the release often occurs in multiple steps at too high temperatures...... materials is the first known high-capacity ternary metal halide ammine, which we have subsequently synthesized and confirmed the ammonia storage properties using temperature-programmed desorption (TPD).......Future energy carriers are needed in order to lower the CO2 emissions resulting from the burning of fossil fuels. One possible energy carrier is ammonia, which can be stored safely and reversibly in metal halide ammines; however, the release often occurs in multiple steps at too high temperatures....... Therefore, there is a need for new materials, releasing the ammonia in a narrow temperature interval. To search for new mixed metal halide chlorides, we use DFT calculations guided by a genetic algorithm (GA) to expedite the search, as the defined search space allowing up to three different metals contains...

  19. Computational investigation and design of coordination compounds for hydrogen storage

    DEFF Research Database (Denmark)

    Hummelshøj, Jens Strabo

    Two classes of high capacity hydrogen storage materials, the metal tetrahydroborates and the metal ammines, were investigated at the atomic scale using density functional theory simulations. It was shown that simple model structures could be used to asses the stabilities of complex systems. Trend...... lithium tetrahydroborate with iodine stabilizes the high temperature phase, in agreement with experiment. Finally, examples on how systematic structural studies of metal halides and hydrides can aid the design of new materials were given.......Two classes of high capacity hydrogen storage materials, the metal tetrahydroborates and the metal ammines, were investigated at the atomic scale using density functional theory simulations. It was shown that simple model structures could be used to asses the stabilities of complex systems. Trends...... in stabilities were reproduced for known systems and the correlations were used to predict the stabilities of unknown systems. Of these, 20 tetrahydroborate systems formed stable mixtures with promising stabilities. A few mixed metal ammine systems showed promising decomposition energies but their stabilities...

  20. Response Behaviour of a Hydrogen Sensor Based on IonicConducting Polymer-metal Interfaces Prepared by the ChemicalReduction Method

    Directory of Open Access Journals (Sweden)

    Werner Weppner


    Full Text Available A solid-state amperometric hydrogen sensor based on a protonated Nafionmembrane and catalytic active electrode operating at room temperature was fabricated andtested. Ionic conducting polymer-metal electrode interfaces were prepared chemically byusing the impregnation-reduction method. The polymer membrane was impregnated withtetra-ammine platinum chloride hydrate and the metal ions were subsequently reduced byusing either sodium tetrahydroborate or potassium tetrahydroborate. The hydrogen sensingcharacteristics with air as reference gas is reported. The sensors were capable of detectinghydrogen concentrations from 10 ppm to 10% in nitrogen. The response time was in therange of 10-30 s and a stable linear current output was observed. The thin Pt films werecharacterized by XRD, Infrared Spectroscopy, Optical Microscopy, Atomic ForceMicroscopy, Scanning Electron Microscopy and EDAX.

  1. Ammonia for hydrogen storage: challenges and opportunities

    DEFF Research Database (Denmark)

    Klerke, Asbjørn; Christensen, Claus H.; Nørskov, Jens Kehlet


    The possibility of using ammonia as a hydrogen carrier is discussed. Compared to other hydrogen storage materials, ammonia has the advantages of a high hydrogen density, a well-developed technology for synthesis and distribution, and easy catalytic decomposition. Compared to hydrocarbons...... and alcohols, it has the advantage that there is no CO2 emission at the end user. The drawbacks are mainly the toxicity of liquid ammonia and the problems related to trace amounts of ammonia in the hydrogen after decomposition. Storage of ammonia in metal ammine salts is discussed, and it is shown...... that this maintains the high volumetric hydrogen density while alleviating the problems of handling the ammonia. Some of the remaining challenges for research in ammonia as a hydrogen carrier are outlined....

  2. Solid solution barium–strontium chlorides with tunable ammonia desorption properties and superior storage capacity

    DEFF Research Database (Denmark)

    Bialy, Agata; Jensen, Peter Bjerre; Blanchard, Didier


    with spray drying and in situ thermogravimetric and structural characterization, we synthesize a range of new, stable barium-strontium chloride solid solutions with superior ammonia storage densities. By tuning the barium/strontium ratio, different crystallographic phases and compositions can be obtained......Metal halide ammines are very attractive materials for ammonia absorption and storage—applications where the practically accessible or usable gravimetric and volumetric storage densities are of critical importance. Here we present, that by combining advanced computational materials prediction...... with different ammonia ab- and desorption properties. In particular it is shown, that in the molar range of 35–50% barium and 65–50% strontium, stable materials can be produced with a practically usable ammonia density (both volumetric and gravimetric) that is higher than any of the pure metal halides...

  3. Towards an ammonia-mediated hydrogen economy?

    DEFF Research Database (Denmark)

    Christensen, Claus H.; Johannessen, Tue; Sørensen, Rasmus Zink;


    Materialization of a hydrogen economy could provide a solution to significant global challenges, In particular. the possibility of improving the efficiency and simultaneously minimizing the environmental impact of energy conversion processes, together with the opportunity to reduce the dependency...... of fossil fuels, are main drivers for the currently increasing research and development efforts. However. significant technological breakthroughs are necessary for making a hydrogen economy feasible. In particular, it is necessary to develop appropriate hydrogen storage and transportation technologies....... Recently, metal ammine salts were proposed as safe, reversible. high-density and low-cost hydrogen carriers. Here, we discuss how this development could provide a platform for using ammonia as a fuel for the hydrogen economy, We do that by comparing various possible hydrogen carriers with respect to energy...

