Sample records for ammines
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Surface adsorption in strontium chloride ammines
DEFF Research Database (Denmark)
Ammitzbøll, Andreas L.; Lysgaard, Steen; Klukowska, Agata
2013-01-01
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, ammonia...... desorption originating from the adsorbed state is directly observed below the bulk desorption temperature, as confirmed by density functional theory calculations. The desorption enthalpy of the adsorbed state of strontium chloride octa-ammine is determined with both techniques to be around 37-39 k...
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Computational screening of mixed metal halide ammines
DEFF Research Database (Denmark)
Jensen, Peter Bjerre; Lysgaard, Steen; Quaade, Ulrich
2013-01-01
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...... selection. The GA is evolving from an initial (random) population and selecting those with highest fitness, a function based on e.g. stability, release temperature and storage capacity. The search space includes all alkaline, alkaline earth, 3d and 4d metals and the four lightest halides. In total...... 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...
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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)
2015-11-15
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%.
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International Nuclear Information System (INIS)
Shin, Jong Kook; Yoon, Cheon Seog; Kim, Hong Suk
2015-01-01
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%
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Synthesis of niobium nitride by pyrolysis of niobium pentachloride ammines
International Nuclear Information System (INIS)
Grebtsova, O.M.; Shulga, Y.M.; Troitskii, V.N.
1986-01-01
This paper investigates the conditions for the preparation of niobium nitride in the thermal decomposition of niobium nitride in the thermal decomposition of niobium pentachloride ammines. The synthesis of the ammines was accomplished by the reaction of powdered NbC1 5 with dry ammonia at 210 K. Thermography and x-ray diffraction, spectral, and chemical analyses were used to identify the ammonolysis products. It was established that the products of ammonolysis of NbC1 5 are a mixture of the x-ray-amorphous complex Nb (NH 2 ) /SUB 5-x/ - (NG 3 ) 3 CL 3 (x≅) and 2 moles of NH 4 C1. The steps in the thermal decomposition of this mixture were studied. The phase transition that is observed in the case of further vacuum heat treatment at 1100-1300 K is presented
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Babak, Maria V; Meier, Samuel M; Legin, Anton A; Adib Razavi, Mahsa S; Roller, Alexander; Jakupec, Michael A; Keppler, Bernhard K; Hartinger, Christian G
2013-03-25
With the aim of systematically studying fundamental structure-activity relationships as a basis for the development of Ru(II) arene complexes (arene = p-cymene or biphenyl) bearing mono-, bi-, or tridentate am(m)ine ligands as anticancer agents, a series of ammine, ethylenediamine, and diethylenetriamine complexes were prepared by different synthetic routes. Especially the synthesis of mono-, di-, and triammine complexes was found to be highly dependent on the reaction conditions, such as stoichiometry, temperature, and time. Hydrolysis and protein-binding studies were performed to determine the reactivity of the compounds, and only those containing chlorido ligands undergo aquation or form protein adducts. These properties correlate well with in vitro tumor-inhibiting potency of the compounds. The complexes were found to be active in anticancer assays when meeting the following criteria: stability in aqueous solution and low rates of hydrolysis and binding to proteins. Therefore, the complexes least reactive to proteins were found to be the most cytotoxic in cancer cells. In general, complexes with biphenyl as arene ligand inhibited the growth of tumor cells more effectively than the cymene analogues, consistent with the increase in lipophilicity. This study highlights the importance of finding a proper balance between reactivity and stability in the development of organometallic anticancer agents. Copyright © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.
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Metal ammine complexes for hydrogen storage
DEFF Research Database (Denmark)
Christensen, Claus H.; Sørensen, Rasmus Zink; Johannessen, Tue
2005-01-01
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....
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Ammonia dynamics in magnesium ammine from DFT and neutron scattering
DEFF Research Database (Denmark)
Tekin, Adem; Hummelshøj, Jens Strabo; Jacobsen, Hjalte Sylvest
2010-01-01
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 (D...
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Reithofer, Michael R; Galanski, Markus; Arion, Vladimir B; Keppler, Bernhard K
2008-03-07
Reaction of (OC-6-13)-bis(2Z-3-carboxyacrylato)dichlorido(ethane-1,2-diamine)platinum(IV) and (OC-6-13)-diamminebis(2Z-3-carboxyacrylato)dichloridoplatinum(IV) with propylamine in the presence of 1,1'-carbonyl diimidazole afforded not the expected amides; instead, beside amide formation, a twofold intramolecular attack of the am(m)ine ligand at the C[double bond, length as m-dash]C bonds was observed involving either both (ethane-1,2-diamine) or only one (ammine) coordinated nitrogen atom(s).
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Indirect, reversible high-density hydrogen storage in compact metal ammine salts
DEFF Research Database (Denmark)
Sørensen, Rasmus Zink; Hummelshøj, Jens Strabo; Klerke, Asbjørn
2008-01-01
The indirect hydrogen storage capabilities of Mg(NH3)(6)Cl-2, Ca(NH3)(6)Cl-2, Mn(NH3)(6)Cl-2, and Ni(NH3)(6)Cl-2 are investigated. All four metal ammine chlorides can be compacted to solid tablets with densities of at least 95% of the crystal density. This gives very high indirect hydrogen...
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Electrochemical and SEM studies of tetra-ammine platinum (II) (Pt(NH3)4)(OH)2 solution
International Nuclear Information System (INIS)
Wan Jeffrey Basirun
2002-01-01
Electrochemical studies include cyclic voltammetry with microelectrodes were done on a solution of tetra-ammine platinum (II) (Pt(NH 3 ) 4 )(OH) 2 at pH 13 and showed that the electrochemical reduction of this compound was no different from the tetra-ammine platinum (II) (Pt(NH 3 ) 4 )(HPO 4 ) at pH 10.4. The solution was instable to high temperatures and results have shown that electroplating can be done at a limited temperature range for longer periods of time or at higher temperatures for short periods of time. Scanning electron microscopy was done on some of the constant current electrodeposited samples at high temperatures and result obtained was satisfactory. (Authors)
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Tailoring the properties of ammine metal borohydrides for solid-state hydrogen storage.
Jepsen, Lars H; Ley, Morten B; Filinchuk, Yaroslav; Besenbacher, Flemming; Jensen, Torben R
2015-04-24
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. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.
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Jensen, Peter Bjerre; Lysgaard, Steen; Quaade, Ulrich J; Vegge, Tejs
2014-09-28
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.
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International Nuclear Information System (INIS)
Bento, M.L.
1985-01-01
The ruthenium (II) complexes trans [Ru(NH 3 ) 4 LL'] (BF 4 ) 2 , where L and L' are 4-picoline, pyridine, isonicatinamide, pyrazine or 4-acetylpyridine are studied. The U.V-visible range spectra, bands in the U.V. and in the visible range is analysed. The spectra and the bands by comparison with other ruthenium (II) ammines are discussed, and a qualitative molecular orbital model is used. (M.J.C.) [pt
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DEFF Research Database (Denmark)
Johannessen, Tue; Schmidt, Henning; Frey, Anne Mette
2009-01-01
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...