  4. Theoretical Study on the Mechanism Properties of a Novel Trans-platinum Antitumor Drug

    Institute of Scientific and Technical Information of China (English)

    HE Qin; ZHOU Li-Xin; ZHANG Zhi-Qiang


    The mechanism properties of a novel trans-platinum (with one or two of the normal ammine ligands replaced by the planar nitrogen ligand) antitumor drug were explored by using the B3LYP method in the present paper, and the interaction for the monofunctional adduct on DNA trans-[Pt(NH3)(QUIN)GCl] (QUIN = quinoline, G = guanine) with N-containing ligands has been theoretically studied and compared with that of S-containing ligands. The results show that the N-containing ligands are more preferred in the gas phase. Environment effect has been investigated systematically using the PCM model with a series of dielectric constants ε (4.9, 9.0 and 78.4) and compared to the gas phase result with a similar trend.

  5. Electrodialytic soil remediation in a small pilot plant (Part II)

    DEFF Research Database (Denmark)

    Karlsmose, Bodil; Hansen, Lene


    (XRD), transmission electron microscope (TEM) and observations with scanning electron microscope (SEM), the last two combined with an EDX analysis unit. The three soil fractions were extracted with am-monia for observa-tion of the copper removal when copper forms copper-tetra-ammine complexes with am......-monia. Ammonia was chosen because it forms strong complexes with copper and to keep the soil basic, so that the carbonates were not dissolved. The bulk soil was treated by electrodialytic reme-dia-tion, and soil treated for seven months was investigated with XRD, TEM and SEM.Malachite was found by use of XRD...... measurements in one of the untreated soil samples. These measurements were supported by EDX measurements (combined with either SEM or TEM), where almost pure copper particles were found. The EDX measurements do not include hydrogen, carbon and oxygen, which make the figures of all other elements higher than...

  6. Modification of Silica Rice Husk Ash to Solid Ammonium Sulphate for Second Generation Biofuels Productions

    Directory of Open Access Journals (Sweden)

    Kasim Mohammed Hello


    Full Text Available A new approach has been demonstrated for the synthesis of solid ammonium sulphate attached to silica rice husk ash. The 3-(aminopropyltriethoxysilane was immobilized onto silica at room temperature to functionalize the silica with ammine end groups (–NH2. The amine group was sulphated with sulphuric acid to produce a novel micro-rod-like shaped acidic catalyst (as seen with TEM designated RHNH3SO4H (RH = rice husk. The TGA analysis shows that the catalyst is stable at temperatures below 200°C. The acidity measurement of the catalyst indicates that it has Brønsted acid sites. Cellulose extracted from waste of rice husk and cellulose extracted from office paper were hydrolysed to glucose in 6 h, and the glucose was hydrolysed afterwards to other products within 13 h. The catalyst is reusable many times without a significant loss of catalytic activity.

  7. Crystal structure of [UO2(NH35]NO3·NH3

    Directory of Open Access Journals (Sweden)

    Patrick Woidy


    Full Text Available Pentaammine dioxide uranium(V nitrate ammonia (1/1, [UO2(NH35]NO3·NH3, was obtained in the form of yellow crystals from the reaction of caesium uranyl nitrate, Cs[UO2(NO33], and uranium tetrafluoride, UF4, in dry liquid ammonia. The [UO2]+ cation is coordinated by five ammine ligands. The resulting [UO2(NH35] coordination polyhedron is best described as a pentagonal bipyramid with the O atoms forming the apices. In the crystal, numerous N—H...N and N—H...O hydrogen bonds are present between the cation, anion and solvent molecules, leading to a three-dimensional network.

  8. Reactions of Cisplatin Hydrolytes with Thiols. 3: Reactions of cis-[Pt(15NH32(H2O2]2+ with Glutathione

    Directory of Open Access Journals (Sweden)

    Sutopo Hadi


    Full Text Available The reaction of cis-[Pt(15NH32(H2O2]2+ (3 with glutathione (GSH was investigated in aqueous solution. In this reaction, the ammine in the platinum complex formed was liberated. Surprisingly two chelate rings were observed, six-membered-S,O-chelate ring complex cis-[Pt(15NH32(SG-S,O (7 and five-membered-S,N-chelate ring complex cis-[Pt(15NH32(SG-S,N] (8. The bis (thiolate platinum(II complex, cis-[Pt(15NH32(SG2] (9 was always present in this reaction in any mole ratio used. The dinuclear sulphur-bridged complex (10, giving a broad peak in 15N NMR, was only present in very tiny amounts.

  9. trans-Diamminedichloridobis(1H-imidazole-κN (3))nickel(II). (United States)

    Kannan, Piskala Subburaman; Ganeshraja, Ayyakannu Sundaram; Rajkumar, Kanniah; Anbalagan, Krishnamoorthy; Subbiahpandi, Arunachalatheva


    The whole mol-ecule of the title compound, [NiCl2(C3H4N2)2(NH3)2], is generated by inversion symmetry. The Ni(II) ion, which is located on an inversion center, has a distorted octa-hedral coordination environment and is surrounded by two ammine N atoms and two Cl atoms in the equatorial plane, with two N atoms of two imidazole groups occupying the axial positions. The imidazole ring makes a dihedral angle of 81.78 (18)° with the Ni/N/Cl equatorial plane. In the crystal, mol-ecules are linked via N-H⋯Cl hydrogen bonds and C-H⋯π inter-actions, forming a three-dimensional network.

  10. Crystal structure of cis-diamminebis(nitrito-κN)platinum(II). (United States)

    Kahlenberg, Volker; Gelbrich, Thomas; Tessadri, Richard; Klauser, Frederik


    Single crystals of cis-[Pt(NO2)2(NH3)2], were obtained by means of hyper-saturation directly out of a plating electrolyte. The square-planar coordination environment of the divalent Pt(II) atom is formed by four N atoms belonging to two ammine and two monodentate nitrite ligands. The ligands adopt a cis configuration. The crystal structure contains stacks of close-packed mol-ecules which run parallel to [001]. There are nine crystallographically independent inter-molecular N-H⋯O hydrogen bonds, resulting in a hydrogen-bonded hxl-type framework in which each mol-ecule serves as an eight-connected node. Four of the nine distinct hydrogen bonds connect complexes which belong to the same close-packed column parallel to [001]. In contrast to the previously reported crystal structure of the trans isomer, the title structure does not display intra-molecular hydrogen bonding.

  11. Crystal structure of [Co(NH36][Co(CO4]2

    Directory of Open Access Journals (Sweden)

    Thomas G. Müller


    Full Text Available Hexaamminecobalt(II bis[tetracarbonylcobaltate(-I], [Co(NH36][Co(CO4]2, was synthesized by reaction of liquid ammonia with Co2(CO8. The CoII atom is coordinated by six ammine ligands. The resulting polyhedron, the hexaamminecobalt(II cation, exhibits point group symmetry -3. The Co-I atom is coordinated by four carbonyl ligands, leading to a tetracarbonylcobaltate(−I anion in the shape of a slightly distorted tetrahedron, with point group symmetry 3. The crystal structure is related to that of high-pressure BaC2 (space group R-3m, with the [Co(NH36]2+ cations replacing the Ba sites and the [Co(CO4]− anions replacing the C sites. N—H...O hydrogen bonds between cations and anions stabilize the structural set-up in the title compound.

  12. A study of the effect of ammonia gas on the solid mono- and dinuclear oxorhenium(V complexes

    Directory of Open Access Journals (Sweden)



    Full Text Available The reaction of ammonia gas with the solid oxorhenium(V complexes [Re2 O3L2Cl4]·2H2O, [Re2O2L3Cl6]·2H2O, [ReOLCl(OH23]Cl2, [ReOL2(OH23]CCl3, [ReOLCl3(OH2], [ReOL(SCN2Cl(OH2]·H2O and [ReOL(SCNCl2(OH2] (where L = 2-benzimadazolethione, yielded the corresponding ammine and/or amine complexes, [Re2O3L2(NH32(NH22]Cl2 (I, [Re2O2L3(NH32(NH24]Cl2 (II, [Re2O3L2(NH32 (NH24]·H2O (III, [Re2O3L4(NH24] (IV, [Re2O3L2(NH32(NH24C (V, [Re2O3L2(SCN4(NH32] (VI and [Re2O3L2(Thio2(NH24] (VII, respectively, (Thio = thiourea where ammonia gas has replaced other ligands such as chlorine and water. In complex VII thiourea replaced the thiocyanate group in the start complex through its reaction with ammonia gas. The obtained ammine and/or amine of rhenium(V complexes have been observed to decompose through several isolatable, as well as non-isolatable complex species as intermediates during heating. [Re2O3L4], [Re2O3L2(NH24] and [Re2O3L2(SCN4], were synthesized pyrolytically in the solid state from the corresponding parent oxorhenium complexes. The electronic absorption spectra and magnetic moments of the complexes show that the Re(V cation has an octahedral configuration. IR,1H-NMR spectroscopy, conductivity measurements and thermal analysies show that ammonia and thiourea behave as neutral monodentate ligands, SCN- and NH2- as monodentate monoanionic ligands, the organic ligand (L as a neutral monodentate or bidentate ligand towards the metal cation.

  13. Tetraammine(carbonato-κ2O,O′cobalt(III nitrate: a powder X-ray diffraction study

    Directory of Open Access Journals (Sweden)

    Armel Le Bail


    Full Text Available Practical chemistry courses at universities very frequently propose the synthesis and characterization of [Co(CO3(NH34]NO3, but this goal is never achieved since students only obtain the hemihydrated form. The anhydrous form can be prepared, however, and its structure is presented here. Similar to the hemihydrate form, the anhydrous phase contains the CoIII ion in an octahedral O2N4 coordination by a chelating carbonate group and four ammine ligands. The structure reveals an intricate array of N—H...O hydrogen bonds involving both the chelating and the non-chelating O atoms of the carbonate ligand as hydrogen-bond acceptors of the amine H atoms, which are also involved in hydrogen-bonding interactions with the nitrate O atoms. The structure of the anhydrous form is close to that of the hemihydrate phase, suggesting a probable topotactic reaction with relatively small rotations and translations of the [Co(CO3(NH34]+ and NO3− groups during the dehydration process, which produces an unusual volume increase of 4.3%.

  14. Vibrational spectroscopy of the double complex salt Pd(NH3)4(ReO4)2, a bimetallic catalyst precursor (United States)

    Thompson, Simon T.; Lamb, H. Henry; Delley, Bernard; Franzen, Stefan


    Tetraamminepalladium(II) perrhenate, a double complex salt, has significant utility in PdRe catalyst preparation; however, the vibrational spectra of this readily prepared compound have not been described in the literature. Herein, we present the infrared (IR) and Raman spectra of tetraamminepalladium(II) perrhenate and several related compounds. The experimental spectra are complemented by an analysis of normal vibrational modes that compares the experimentally obtained spectra with spectra calculated using DFT (DMol3). The spectra are dominated by features due to the ammine groups and the Resbnd O stretch in Td ReO4-; lattice vibrations due to the D4h Pd(NH3)42+ are also observed in the Raman spectrum. Generally, we observe good agreement between ab initio calculations and experimental spectra. The calculated IR spectrum closely matches experimental results for peak positions and their relative intensities. The methods for calculating resonance Raman intensities are implemented using the time correlator formalism using two methods to obtain the excited state displacements and electron-vibration coupling constants, which are the needed inputs in addition to the normal mode wave numbers. Calculated excited state energy surfaces of Raman-active modes correctly predict relative intensities of the peaks and Franck-Condon activity; however, the position of Raman bands are predicted at lower frequencies than observed. Factor group splitting of Raman peaks observed in spectra of pure compounds is not predicted by DFT.