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PPY-PVA Blend Thin Films as a Ammines Gas Sensor
Directory of Open Access Journals (Sweden)
D. B. DUPARE
2009-06-01
Full Text Available Synthesis of polypyrrole–polyvinyl alcohol blend thin by in situ chemical oxidative polymerization, on glass substrate for development of Ammonia and Trimethyl ammine hazardous gas sensor. The all experimental process carried out at room temperature (304 k. These polymer materials were characterized by Chemical analyses, spectral studies (UV-visible and IR and conductivity measurement by four –probe technique. The surface morphology as seen in the SEM image was observed to be granular, tubular, uniformly covering the entire substrate surface having porous in nature. The current–voltage characterization show that these thin films have conducting in nature having ohmic behaviors. The sensor was used for different concentration (ppm of TMA and Ammonia gas investigation at room temperature (304 k. This study found to possess improved electrical, mechanical and environmental stability PPY-PVA films.
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Chen, Jiayuan; Wu, Xiaofeng; Gong, Yan; Wang, Pengfei; Li, Wenhui; Mo, Shengpeng; Peng, Shengpan; Tan, Qiangqiang; Chen, Yunfa
2018-02-09
We present a general and facile synthesis strategy, on the basis of metal-ammine complex chemistry, for synthesizing hollow transition-metal oxides (Co 3 O 4 , NiO, CuO-Cu 2 O, and ZnO)/nitrogen-doped graphene hybrids, potentially applied in high-performance lithium-ion batteries. The oxygen-containing functional groups of graphene oxide play a prerequisite role in the formation of hollow transition-metal oxides on graphene nanosheets, and a significant hollowing process occurs only when forming metal (Co 2+ , Ni 2+ , Cu 2+ , or Zn 2+ )-ammine complex ions. Moreover, the hollowing process is well correlated with the complexing capacity between metal ions and NH 3 molecules. The significant hollowing process occurs for strong metal-ammine complex ions including Co 2+ , Ni 2+ , Cu 2+ , and Zn 2+ ions, and no hollow structures formed for weak and/or noncomplex Mn 2+ and Fe 3+ ions. Simultaneously, this novel strategy can also achieve the direct doping of nitrogen atoms into the graphene framework. The electrochemical performance of two typical hollow Co 3 O 4 or NiO/nitrogen-doped graphene hybrids was evaluated by their use as anodic materials. It was demonstrated that these unique nanostructured hybrids, in contrast with the bare counterparts, solid transition-metal oxides/nitrogen-doped graphene hybrids, perform with significantly improved specific capacity, superior rate capability, and excellent capacity retention. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.
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Electron capture Auger aftereffect of ammine cobalt complex
International Nuclear Information System (INIS)
Harada, Masayuki; Sano, Hirotoshi
1976-01-01
The study of ammine cobalt complex by luminescent Moessbauer spectrometry method was performed. The method was compared with hot atom chemistry method. The electron states in atoms are changed by the aftereffect on Auger emission following the electron capture process. The state of oxidation of disintegration products is usually higher than that of parent nuclei. However, sometimes, lower oxidation is seen in Fe-57, the daughter nuclei of Co-57. This phenomenon may be due to radiation chemistry process, and this effect can be observed by the luminescent Moessbauer spectrometry method. However, the range of the effect can not be seen by the Moessbauer method. Estimation showed that the Auger electrons stay within the surrounding area of the disintegration atom, and the effect does not reach to distant places. The yield of Fe-57 in the electron capture process of Co-57 in cobalt complex, the G-value, and the hot atom chemical yield were obtained. It is concluded that the aftereffect of the Auger process is the localized radiation chemistry effect. Good correlation was seen between the present method and the hot atom chemistry method. (Kato, T.)
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DEFF Research Database (Denmark)
Jensen, Peter Bjerre; Lysgaard, Steen; Quaade, Ulrich J.
2014-01-01
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......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...
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Trans labilization of am(m)ine ligands from platinum(II) complexes by cancer cell extracts.
Kasherman, Yonit; Sturup, Stefan; Gibson, Dan
2009-03-01
Cisplatin, cis-[Pt(NH(3))(2)Cl(2)], is an effective anticancer agent in wide clinical use whose efficacy is affected by cellular interactions with sulfur-containing nucleophiles. These interactions can potentially enhance the efficacy of the drug by mediating its delivery to nuclear DNA or inactivate the drug by binding to it irreversibly or by labilizing the NH(3) ligands. Despite the potential importance of trans-labilization reactions in the mechanism of action of the drug, few detailed studies on trans labilization of the ammines have been conducted. We used 2D NMR to show that some trans labilization occurs in proliferating cells and that aqueous extracts of cancer cells labilized 20% of the amine ligands of cis-[PtCl(2)((13)CH(3)NH(2))(2)] after a 12-h incubation. Both low molecular mass nucleophiles (less than 3 kDa) and high molecular mass nucleophiles (more than 3 kDa) labilize the amines with similar efficiency. Studies with model compounds show that thiols and thioethers bind to platinum(II) at similar rates, but thioethers are significantly more efficient at labilizing the am(m)ine at lower pH. N-Acetylcysteine is a more efficient trans-labilizer than glutathione, suggesting that the displacement of the amine proceeds through an associative mechanism. The lag time, the time that elapses from the formation of the Pt-S bond till the release of the amine trans to the sulfur, depends on the pH (for thiols), increasing at lower pH. Quantification of the platinum adducts obtained from incubation of cisplatin with cell extracts indicates that two thirds of the platinum is bound to cellular components with molecular mass greater than 3 kDa.
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Energy Technology Data Exchange (ETDEWEB)
Ningthoujam, R.S. [Department of Chemistry, Indian Institute of Technology, Kanpur 208016 (India); Chemistry Division, Bhabha Atomic Research Centre, Mumbai 400085 (India); Panda, R.N., E-mail: rnp@bits-goa.ac.in [Chemistry Group, Birla Institute of Technology and Science-Pilani, Goa Campus, Zuari Nagar, Goa 403726 (India); Gajbhiye, N.S. [Department of Chemistry, Indian Institute of Technology, Kanpur 208016 (India)
2012-05-15
Highlights: Black-Right-Pointing-Pointer Variation of intrinsic magnetic parameters of Co-N. Black-Right-Pointing-Pointer Synthesis by hexa-ammine cobalt complex route. Black-Right-Pointing-Pointer Tuning of coercivity by variation of size. - Abstract: We report the variation of Curie temperature (T{sub c}) and coercivity (H{sub c}) of the single domain Co-N interstitial materials synthesized via nitridation of the hexa-ammine Cobalt(III) nitrate complex at 673 K. Co-N materials crystallize in the fcc cubic structure with unit cell parameter, a = 3.552 Angstrom-Sign . The X-ray diffraction (XRD) peaks are broader indicating the materials to be nano-structured with crystallite sizes of 5-14 nm. The scanning electron microscopy (SEM) and transmission electron microscopy (TEM) studies confirm the nanocrystalline nature of the materials. TEM images show chain-like clusters indicating dipolar interactions between the particles. Magnetic studies focus on the existence of giant magnetic Co atoms in the Co-N lattice that are not influenced by the thermal relaxation. The values of the H{sub c} could be tuned with the dimension of the particles. The values of T{sub c} of the nitride materials are masked by the onset of the ferromagnetic to superparamagnetic transition at higher temperatures. Thermomagnetic studies show an increasing trend in the Curie temperature, T{sub c}, with decrease in particle dimension. This result has been explained qualitatively on the basis of ferromagnetic to superparamagnetic transition and finite size scaling effects.