  15. Amine ligand-based hydrothermal synthesis of Co3O4 nanoparticles, characterization and magnetic study (United States)

    Mansournia, Mohammadreza; Rakhshan, Narges


    Cobalt(II,III) oxid (Co3O4) nanostructures have been successfully synthesized using [Co(NH3)6]Cl3 and [Co(en)3]Cl3 (en: ethylenediamine) as the single precursors via hydrothermal method, and CoCl2·6H2O through a facile ammonia-assisted approach. Indeed, ammine and en ligands, as well as ammonia vapor, act as the sources of hydroxide ion in the preparation of Co3O4 nanoparticles. The structure of products was confirmed by X-ray diffraction (XRD) technique and Fourier-transform infrared (FT-IR) spectroscopy and their morphologies were examined by scanning electron microscopy (SEM). The optical study of the as-prepared Co3O4 nanostructures using UV-Vis diffused reflectance spectroscopy (DRS) exhibited their semiconducting property by revealing one optical band gap in 3.3 eV. Moreover, the vibrating sample magnetometry (VSM) measurements showed a weak ferromagnetic behavior that could be attributed to uncompensated surface spins and/or finite-size effects. Further, the effects of the nature of the precursor, its concentration, temperature and reaction time on the size and morphology of the samples were studied in detail.

  16. Preparation of silver tin oxide powders by hydrothermal reduction and crystallization

    Institute of Scientific and Technical Information of China (English)


    Silver tin oxide composite powders were synthesized by the hydrothermal method with a silver ammine solution and a Na2SnO3 solution as raw marrials. H2C2O4 was used as the co-precipitator of silver ions and tin ions. The co-precipitation conditions were investigated. The results show that the co-precipitate of Ag2C2O4 and Sn(OH)4 is available when the pH value of the solution is 4.27-8.36. Using the obtained precipitate as precursor, the reduction of Ag+ and the crystallization of tin oxide were carried out simultaneonsly by the hydrothermal method and silver tin oxide composite powders were obtained. The composite powders were characterized by X-ray diffraction (XRD) analysis, scanning electron microscope (SEM), and energy spectrum analysis. The results show that the silver tin oxide composite powders are small with a diameter of about 2 μm and with homogeneous distribution of tin.

  17. Recyclable epoxy resins: An example of green approach for advanced composite applications (United States)

    Cicala, Gianluca; Rosa, Daniela La; Musarra, Marco; Saccullo, Giuseppe; Banatao, Rey; Pastine, Stefan


    Automotive composite applications are increasingly growing due to demand for lightweight structures to comply to the requirements for fuel reduction. HP-RTM is gaining relevance as one of the preferred production technologies for high volume applications. The BMW i3 life module being a notable example of HP-RTM application. The key aspects of HP-RTM are the short injection times (i.e. less than 1min) and the fast curing of the thermoset resins (i.e. less than 10min). The choice of using thermosets poses relevant issues for their limited recycling options. The standard recycling solution is the incineration but, this solution poses some concerns in terms of global environmental impact. Novel solutions are presented in this work based on the use of recyclable epoxy systems. In our work the results of experimentation carried out by our group with cleavable ammines by Connora Technologies and bioepoxy resins by Entropy Resins will be discussed. The multiple uses of recycled matrices obtained treating the recyclable epoxy resins are discussed in the framework of a "cradle" to "crave" approach. Finally, Life Cycle Assessment (LCA) is used to evaluate the environmental benefits of the proposed approach.

  18. Polyvinyl alcohol electrospun nanofibers containing Ag nanoparticles used as sensors for the detection of biogenic amines (United States)

    Marega, Carla; Maculan, Jenny; Rizzi, Gian Andrea; Saini, Roberta; Cavaliere, Emanuele; Gavioli, Luca; Cattelan, Mattia; Giallongo, Giuseppe; Marigo, Antonio; Granozzi, Gaetano


    Polyvinyl alcohol (PVA) electrospun nanofibers containing Ag nanoparticles (NPs) have been deposited on glass substrates. The aim of the work was to test the feasibility of this approach for the detection of biogenic amines by using either the Ag localized surface plasmon resonance quenching caused by the adsorption of amines on Ag NPs or by detecting the amines by surface enhanced Raman spectroscopy (SERS) after adsorption, from the gas phase, on the metal NPs. Two different approaches have been adopted. In the first one an ethanol/water solution containing AgNO3 was used directly in the electrospinning apparatus. In this way, a simple heat treatment of the nanofibers mat was sufficient to obtain the formation of Ag NPs inside the nanofibers and a partial cross-link of PVA. In the second procedure, the Ag NPs were deposited on PVA nanofibers by using the supersonic cluster beam deposition method, so that a beam of pure Ag NPs of controlled size was obtained. Exposure of the PVA mat to the beam produced a uniform distribution of the NPs on the nanofibers surface. Ethylendiamine vapors and volatile amines released from fresh shrimp meat were chemisorbed on the nanofibers mats. A SERS spectrum characterized by a diagnostic Ag-N stretching vibration at 230 cm-1 was obtained. The results allow to compare the two different approaches in the detection of ammines.

  19. Antiproliferative Pt(IV) complexes: synthesis, biological activity, and quantitative structure-activity relationship modeling. (United States)

    Gramatica, Paola; Papa, Ester; Luini, Mara; Monti, Elena; Gariboldi, Marzia B; Ravera, Mauro; Gabano, Elisabetta; Gaviglio, Luca; Osella, Domenico


    Several Pt(IV) complexes of the general formula [Pt(L)2(L')2(L'')2] [axial ligands L are Cl-, RCOO-, or OH-; equatorial ligands L' are two am(m)ine or one diamine; and equatorial ligands L'' are Cl- or glycolato] were rationally designed and synthesized in the attempt to develop a predictive quantitative structure-activity relationship (QSAR) model. Numerous theoretical molecular descriptors were used alongside physicochemical data (i.e., reduction peak potential, Ep, and partition coefficient, log Po/w) to obtain a validated QSAR between in vitro cytotoxicity (half maximal inhibitory concentrations, IC50, on A2780 ovarian and HCT116 colon carcinoma cell lines) and some features of Pt(IV) complexes. In the resulting best models, a lipophilic descriptor (log Po/w or the number of secondary sp3 carbon atoms) plus an electronic descriptor (Ep, the number of oxygen atoms, or the topological polar surface area expressed as the N,O polar contribution) is necessary for modeling, supporting the general finding that the biological behavior of Pt(IV) complexes can be rationalized on the basis of their cellular uptake, the Pt(IV)-->Pt(II) reduction, and the structure of the corresponding Pt(II) metabolites. Novel compounds were synthesized on the basis of their predicted cytotoxicity in the preliminary QSAR model, and were experimentally tested. A final QSAR model, based solely on theoretical molecular descriptors to ensure its general applicability, is proposed.

  20. Comparison of the binding behavior of oxaliplatin, cisplatin and analogues to 5'-GMP in the presence of sulfur-containing molecules by means of capillary electrophoresis and electrospray mass spectrometry. (United States)

    Küng, A; Strickmann, D B; Galanski, M; Keppler, B K


    Capillary electrophoresis as well as ESI-MS has been applied for investigating the influence of the sulfur-containing amino acids L-cysteine and L-methionine on the binding behavior of oxaliplatin (trans-R,R-diaminocyclohexane(oxalato)platinum(II)), cisplatin (cis-diamminedichloroplatinum(II)), carboplatin (cis-diammine-1,1-cyclobutanedicarboxylatoplatinum(II)), cis-diammine(malonato)platinum(II) and cis-diammine(2-hydroxymalonato)platinum(II) to 5'-GMP. The presence of L-methionine resulted in a different kind of adduct formation which involves ammine release due to the trans-effect of sulfur. In addition, the time-dependent behavior of the reaction with 5'-GMP changed significantly. Due to the high stability of the diaminocyclohexane (DACH) platinum fragment, oxaliplatin showed a completely different behavior in comparison to diammine platinum complexes. Formation of [Pt(DACH)(L-Met-S,N)](+) inhibits coordination of 5'-GMP. Displacement of L-Met by 5'-GMP does not occur. Differences concerning the mode of action of oxaliplatin are expected. Characterization of the analytes was performed by UV, NMR and mass spectrometry.

  1. A monofunctional trinuclear platinum complex with steric hindrance demonstrates strong cytotoxicity against tumor cells. (United States)

    Wu, Shangnong; Wang, Xiaoyong; He, Yafeng; Zhu, Zhenzhu; Zhu, Chengcheng; Guo, Zijian


    Polynuclear platinum complexes constitute a special class of hopeful antitumor agents. In this study, a Y-type monofunctional trinuclear platinum complex (MTPC) with 1,3,5-tris(pyridin-2-ylmethoxy)benzene, ammine and chloride as ligands was synthesized and characterized by (1)H NMR and electrospray ionization mass spectrometry (ESI-MS). The DNA binding mode of MTPC was investigated using circular dichroism spectroscopy and gel electrophoresis, and the reactivity of MTPC towards glutathione was studied by (1)H NMR and ESI-MS. The results show that MTPC can affect the conformation of calf-thymus DNA (CT-DNA) significantly and tends to form 1,4-GG rather than 1,2-GG intrastrand crosslinks, which are different from the instance of cisplatin. MTPC reacts with glutathione quite slowly in comparison with cisplatin because of the steric hindrance. The cytotoxicity of MTPC was tested on the human breast cancer cell line MCF-7, the human non-small-cell lung cancer cell line A549, and the human ovarian cancer cell line Skov-3 by the MTT [3-(4,5-dimethylthiazol-2-yl)-2,5-diphenyltetrazolium bromide] assay. MTPC is more potent than or comparable to cisplatin. The cellular inhibition mode of MTPC was examined by flow cytometry using MCF-7 cells. MTPC arrests the cell cycle mainly in G2 or M phase, while cisplatin arrests the cell cycle in S phase. Similar to cisplatin, MTPC kills the cells predominantly through an apoptotic pathway.

  2. The effect of anhydrite saturation on the fate of sulfur during fluid-present melting of subducting basaltic crust (United States)

    Jego, S.; Dasgupta, R.


    and will be presented. [1] Kelley and Cottrell (2009), Science 325, 605-607; [2] Jégo and Dasgupta (GCA, under review); [3] Jakobsson (2012), CMP, in press; [4] Médard et al. (2008), AmMin 93, 1838-1844; [5] Balta et al. (2011), AmMin 96, 1467-1474; [6] Li and Ripley (2009), EconGeol 104, 405-412; [7] Baker and Moretti (2011), RiMG 73, 167-213.