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Directory of Open Access Journals (Sweden)
Duncan H. Gregory
2012-04-01
Full Text Available Hexa-ammine complexes, Mn(NH36X2 (X = Cl, Br, have been synthesized by ammoniation of the corresponding transition metal halide and characterized by Powder X-ray diffraction (PXRD and Raman spectroscopy. The hexa-ammine complexes are isostructural (Cubic, Fm-3m, Z = 4; a = 10.2742(6 Å and 10.527(1 Å for X = Cl, Br respectively. Temperature programmed desorption (TPD demonstrated that ammonia release from Mn(NH36X2 complexes occurred in three stages corresponding to the release of 4, 1 and 1 NH3 equivalents respectively. The chloride and bromide both exhibit a deammoniation onset temperature below 323 K. The di-ammoniates from the first desorption step were isolated during TPD measurements and their crystal structures determined by Rietveld refinement against PXRD data (X = Cl: orthorhombic Cmmm, a = 8.1991(9 Å, b = 8.2498(7 Å, c = 3.8212(4 Å, Z = 2; X = Br: orthorhombic Pbam, a = 6.0109(5 Å, b = 12.022(1 Å, c = 4.0230(2 Å, Z = 2.
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Tetra-ammine-(carbonato-κ(2) O,O')cobalt(III) nitrate: a powder X-ray diffraction study.
Le Bail, Armel
2013-01-01
Practical chemistry courses at universities very frequently propose the synthesis and characterization of [Co(CO3)(NH3)4]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 Co(III) 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 inter-actions 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)(NH3)4](+) and NO3 (-) groups during the dehydration process, which produces an unusual volume increase of 4.3%.
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Directory of Open Access Journals (Sweden)
Eko Sri Kunarti
2015-11-01
24,66 kJ/mol. ABSTRACT Chromium (VI is a heavy metal pollutant that is harmful to health and the environment, therefore Cr(VI ions in aqueous solution removal is important to overcome the environmental pollution. Adsorption process is one of simple techniques that can be used to take metal ions. Adsorption study of dichromate ions as a wastewater model of Cr(VI has been conducted in this research by using ammine modified natural zeolite as adsorbents. The research was initiated by preparation of adsorbent of ammine-modified natural zeolites. The preparation was started by washing the natural zeolite (Z using distilled water and refluxing by 3M hydrochloric acid. Refluxed zeolites (ZA were modified by a quaternary ammonium salt, N-cethyl-N,N,N-trimethylammonium bromide (CTAB, and a primary amine, propylamine (PA. The natural zeolite (Z, acid activated zeolite (ZA and amine-modified zeolites were then applied for adsorption of dichromate ions. Characterization of zeolite samples was performed by infrared spectroscopy and X-ray diffraction methods to confirm the crystal structure, and atomic absorption spectroscopy method to analyze the adsorbed dichromate ions. Results showed that all zeolite samples contain clinoptilolite, mordernite and quartz minerals. The zeolite structure was not changed by heat and chemical treatments. Modification of zeolites enhanced the adsorption efficiency of natural zeolites. The dichromate ions were better adsorbed on ammine modified-zeolites compared to that of unmodified-zeolite with adsorption ability of CTAB modified zeolite (CTAB-Z was greater than that of propylammine modified zeolite (PA-Z. The adsorption of dichromate on zeolite samples was achieved in the order of CTAB-Z > PA-Z > ZA > Z, with the adsorption efficiency was about 1.96; 1.74; 0.90 and 0.48 mg/g, respectively. The dichromate ions adsorption by CTAB modified zeolite is chemical adsorption (chemisorption with the adsorption energy of 24.66 kJ/mol.
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Tetraammine(carbonato-κ2 O,O′)cobalt(III) nitrate: a powder X-ray diffraction study
Le Bail, Armel
2013-01-01
Practical chemistry courses at universities very frequently propose the synthesis and characterization of [Co(CO3)(NH3)4]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)(NH3)4]+ and NO3 − groups during the dehydration process, which produces an unusual volume increase of 4.3%. PMID:24046543
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International Nuclear Information System (INIS)
Pavelka, Matej; Burda, Jaroslav V.
2005-01-01
This work is devoted to investigate the interactions of the Cu(I)/Cu(II) cation with variable ammonia-water ligand field by the quantum chemical approach. For that purpose, the optimization of the [Cu(NH 3 ) m (H 2 O) n ] 2+/+ complexes (where n varies from 0 to 4 or 6 and m + n = 4 or 6) has been performed at the DFT/6-31+G(d) level of theory in conjunction with the B3PW91 hybrid functional. Based on the results of the single-point B3LYP/6-311++G(2df,2pd) calculations, the stabilization energies were determined. The two-coordinated copper(I) complexes appeared to be the most stable compounds with the remaining water or ammonia molecules in the second solvation shell. In the case of the Cu(II) systems, four-coordinated complexes were found to be the most stable. In order to examine and explain bonding characteristics, Morokuma interaction energy decomposition (for selected Cu + complexes) and Natural Population Analysis for all systems were performed. It was found that the most stable structures correlate with the highest donation effects. Therefore, more polarizable ammonia molecules exhibit higher donation than water and thus make stronger bonds to copper. This can be demonstrated by the fact that the NH 3 molecule always tries to occupy the first solvation shell in mixed ammine-aqua complexes
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14N NMR of amminecobalt(III) compounds
DEFF Research Database (Denmark)
Kofod, Pauli
2003-01-01
Directly detected ammine 14N NMR chemical shifts of 20 amminecobalt(III) compounds are reported. The coordination shifts, δCS = δcoord − δfree, are in all cases negative and range from −4.4 ppm for the trans ammine ligand in [Co(NH3)5(CH3)]2+ to −73.6 ppm for the trans ammine ligand in [Co(NH3)5(F...
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Ammonia release method for depositing metal oxides
Energy Technology Data Exchange (ETDEWEB)
Silver, G.L.; Martin, F.S.
1993-12-31
A method of depositing metal oxides on substrates which is indifferent to the electrochemical properties of the substrates and which comprises forming ammine complexes containing metal ions and thereafter effecting removal of ammonia from the ammine complexes so as to permit slow precipitation and deposition of metal oxide on the substrates.
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Directory of Open Access Journals (Sweden)
Qianni Zhang
2018-01-01
Full Text Available The aqueous-based Zn-ammine complex solutions represent one of the most promising routes to obtain the ZnO electron transport layer (ETL at a low temperature in inverted organic solar cells (OSCs. However, to dope the ZnO film processed from the Zn-ammine complex solutions is difficult since the introduction of metal ions into the Zn-ammine complex is a nontrivial process as ammonium hydroxide tends to precipitate metal salts due to acid-base neutralization reactions. In this paper, we investigate the inverted OSCs with Al-doped-ZnO ETL made by immersion of metallic Al into the Zn-ammine precursor solution. The effects of ZnO layer with different immersion time of Al on film properties and solar cell performance have been studied. The results show that, with the Al-doped-ZnO ETL, an improvement of the device performance could be obtained compared with the device with the un-doped ZnO ETL. The improved device performance is attributed to the enhancement of charge carrier mobility leading to a decreased charge carrier recombination and improved charge collection efficiency. The fabricated thin film transistors with the same ZnO or AZO films confirm the improved electrical characteristics of the Al doped ZnO film.
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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...... selection. The GA is evolving from an initial (random) population and selecting those with highest fitness, a function based on e.g. stability, release temperature, storage capacity and the price of the elements. The search space includes all alkaline earth, 3d and 4d metals in combination with chloride......, bromide or iodide, and mixtures thereof. In total the search space consists of thousands of 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...
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Effects of Copper Exchange Levels on Complexation of Ammonia in ...
African Journals Online (AJOL)
NJD
Cation exchange, catalysis, copper, complexation, copper ammines. 1. Introduction ... ammonia is able to de-link Cu2+ ions away from the influence of .... Figure 1 DRS of CuX at different concentration levels of Cu/UC: (a). 38 Cu/UC, (b) 24 ...
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Handheld hydrogen - a new concept for hydrogen storage
DEFF Research Database (Denmark)
Johannessen, Tue; Sørensen, Rasmus Zink
2005-01-01
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...
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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. Trends...
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JCSC_128_11_1703_1707_SI_a.docx
Indian Academy of Sciences (India)
dell
Finally, the reaction was neutralized by triethyl ammine and the solution passed through a small basic alumina column. The reaction mixture was concentrated and 8 was separated by silica gel column chromatography using DCM/Hexane as eluent. 8 was crystallised with DCM/Hexane system. [8]2+ was generated by ...
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High-Voltage Polymers for High-Power Supercapacitors. Version 1
2006-05-30
affect the supercapacitor’s performance. Subsequently, our efforts focused on fabricating polymers with high oxidation potentials to increase the power...including spin activation with out significant modifications. Electroactive polymers such as polythiophene, polyacetylene, or polyaniline can be...potentials in excess of 2 V for facile polymerization. In the present case, the triaryl ammine functionality of 2 and 3 is oxidized at the low
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Computational Screening of Mixed Metal Halide Ammines
DEFF Research Database (Denmark)
Jensen, Peter Bjerre; Lysgaard, Steen; Quaade, Ulrich
selected by a Genetic Algorithm (GA), relying on biological principles of natural selection. The GA is evolving from an initial (random) population and selecting those with highest fitness, e.g. stability, release temperature and storage capacity. The search space includes all alkaline, alkaline earth, 3d...
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International Nuclear Information System (INIS)
Weaver, M.J.; Nettles, S.M.
1980-01-01
The effects of substituting D 2 O for H 2 O as solvent upon the formal potentials of a number of transition-metal redox couples containing aquo, ammine, and simple chelating ligands have been investigated with the intention of evaluating the importance of specific solvation factors in the thermodynamics of such couples. The solvent liquid junction formed between H 2 O and D 2 O was shown to have a negligible effect on the measured formal potentials. Substantial solvent isotope effects were observed for a number of these systems, particularly for couples containing aquo ligands. The effects of separately deuterating the ligands and the surrounding solvent were investigated for some ammine couples. Possible origins of the solvent isotope effects are discussed in terms of changes in metal-ligand and ligand-solvent interactions. It is tentatively concluded that the latter influence provides the predominant contribution to the observed effects for aquo couples arising from increases in the extent of hydrogen bonding between the aquo ligands and surrounding solvent when D 2 O replaces H 2 O. The implications of these results in unraveling the solvent isotope effects upon the kinetics of simple redox reactions are also considered
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International Nuclear Information System (INIS)
Espinoza R, R.L.
1985-01-01
Some studies on the interaction of benzotriazole with the aquapentacyanoferrate (II), aquapentaamminruthenium (II) and cis-and trans-(NH 3 ) 4 Ru(H 2 O) 2 2+ complexes are described. The reactions, substituted products and complexes production are demonstrated. The absorption bands for the ammine (benzotriazole) and ruthenium (II) complexes as well as the activation parameters and kinetics of reactions are discussed. (M.J.C.) [pt
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International Nuclear Information System (INIS)
1994-01-01
This International Standard specifies an analytical method for determining the nitrogen content in uranium metal and uranium dioxide powder and pellets. It is applicable to the determination of nitrogen, present as nitride, in uranium metal and uranium dioxide powder and pellets. The concentration range within which the method can be used is between 9 μg and 600 μg of nitrogen per gram. Interference can occur from metals which form complex ammines, but these are not normally present in significant amounts
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Proton magnetic resonance spectra of metal ammine complexes, 8
International Nuclear Information System (INIS)
Taura, Toshiaki; Sakaguchi, Ushio; Yoneda, Hayami
1976-01-01
The rates of amine hydrogen isotopic exchange in the [Co(O) 2 (N) 4 ] + complex ions, where (O) 2 represents carbonate, oxalate, or malonate ions, and (N) 4 , tetraamine, bis(ethylenediamine), or bis(trimethylenediamine), were measured in D 2 O at 35 0 C by the PMR technique. It was found that: (1) the rates for trans (to oxygen) amines are faster than those for cis amines; (2) the rates, especially for trans amines, in the carbonato complexes are slower than those in the oxalato and malonato analogs, and (3) the difference between the rates for cis and trans amines is smaller in the bis(diamine) complexes than in the tetraammine complexes. These results are discussed in terms of the influence of the chelate geometry in the complex on the exchange reaction. (auth.)
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Energy Technology Data Exchange (ETDEWEB)
Lieberman, M.L.; Fleming, W.
1986-01-01
The compound 2-(5-cyanotetrazolato)pentaamminecobalt(III) perchlorate (CP) has been utilized in low-voltage detonators because it reliably undergoes deflagration-to-detonation transition (DDT). In the present investigation, we have compared the performance of over a dozen similar compounds. These compounds all have cobalt as the coordinating metal, most are ammine complexes, and all except one incorporate the perchlorate anion as an oxidizer. Chemical factors such as fuel-to-oxidizer ratio, trigger group, and organic content have been varied. 18 refs., 7 figs., 2 tabs.
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International Nuclear Information System (INIS)
Artyukhin, P.I.; Shavinskij, B.M.; Mityakin, Yu.L.