  3. Solid solution barium–strontium chlorides with tunable ammonia desorption properties and superior storage capacity

    Energy Technology Data Exchange (ETDEWEB)

    Bialy, Agata [Amminex Emissions Technology A/S, Gladsaxevej 363, 2860 Soeborg (Denmark); Jensen, Peter B. [Department of Energy Conversion and Storage, Technical University of Denmark, Frederiksborgvej 399, DK-4000 Roskilde (Denmark); Center for Atomic-scale Materials Design, Department of Physics, Technical University of Denmark, Fysikvej 311, DK-2800 Kgs. Lyngby (Denmark); Blanchard, Didier [Department of Energy Conversion and Storage, Technical University of Denmark, Frederiksborgvej 399, DK-4000 Roskilde (Denmark); Vegge, Tejs, E-mail: [Department of Energy Conversion and Storage, Technical University of Denmark, Frederiksborgvej 399, DK-4000 Roskilde (Denmark); Quaade, Ulrich J., E-mail: [Amminex Emissions Technology A/S, Gladsaxevej 363, 2860 Soeborg (Denmark)


    Metal halide ammines are very attractive materials for ammonia absorption and storage—applications where the practically accessible or usable gravimetric and volumetric storage densities are of critical importance. Here we present, that by combining advanced computational materials prediction with spray drying and in situ thermogravimetric and structural characterization, we synthesize a range of new, stable barium-strontium chloride solid solutions with superior ammonia storage densities. By tuning the barium/strontium ratio, different crystallographic phases and compositions can be obtained with different ammonia ab- and desorption properties. In particular it is shown, that in the molar range of 35–50% barium and 65–50% strontium, stable materials can be produced with a practically usable ammonia density (both volumetric and gravimetric) that is higher than any of the pure metal halides, and with a practically accessible volumetric ammonia densities in excess of 99% of liquid ammonia. - Graphical abstract: Thermal desorption curves of ammonia from Ba{sub x}Sr{sub (1−x)}Cl{sub 2} mixtures with x equal to 0.125, 0.25 and 0.5 and atomic structure of Sr(NH{sub 3}){sub 8}Cl{sub 2}. - Highlights: • Solid solutions of strontium and barium chloride were synthesized by spray drying. • Adjusting molar ratios led to different crystallographic phases and compositions. • Different molar ratios led to different ammonia ab-/desorption properties. • 35–50 mol% BaCl{sub 2} in SrCl{sub 2} yields higher ammonia density than any other metal halide. • DFT calculations can be used to predict properties of the mixtures.

  4. Molecular insights into the local anesthetic receptor within voltage-gated sodium channels using hydroxylated analogues of mexiletine

    Directory of Open Access Journals (Sweden)

    Jean-François eDesaphy


    Full Text Available We previously showed that the β-adrenoceptor modulators, clenbuterol and propranolol, directly blocked voltage-gated sodium channels, whereas salbutamol and nadolol did not (Desaphy et al., 2003, suggesting the presence of two hydroxyl groups on the aromatic moiety of the drugs as a molecular requisite for impeding sodium channel block. To verify such an hypothesis, we synthesized five new mexiletine analogues by adding one or two hydroxyl groups to the aryl moiety of the sodium channel blocker and tested these compounds on hNav1.4 channels expressed in HEK293 cells. Concentration-response relationships were constructed using an holding potential of -120 mV at 0.1 Hz (tonic block and 10 Hz (use-dependent block stimulation frequencies. The half-maximum inhibitory concentrations (IC50 were linearly correlated to drug lipophilicity: the less lipophilic the drug, minor was the block. The same compounds were also tested on F1586C and Y1593C hNav1.4 channel mutants, to gain further information on the molecular interactions of mexiletine with its receptor within the sodium channel pore. Alteration of tonic block suggests that the aryl moiety of mexiletine may interact either directly or indirectly with Phe1586 in the closed sodium channel to produce low-affinity binding block, and that this interaction depends on the electrostatic potential of the drug aromatic tail. Alteration of use-dependent block suggests that addition of hydroxyl groups to the aryl moiety may modify high-affinity binding of the drug ammine terminal to Phe1586 through cooperativity between the two pharmacophores, this effect being mainly related to drug lipophilicity. Mutation of Tyr1593 further impaired such cooperativity. In conclusion, these results confirm our former hypothesis showing that the presence of hydroxyl groups to the aryl moiety of mexiletine greatly reduced sodium channel block, and provide molecular insights into the intimate interaction of local anesthetics with

  5. Bimetallic Pt-Ni catalysts supported on usy zeolite for n-hexane isomerization

    Directory of Open Access Journals (Sweden)

    F. V. Barsi


    Full Text Available Isomerization of linear alkanes has had considerable importance for the refining industry because the isomers formed in this reaction have high octane number. Most works reported in the literature studied the use of bifunctional catalysts, i.e., ones that have acid sites and metallic sites. In this study, bifunctional monometallic (Ni or Pt and bimetallic catalysts (Pt-Ni, using HUSY zeolite as the support, were prepared in order to verify the role of the metal content and composition on the catalytic properties for n-hexane isomerization. The method used for metal dispersion in the zeolite was competitive ion exchange using ammine complexes [Ni(NH36]Cl2 and [Pt(NH34]Cl2 as precursors. Four series of catalysts with constant atomic metal content had total metal amounts between 130 and 280 µmol M/g cat. Catalysts were characterized by temperature programmed reduction (TPR and subjected to catalytic evaluation for n-hexane isomerization at 250 ºC and 1 atm using H2/C6 = 9 molar ratio. TPR results show an easier reducibility of Ni+2 cations in the presence of Pt, which was evidenced by the displacement of the reduction peak of those cations towards lower temperatures in bimetallic catalysts. The bimetallic catalysts presented a higher activity in the isomerization of n-hexane when compared to the monometallic ones, as well better stability as the Pt content in the solid increases. The results of the activity as a function of the Pt content in the bimetallic catalysts show a maximum value around 50% of Pt. An addition of Pt above this critical value leads to a small decrease of the catalytic activity.