1979-01-01
The technique of neutron activation determination of 15 impurity elements (Au, Ag, Ba, Cd, Co, Cs, Cu, Hg, K, Na, Ni, Se, Sr, Te, Zn) in high-purity bismuth (impurity content is approximately 10 -6 -10 -10 %) is presented. Bismuth hydroxide precipitation by ammonia from nitric acid solutions was used to separate bismuth from alkali, alkaline earth metals and elements forming stable ammines. Gold, selenium and tellurium are isolated in the form of metals at reduction by muriatic hydrazine. Results of analyzing two samples of special purity bismuth are presented. Neutron flux comprised 0.8-1x10 13 n/cm 2 xs. Radiation time was equal to 90 hours
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International Nuclear Information System (INIS)
Sano, Hirotoshi; Harada, Masayuki; Endo, Kazutoyo
1978-01-01
The yields of 57 Fe(II)-species produced after EC-decay were compared with those of 60 Co(II)-species produced in the 59 Co(n, γ) 60 Co reaction for twelve cobalt(III) coordination compounds. The results indicate that the radiochemical yield of 60 Co(II)-species correlates with the yield of 57 Fe(II)-species except in the case of [Co(NH 3 ) 6 ] 2 (CrO 4 ) 3 . The anomalously low yield of 57 Fe(II)-species in [Co(NH 3 ) 6 ] 2 (CrO 4 ) 3 is ascribed to the reaction of chromate anions with ammine ligands initiated by the nuclear transformation in a solid. (author)
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Crystal structure of [UO2(NH35]NO3·NH3
Directory of Open Access Journals (Sweden)
Patrick Woidy
2016-12-01
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.
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Evaluation of radiolabeled ruthenium compounds as tumor-localizing agents
International Nuclear Information System (INIS)
Srivastava, S.C.; Richards, P.; Meinken, G.E.; Som, P.; Atkins, H.L.; Larson, S.M.; Grunbaum, Z.; Rasey, J.S.; Clarke, M.H.; Dowling, M.
1979-01-01
This work introduces a new class of radiopharmaceuticals based on ruthenium-97. The excellent physical properties of Ru-97, the high chemical reactivity of Ru, the potential antitumor activity of several Ru coordination compounds, and BLIP production of Ru-97, provide a unique combination for the application of this isotope in nuclear oncology. A systematic study was undertaken on the synthesis, characterization, and evaluation of a number of ruthenium-labeled compounds. In a variety of animal tumor models, several compounds show considerable promise as tumor-localizing agents when compared to gallium-67 citrate. The compounds studied (with Ru in different oxidation states) include ionic Ru, a number of hydrophilic and lipophilic chelates, and various ammine derivatives
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Metal Oxides Doped PPY-PVA Blend Thin Films Based Gas Sensor
Directory of Open Access Journals (Sweden)
D. B. DUPARE
2009-02-01
Full Text Available Synthesis of metal oxides doped polypyrrole–polyvinyl alcohol blend thin films by in situ chemical oxidative polymerization, using microwave oven on glass substrate for development of Ammonia and Trimethyl ammine hazardous gas sensor. The all experimental process carried out at room temperature(304 K. These polymer materials were characterized by Chemical analyses, spectral studies (UV-visible and IR and conductivity measurement by four –probe technique. The surface morphology as observed in the SEM image was observed to be uniformly covering the entire substrate surface. The sensor was used for different concentration (ppm of TMA and Ammonia gas investigation at room temperature (304 k. This study found to possess improved electrical, mechanical and environmental stability metal oxides doped PPY-PVA films.
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Directory of Open Access Journals (Sweden)
Piotr Brzezinski
2018-02-01
Full Text Available Scope ouf our study is to treat with natural remedies vaginitis in woman, when it has been detected the disease originates from bacterical assault (Gardnerella vaginalis and/or Streptococca spp. in order to avoid the administration of perilous antibiotics and elicit sexual desire and eliminate pain during urination in the woman who has suffered from this disease after 4-5 days only. We have to proceed with the preliminary phase of a simplest test (the ammin whiff test and determine the type of vaginitis and thus treat it using champagne or cider vinegar to adjust mucosal pH and kefir, a fermented beverage, that is extremely rich in mesophyllic bacteria, apt to reveal an important and suggestive function regard vaginal microbes.
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Ammonia for hydrogen storage: challenges and opportunities
DEFF Research Database (Denmark)
Klerke, Asbjørn; Christensen, Claus H.; Nørskov, Jens Kehlet
2008-01-01
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....
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Computational analysis of gas-solid interactions in materials for energy storage and conversion
DEFF Research Database (Denmark)
Lysgaard, Steen
. The focus is specifically on the investigation of catalytic materials for electrochemical CO2 fixation into fuels as well as ammonia storage materials, using computational methods relying on density functional theory (DFT) and effective medium theory (EMT) calculations as well as a genetic algorithm....... Nanoparticles of binary alloys have previously been shown to be catalytically active for electrochemical CO2 fixation. The stability of the nanoparticles is critical for a catalytic system. We have developed a method to determine the structure and composition of nanoparticles under reactive conditions...... found in certain experiments. We have furthermore determined a stable surface state of ammonia in SrCl2 ammines and identified its implications on the ab- and desorption kinetics. Metal salts often bind ammonia and water molecules in a similar structural coordination. We have studied the competitive...
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International Nuclear Information System (INIS)
Kasamatsu, Yoshitaka; Yokokita, Takuya; Toyomura, Keigo; Shigekawa, Yudai; Haba, Hiromitsu; Kanaya, Jumpei; Huang, Minghui; Ezaki, Yutaka; Yoshimura, Takashi; Morita, Kosuke; Shinohara, Atsushi
2016-01-01
To establish a new methodology for superheavy element chemistry, the coprecipitation behaviors of 34 elements with samarium hydroxide were investigated using multitracer produced by a spallation of Ta. The chemical reactions were rapidly equilibrated within 10 s for many elements. In addition, these elements exhibited individual coprecipitation behaviors, and the behaviors were qualitatively related to their hydroxide precipitation behaviors. It was demonstrated that the ammine and hydroxide complex formations of superheavy elements could be investigated using the established method. - Highlights: • We established a new methodology for superheavy element (SHE) chemistry. • Coprecipitation behaviors of 34 elements with Sm hydroxide could be simultaneously investigated by using multitracer. • The complex formations were investigated from the coprecipitation behaviors. • The established method will lead to the study on various precipitates of SHEs.
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International Nuclear Information System (INIS)
Fang, Hongmei; Zhao, Li; Yue, Wenbo; Wang, Yuan; Jiang, Yang; Zhang, Yuan
2015-01-01
Graphene-based metal oxides are desirable as potential anode materials for lithium-ion batteries (LIBs) owing to their superior electrochemical properties. In this work, sandwich-structured graphene-metal oxide (ZnO, NiO) composites are facilely synthesized on a large scale through self-assembly of graphene oxide nanosheets and metal ammine complexes, and then thermal decomposition of the self-assembled products. ZnO or NiO nanoparticles with diameters of 5∼10 nm are immobilized between the layers of graphene nanosheets, which may provide the space for accommodating the volume change of metal oxides during cycles, and highly improve the electronic conductivity of the composites. Accordingly, these sandwich-structured composites exhibit enhanced electrochemical performances compared to metal oxide particles or stacked graphene nanosheets. This facile synthesis method is very suitable for the large-scale production of three-dimensional graphene-based composites as high-performance anodes for LIBs.
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Directory of Open Access Journals (Sweden)
Joachim Breternitz
2018-06-01
Full Text Available Nickel nitrate diammine, Ni(NH32(NO32, can be synthesised from the thermal decomposition of nickel nitrate hexammine, Ni[(NH36](NO32. The hexammine decomposes in two distinct major stages; the first releases 4 equivalents of ammonia while the second involves the release of NOx, N2, and H2O to yield NiO. The intermediate diammine compound can be isolated following the first deammoniation step or synthesised as a single phase from the hexammine under vacuum. Powder X-ray diffraction (PXD experiments have allowed the structure of Ni(NH32(NO32 to be solved for the first time. The compound crystallises in orthorhombic space group Pca21 (a = 11.0628 (5 Å, b = 6.0454 (3 Å, c = 9.3526 (4 Å; Z = 4 and contains 11 non-hydrogen atoms in the asymmetric unit. Fourier transform infrared (FTIR spectroscopy demonstrates that the bonding in the ammine is consistent with the structure determined by PXD.
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Woidy, Patrick; Bühl, Michael; Kraus, Florian
2015-04-28
Pentaammine dioxido uranium(VI) dibromide ammonia (1/1), [UO2(NH3)5]Br2·NH3, was synthesized in the form of yellow crystals by the reaction of uranyl bromide, UO2Br2, with dry liquid ammonia. The compound crystallizes orthorhombic in space group Cmcm and is isotypic to [UO2(NH3)5]Cl2·NH3 with a = 13.2499(2), b = 10.5536(1), c = 8.9126(1) Å, V = 1246.29(3) Å(3) and Z = 4 at 123 K. The UO2(2+) cation is coordinated by five ammine ligands and the coordination polyhedron can be best described as pentagonal bipyramid. Car-Parrinello molecular dynamics simulations are reported for [UO2(NH3)5](2+) in the gas phase and in liquid NH3 solution (using the BLYP density functional). According to free-energy simulations, solvation by ammonia has only a small effect on the uranyl-NH3 bond strength.
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Tetraammine(carbonato-κ2O,O′cobalt(III nitrate: a powder X-ray diffraction study
Directory of Open Access Journals (Sweden)
Armel Le Bail
2013-07-01
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%.
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Recyclable epoxy resins: An example of green approach for advanced composite applications
Cicala, Gianluca; Rosa, Daniela La; Musarra, Marco; Saccullo, Giuseppe; Banatao, Rey; Pastine, Stefan
2016-05-01
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.
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Ammonia Synthesis at Low Pressure.
Cussler, Edward; McCormick, Alon; Reese, Michael; Malmali, Mahdi
2017-08-23
Ammonia can be synthesized at low pressure by the use of an ammonia selective absorbent. The process can be driven with wind energy, available locally in areas requiring ammonia for synthetic fertilizer. Such wind energy is often called "stranded," because it is only available far from population centers where it can be directly used. In the proposed low pressure process, nitrogen is made from air using pressure swing absorption, and hydrogen is produced by electrolysis of water. While these gases can react at approximately 400 °C in the presence of a promoted conventional catalyst, the conversion is often limited by the reverse reaction, which makes this reaction only feasible at high pressures. This limitation can be removed by absorption on an ammine-like calcium or magnesium chloride. Such alkaline metal halides can effectively remove ammonia, thus suppressing the equilibrium constraints of the reaction. In the proposed absorption-enhanced ammonia synthesis process, the rate of reaction may then be controlled not by the chemical kinetics nor the absorption rates, but by the rate of the recycle of unreacted gases. The results compare favorably with ammonia made from a conventional small scale Haber-Bosch process.
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Energy Technology Data Exchange (ETDEWEB)
Jalilehvand, F.; Laffin, L.J.
2009-05-18
Careful analysis of Pt L{sub 3}-edge extended X-ray absorption fine structure (EXAFS) spectra shows that the hydrated platinum(II) ion in acidic (HClO{sub 4}) aqueous solution binds four water molecules with the Pt-O bond distance 2.01(2) {angstrom} and one (or two) in the axial position at 2.39(2) {angstrom}. The weak axial water coordination is in accordance with the unexpectedly small activation volume previously reported for water exchange in an interchange mechanism with associative character. The hydrated cis-diammineplatinum(II) complex has a similar coordination environment with two ammine and two aqua ligands strongly bound with Pt-O/N bond distances of 2.01(2) {angstrom} and, in addition, one (or two) axial water molecule at 2.37(2) {angstrom}. This result provides a new basis for theoretical computational studies aiming to connect the function of the anticancer drug cis-platin to its ligand exchange reactions, where usually four-coordinated square planar platinum(II) species are considered as the reactant and product. {sup 195}Pt NMR spectroscopy has been used to characterize the Pt(II) complexes.
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Diffusion of Water through Olivine and Clinopyroxene: Implications for Melt Inclusion Fidelity
Plank, T. A.; Lloyd, A. S.; Ferriss, E.
2016-12-01
The maximum H2O concentrations measured in olivine-hosted melt inclusions (MIs) from arc tephra fall within a narrow range of 3-5 wt%. A major question is whether this reflects parental water concentrations or diffusive exchange through the host crystal during storage and ascent. Laboratory experiments have shown that water can diffuse through 500 micron olivine in minutes to days at 1100°C. We have tested these predictions with a natural experiment using volatile (H2O, CO2, S) diffusion along melt embayments to constrain ascent rates during the 1974 eruption of Volcan Fuego to 5-8 minutes from 7 km depth [1]. Thus, olivine-hosted MIs may move from their storage region to the surface during some eruptions rapidly enough to retain almost all of their original water. Only the smallest MIs (500 microns) and large melt inclusions (>50 microns), and 4) rapid post-eruptive cooling (< 1min, clast sizes < 1 cm). The rapid diffusion of H through olivine and cpx presents a challenge to MI fidelity, but not necessarily if the above conditions are met. [1] Lloyd et al., 2014, JVGR. [2] Ferriss et al., 2016, AmMin.