  6. Fluoridonitrosyl complexes of technetium(I) and technetium(II). Synthesis, characterization, reactions, and DFT calculations. (United States)

    Balasekaran, Samundeeswari Mariappan; Spandl, Johann; Hagenbach, Adelheid; Köhler, Klaus; Drees, Markus; Abram, Ulrich


    A mixture of [Tc(NO)F5](2-) and [Tc(NO)(NH3)4F](+) is formed during the reaction of pertechnetate with acetohydroxamic acid (Haha) in aqueous HF. The blue pentafluoridonitrosyltechnetate(II) has been isolated in crystalline form as potassium and rubidium salts, while the orange-red ammine complex crystallizes as bifluoride or PF6(-) salts. Reactions of [Tc(NO)F5](2-) salts with HCl give the corresponding [Tc(NO)Cl4/5](-/2-) complexes, while reflux in neat pyridine (py) results in the formation of the technetium(I) cation [Tc(NO)(py)4F](+), which can be crystallized as hexafluoridophosphate. The same compound can be synthesized directly from pertechnetate, Haha, HF, and py or by a ligand-exchange procedure starting from [Tc(NO)(NH3)4F](HF2). The technetium(I) cation [Tc(NO)(NH3)4F](+) can be oxidized electrochemically or by the reaction with Ce(SO4)2 to give the corresponding Tc(II) compound [Tc(NO)(NH3)4F](2+). The fluorido ligand in [Tc(NO)(NH3)4F](+) can be replaced by CF3COO(-), leaving the "[Tc(NO)(NH3)4](2+) core" untouched. The experimental results are confirmed by density functional theory calculations on [Tc(NO)F5](2-), [Tc(NO)(py)4F](+), [Tc(NO)(NH3)4F](+), and [Tc(NO)(NH3)4F](2+).

  7. Phase transfer of hydrophobic QDs for water-soluble and biocompatible nature through silanization

    Energy Technology Data Exchange (ETDEWEB)

    Yang, Ping, E-mail: [School of Material Science and Engineering, University of Jinan, Jinan 250022 (China); Zhou, Guangjun [State Key Laboratory of Crystal Materials, Shandong University, Jinan 250100 (China)


    Graphical abstract: A facile and novel method has been developed for creating water-soluble and biocompatible CdSe/ZnS quantum dots with a small hydrodynamic diameter (less than 10 nm) via silanization. Highlights: Black-Right-Pointing-Pointer A facile and novel method has been developed for creating water-soluble and biocompatible CdSe/ZnS quantum dots (QDs) with a small hydrodynamic diameter (less than 10 nm). Black-Right-Pointing-Pointer The control of ligand exchange plays an important role to retain high fluorescence quantum yields. Black-Right-Pointing-Pointer The functional SiO{sub 2}-coated QDs were conjugated with immunoglobin G antibody by using biotin-streptavidin as linkers. Black-Right-Pointing-Pointer The QD phase transfer by silanization is a well-established method for generating biocompatible QDs. -- Abstract: A novel method has been developed for creating water-soluble and biocompatible CdSe/ZnS quantum dots (QDs) with a small hydrodynamic diameter (less than 10 nm). The silanization of the QDs was carried out by using partially hydrolyzed tetraethyl orthosilicate (TEOS) to replace organic ammine or tri-n-octylphosphine oxide on the surface of the QDs. The partially hydrolyzed 3-mercaptopropyltrimethoxysilane attached to the hydrolyzed TEOS layer on the QDs prevented the QDs from agglomeration when the QDs were transferred into water. The functional SiO{sub 2}-coated QDs were conjugated with immunoglobin G antibody by using biotin-streptavidin as linkers. The SiO{sub 2}-coated QDs exhibited the same absorption and photoluminescence (PL) spectra as those of initial QDs in organic solvents. The SiO{sub 2}-coated QDs preserved PL intensities, is colloidally stable over a wide pH range (pH 6-11). Because the mean diameter of amphiphilic polymer-coated QDs was almost 2 times of that of functional SiO{sub 2}-coated QDs, the QD phase transfer by silanization is a well-established method for generating biocompatible QDs.

  8. Reactivity of organic-rich sediment in seawater at 350°c, 500 bars: experimental and theoretical constraints and implications for the guaymas basin hydrothermal system (United States)

    Thornton, Edward C.; Seyfried, W. E., Jr.


    Hydrothermal alteration of organic-rich diatomaceous sediment by seawater was modelled experimentally at 350°C, 500 bars and seawater/sediment mass ratio of 3. The experiment was performed to assess the effect of organic matter reactivity on solution speciation and sediment alteration processes at an elevated temperature and pressure and provide requisite data to better understand the chemistry of hydrothermal fluids issuing from vents in the Guaymas Basin, Gulf of California. Seawater chemistry changed greatly during the experiment. In particular, Na, Mg and SO 4 decreased, while ∑ CO 2, ∑ NH 3, ∑ H 2S, SiO 2, Ca, K, H 2, CH 4 and heavy and base metals increased. Moreover, owing to the thermal alteration of sediment organic matter, organic acids, phenolic derivatives and phthlate were released to solution. Examination of solid alteration products revealed the effects of extensive dissolution and precipitation processes characterized by total elimination of diatoms and formation of cristobalite, quartz (?), pyrite, pyrrhotite, mixed layer chlorite/smectite and calcite. Plagioclase feldspar (An 40) recrystallized to a more albitic form owing to Na fixation and Ca cycling to calcite. A graphitic residue was also present in the products of the experiment. Mg and Na fixation reactions during the experiment generated significant H +, although the pH measured at 25°C was approximately 6.2. SO 4 reduction and thermal alteration and dissolution of organics, however, consume H + and are chiefly responsible for the near neutral pH for the overall reaction. Speciation calculations including ammine and acetate protonation reactions give a pH at experimental conditions of approximately 5.1, while mineral solubility relations involving virtually all alteration phases require a pH of 5.57 to 5.94. A near neutral pH at experimental conditions constrains the mobility of Fe, Mn, Zn, Cu and Ni, which existed in solution as chloro-complexes. Dissolved concentrations of Pb and