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Boubekeur-Lecaque, Leïla; Coe, Benjamin J; Harris, James A; Helliwell, Madeleine; Asselberghs, Inge; Clays, Koen; Foerier, Stijn; Verbiest, Thierry
2011-12-19
Nine nonlinear optical (NLO) chromophores with pyridinium electron acceptors have been synthesized by complexing new proligands with {Ru(II)(NH(3))(5)}(2+) electron-donor centers. The presence of long alkyl/fluoroalkyl chain substituents imparts amphiphilic properties, and these cationic complexes have been characterized as their PF(6)(-) salts by using various techniques including electronic absorption spectroscopy and cyclic voltammetry. Each complex shows three reversible/quasireversible redox processes; a Ru(III/II) oxidation and two ligand-based reductions. The energies of the intense visible d → π* metal-to-ligand charge-transfer (MLCT) absorptions correlate to some extent with the ligand reduction potentials. (1)H NMR spectroscopy also provides insights into the relative electron-withdrawing strengths of the new ligands. Single crystal X-ray structures have been determined for two of the proligand salts and one complex salt, [Ru(II)(NH(3))(5)(4-C(16)H(33)PhQ(+))]Cl(3)·3.25H(2)O (PhQ(+) = N-phenyl-4,4'-bipyridinium), showing centrosymmetric packing structures in each case. The PF(6)(-) analogue of the latter complex has been used to deposit reproducibly high-quality, multilayered Langmuir-Blodgett (LB) thin films. These films show a strong second harmonic generation (SHG) response from a 1064 nm laser; their MLCT absorbance increases linearly with the number of layers (N) and I(2ω)/I(ω)(2) (I(2ω) = intensity at 532 nm; I(ω) = intensity at 1064 nm) scales quadratically with N, consistent with homogeneous deposition. LB films on indium tin oxide (ITO)-coated glass show electrochemically induced switching of the SHG response, with a decrease in activity of about 50% on Ru(II) → Ru(III) oxidation. This effect is reversible, but reproducible over only a few cycles before the signal from the Ru(II) species diminishes. This work extrapolates our original solution studies (Coe, B. J. et al. Angew. Chem., Int. Ed.1999, 38, 366) to the first demonstration of redox-switching of NLO activity in a molecular material. © 2011 American Chemical Society
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Khazeni, Naasser
This study explores the potential of Zn(NH3)(CO3) for selective CO2 separation. It develops a novel, highly controllable, single-pot synthesis approach based on urea hydrolysis and solvothermal aging to increase the feasibility of synthesizing Zn(NH3)(CO3), determines the structure of Zn(NH3)(CO3) in detail through single crystal X-ray diffraction and powder X-ray diffraction analyses, and performs adsorption analyses for the compound using CO2, N 2, H2, O2, and CH4 as adsorptives. Through adsorptive characterization, a systematic adsorbent selection screening is performed to assess the potential application of Zn(NH3)(CO 3) for adsorptive separation of CO2 from an upstream gas mixture of power generation, hydrogen production, and natural gas industries. Structural analysis shows Zn(NH3)(CO3) to have an inorganic helical framework that consists of a small helix of (ZnOCO) 2 and a large helix of (ZnOCO)4 with two ammines (NH 3) pendant from every other zinc. In terms of adsorption capacity and CO2 selectivity, Zn(NH3)(CO3) adsorbed 0.550 mmole/g CO2 at 293 K and 4500 mmHg, but only 0.047 mmole/g N 2, 0.084 mmole/g H2, 0.207 mmole/g 02, and 0.060 mmole/g CH4 at the same temperature and pressure. This behavior demonstrates considerable equilibrium selectivities - 36, 31, 63, and 11 - for separating CO2 from CH4, CO2 from H 2, CO2 from N2, and CO2 from 02, respectively. During adsorption, the pendant ammines act as the gates of check-valves: applied pressure opens the gates for adsorption; and during desorption, the gates are closed, trapping the adsorbates, until a reduction of pressure to near-atmospheric levels. Therefore, Zn(NH3)(CO3) exhibits low-pressure H3 or H4 hysteresis, indicating that the Zn(NH3)(CO3) framework can achieve gas storage at near-atmospheric pressures. Additionally, the compound proves structurally stable, with an adsorption decrease of 0.8% after 20 adsorption/desorption cycles - a factor that, considered with the other characteristics of Zn
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Balasekaran, Samundeeswari Mariappan; Spandl, Johann; Hagenbach, Adelheid; Köhler, Klaus; Drees, Markus; Abram, Ulrich
2014-05-19
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+).
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Structural and functional organization of ribosomal genes within the mammalian cell nucleolus.
Derenzini, Massimo; Pasquinelli, Gianandrea; O'Donohue, Marie-Françoise; Ploton, Dominique; Thiry, Marc
2006-02-01
Data on the in situ structural-functional organization of ribosomal genes in the mammalian cell nucleolus are reviewed here. Major findings on chromatin structure in situ come from investigations carried out using the Feulgen-like osmium ammine reaction as a highly specific electron-opaque DNA tracer. Intranucleolar chromatin shows three different levels of organization: compact clumps, fibers ranging from 11 to 30 nm, and loose agglomerates of extended DNA filaments. Both clumps and fibers of chromatin exhibit a nucleosomal organization that is lacking in the loose agglomerates of extended DNA filaments. In fact, these filaments constantly show a thickness of 2-3 nm, the same as a DNA double-helix molecule. The loose agglomerates of DNA filaments are located in the fibrillar centers, the interphase counterpart of metaphase NORs, therefore being constituted by ribosomal DNA. The extended, non-nucleosomal configuration of this rDNA has been shown to be independent of transcriptional activity and characterizes ribosome genes that are either transcribed or transcriptionally silent. Data reviewed are consistent with a model of control for ribosome gene activity that is not mediated by changes in chromatin structure. The presence of rDNA in mammalian cells always structurally ready for transcription might facilitate a more rapid adjustment of the ribosome production in response to the metabolic needs of the cell.
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Wijeyasinghe, Nilushi
2017-07-28
This study reports the development of copper(I) thiocyanate (CuSCN) hole-transport layers (HTLs) processed from aqueous ammonia as a novel alternative to conventional n-alkyl sulfide solvents. Wide bandgap (3.4–3.9 eV) and ultrathin (3–5 nm) layers of CuSCN are formed when the aqueous CuSCN–ammine complex solution is spin-cast in air and annealed at 100 °C. X-ray photoelectron spectroscopy confirms the high compositional purity of the formed CuSCN layers, while the high-resolution valence band spectra agree with first-principles calculations. Study of the hole-transport properties using field-effect transistor measurements reveals that the aqueous-processed CuSCN layers exhibit a fivefold higher hole mobility than films processed from diethyl sulfide solutions with the maximum values approaching 0.1 cm2 V−1 s−1. A further interesting characteristic is the low surface roughness of the resulting CuSCN layers, which in the case of solar cells helps to planarize the indium tin oxide anode. Organic bulk heterojunction and planar organometal halide perovskite solar cells based on aqueous-processed CuSCN HTLs yield power conversion efficiency of 10.7% and 17.5%, respectively. Importantly, aqueous-processed CuSCN-based cells consistently outperform devices based on poly(3,4-ethylenedioxythiophene) polystyrene sulfonate HTLs. This is the first report on CuSCN films and devices processed via an aqueous-based synthetic route that is compatible with high-throughput manufacturing and paves the way for further developments.
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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: teve@dtu.dk [Department of Energy Conversion and Storage, Technical University of Denmark, Frederiksborgvej 399, DK-4000 Roskilde (Denmark); Quaade, Ulrich J., E-mail: ujq@amminex.com [Amminex Emissions Technology A/S, Gladsaxevej 363, 2860 Soeborg (Denmark)
2015-01-15
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.