  9. Fabrication of Zinc Oxide Thin Film Transistors via Low-Temperature Solution Processing%低温溶液加工法制备氧化锌薄膜晶体管

    Institute of Scientific and Technical Information of China (English)

    兰林锋; 宋威; 史文; 彭俊彪


    为适应柔性有源有矩阵有机发光二极管(AMOLED)等新型显示技术发展的需要,将低温溶液处理的氧化锌作为半导体层、电化学氧化的氧化铝钕作为栅绝缘层,制备了氧化锌薄膜晶体管(TFT).制备氧化锌半导体层所用的前驱体溶液为无碳的 Zn(OH)x-(NH3)y(2-x)+水溶液,这种氨络合物溶液制备简单、成本低,并且由于容易形成高活性的氢氧自由基,使得氨-金属之间的分解所需要的活化能较低,生成氧化锌所需的能量较小,可以在180℃的较低温度下获得氧化锌多晶薄膜.所制备的 TFT 器件的最高迁移率可达0.9 cm2/(V·s).这种低温氧化锌薄膜工艺与室温电化学氧化的栅绝缘层工艺相结合,具有温度低和迁移率高的特点,完全能与柔性衬底兼容,在柔性显示中具有很大的应用前景.%In order to meet the requirements of novel display technologies such as flexible active-matrix organic light-emitting diodes (AMOLED),thin film transistors (TFTs)are fabricated,with low-temperature solution-pro-cessed ZnO as the semiconductor layer and with electrochemical oxidized alumina neodymium as the gate dielectric layer.In the preparation of ZnO semiconductor layer,carbon-free aqueous Zn(OH)x (NH3 )y(2 -x)+ solution with low cost and fabrication simplicity is employed,and,more importantly,the energy for metal-ammine dissociation and ZnO formation is rather low thanks to the highly activated hydroxyl radicals.As a result,ZnO polycrystalline films can be realized at a relatively low temperature,namely 1 80℃.The proposed low-temperature solution-pro-cessed ZnO fabrication method combining with room-temperature electrochemically-oxidized gate dielectric layer helps achieve high mobility up to 0.9 cm2 /(V·s),and is completely compatible with flexible substrates,so that it meets the demand of flexible electronic devices well.

  10. Element exchange between minerals at hydrothermal conditions: A case study with spinel (United States)

    Jonas, L.; Muller, T.; Dohmen, R.


    and for the mineral fluid interaction a pure exchange of elements is considered without any mass transfer. From the simulations we obtain constraints for the effective transport rate of Fe through the fluid, which is basically controlled by the diffusion coefficient in the fluid and the solubility of Fe. Our calculations suggest that the concentration of dissolved Fe is up to two orders of magnitude higher than predicted by theoretical solubility calculations. The reaction mechanism map reveals that the reaction is controlled by diffusion in both the solid and the fluid. These results highlight the importance of the concentration of dissolved species for the exchange process. The solubility of the mineral phases is an important factor controlling the development of compositional profiles and may even control the reaction mechanism. This study demonstrates that the following common wisdoms are wrong in the general case: (I) The presence of fluid enhances the rate of the overall exchange reaction. (II) The presence of H2O enhances diffusion in the solid phase. [1] Dohmen & Chakraborty (2003), AmMin, 88, pp. 1251-1270; [2] Vogt (2009), Msc-Thesis, Ruhr-Universität Bochum, p.78

  11. Technological aspects of corrosion control in metallic systems (United States)

    Taylor, Matthew Logan

    Three corrosion control technologies were investigated, including the effect of nitrogen on the passivity of chromium in sulfate solutions, possible issues associated with the use of amines in steam turbine environments and the microstructure of naval advanced amorphous coatings. Nitrogen (N) is a minor alloying element commonly used to increase the strength of steels by stabilizing the austenite phase. Physical vapor deposited chromium + nitrogen (0, 6.8 and 8.9 at.%N) coatings were investigated as a model system, to test the model. Because Cr passive films have been observed to be generally n-type semiconductors, an impedance function containing a n-type Faradaic impedance was constructed and optimized to electrochemical impedance spectra for the model system at pH 4,7 and 10 1M sulfate solution at 30°C. An apparent deviation from theory was observed, however. The n-type model predicted steady state currents which were independent of potential, while the observed current densities had a positive correlation with potential. Mott-Schottky analysis revealed that the test potentials were within the n-p transition and p-type potential range, which resolves the apparent deviation. Despite this difficulty, however, the impedance model produced reasonably accurate results, calculating current densities to within one order of magnitude of the measured steady state currents where anodic currents were available and passive film thicknesses on the order of 1-2 nm. Various amines are commonly used to inhibit corrosion in thermal power generation systems, including steam turbines, by increasing the pH. However, during the shutdown phase of the power plant, it is possible for these inhibitors to concentrate and cause corrosion of the turbine rotor. The effect of two ammine inhibitors (monoethanolamine and dimethylamine) on the passivity of ASTM A470/471 steel is investigated in a simulated turbine environment at pH 7, and temperatures of 95°C and at 175°C. Potentiodynamic