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Varadwaj, Pradeep R; Marques, Helder M
2010-03-07
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.
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Man, Wai-Lun; Lam, William W Y; Kwong, Hoi-Ki; Peng, Shie-Ming; Wong, Wing-Tak; Lau, Tai-Chu
2010-01-04
The reaction of [Ru(VI)(N)(L)(MeOH)](PF(6)) [1; L = N,N'-bis(salicylidene)-o-cyclohexyldiamine dianion] with a stoichiometric amount of RSH in CH(3)CN gives the corresponding (salen)ruthenium(IV) sulfilamido species [Ru(IV){N(H)SR}(L)(NCCH(3))](PF(6)) (2a, R = (t)Bu; 2b, R = Ph). Metathesis of 2a with NaN(3) in methanol affords [Ru(IV){N(H)S(t)Bu}(L)(N(3))] (2c). 2a undergoes further reaction with 1 equiv of RSH to afford a (salen)ruthenium(III) sulfilamine species, [Ru(III){N(H)(2)S(t)Bu}(L)(NCCH(3))](PF(6)) (3). On the other hand, 2b reacts with 2 equiv of PhSH to give a (salen)ruthenium(III) ammine species [Ru(III)(NH(3))(L)(NCCH(3))](PF(6)) (4); this species can also be prepared by treatment of 1 with 3 equiv of PhSH. The X-ray structures of 2c and 4 have been determined. Kinetic studies of the reaction of 1 with excess RSH indicate the following schemes: 1 --> 2a --> 3 (R = (t)Bu), 1 --> 2b --> 4 (R = Ph). The conversion of 1 to 2 probably involves nucleophilic attack of RSH at the nitrido ligand, followed by a proton shift. The conversions of 2a to 3 and 2b to 4 are proposed to involve rate-limiting H-atom abstraction from RSH by 2a or 2b. 2a and 2b are also able to abstract H atoms from hydrocarbons with weak C-H bonds. These reactions occur with large deuterium isotope effects; the kinetic isotope effect values for the oxidation of 9,10-dihydroanthracene, 1,4-cyclohexadiene, and fluorene by 2a are 51, 56, and 11, respectively.
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Photocytotoxic trans-diam(m)ine platinum(IV) diazido complexes more potent than their cis isomers.
Farrer, Nicola J; Woods, Julie A; Munk, Vivienne P; Mackay, Fiona S; Sadler, Peter J
2010-02-15
The photocytotoxicity of a series of anticancer trans-dihydroxido [Pt(N(3))(2)(OH)(2)(NH(3))(X)] (X = alkyl or aryl amine) platinum(IV) diazido complexes has been examined, and the influence of cis-trans isomerism has been investigated. A series of photoactivatable Pt(IV)-azido complexes has been synthesized: The synthesis, characterization, and photocytotoxicity of six mixed-ligand ammine/amine Pt(IV) diazido complexes, cis,trans,cis-[Pt(N(3))(2)(OH)(2)(NH(3))(X)] where X = propylamine (4c), butylamine (5c), or pentylamine (6c) and aromatic complexes where X = pyridine (7c), 2-methylpyridine (8c), or 3-methylpyridine (9c) are reported. Six all-trans isomers have also been studied where X = methylamine (2t), ethylamine (3t), 2-methylpyridine (8t), 4-methylpyridine (10t), 3-methylpyridine (9t), and 2-bromo-3-methylpyridine (11t). All of the complexes exhibit intense azide-to-Pt(IV) LMCT bands (ca. 290 nm for trans and ca. 260 nm for cis). When irradiated with UVA light (365 nm), the Pt(IV) complexes undergo photoreduction to Pt(II) species, as monitored by UV-vis spectroscopy. The trans isomers of complexes containing aliphatic or aromatic amines were more photocytotoxic than their cis isomers. One of the cis complexes (9c) was nonphotocytotoxic despite undergoing photoreduction. Substitution of NH(3) ligands by MeNH(2) or EtNH(2) results in more potent photocytotoxicity for the all-trans complexes. The complexes were all nontoxic toward human keratinocytes (HaCaT) and A2780 human ovarian cancer cells in the dark, apart from the 3-methylpyridine (9t), 2-bromo-3-methylpyridine (11t), and 4-methylpyridine (10t) derivatives.
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Reduction of RuVI≡N to RuIII-NH3 by Cysteine in Aqueous Solution.
Wang, Qian; Man, Wai-Lun; Lam, William W Y; Yiu, Shek-Man; Tse, Man-Kit; Lau, Tai-Chu
2018-05-21
The reduction of metal nitride to ammonia is a key step in biological and chemical nitrogen fixation. We report herein the facile reduction of a ruthenium(VI) nitrido complex [(L)Ru VI (N)(OH 2 )] + (1, L = N, N'-bis(salicylidene)- o-cyclohexyldiamine dianion) to [(L)Ru III (NH 3 )(OH 2 )] + by l-cysteine (Cys), an ubiquitous biological reductant, in aqueous solution. At pH 1.0-5.3, the reaction has the following stoichiometry: [(L)Ru VI (N)(OH 2 )] + + 3HSCH 2 CH(NH 3 )CO 2 → [(L)Ru III (NH 3 )(OH 2 )] + + 1.5(SCH 2 CH(NH 3 )CO 2 ) 2 . Kinetic studies show that at pH 1 the reaction consists of two phases, while at pH 5 there are three distinct phases. For all phases the rate law is rate = k 2 [1][Cys]. Studies on the effects of acidity indicate that both HSCH 2 CH(NH 3 + )CO 2 - and - SCH 2 CH(NH 3 + )CO 2 - are kinetically active species. At pH 1, the reaction is proposed to go through [(L)Ru IV (NHSCH 2 CHNH 3 CO 2 H)(OH 2 )] 2+ (2a), [(L)Ru III (NH 2 SCH 2 CHNH 3 CO 2 H)(OH 2 )] 2+ (3), and [(L)Ru IV (NH 2 )(OH 2 )] + (4) intermediates. On the other hand, at pH around 5, the proposed intermediates are [(L)Ru IV (NHSCH 2 CHNH 3 CO 2 )(OH 2 )] + (2b) and [(L)Ru IV (NH 2 )(OH 2 )] + (4). The intermediate ruthenium(IV) sulfilamido species, [(L)Ru IV (NHSCH 2 CHNH 3 CO 2 H)(OH 2 )] 2+ (2a) and the final ruthenium(III) ammine species, [(L)Ru III (NH 3 )(MeOH)] + (5) (where H 2 O was replaced by MeOH) have been isolated and characterized by various spectroscopic methods.
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Chen, Yuan-Jang; Xie, Puhui; Endicott, John F; Odongo, Onduru S
2006-06-29
The effects of ligand perdeuteration on the metal-to-ligand charge-transfer (MLCT) excited-state emission properties at 77 K are described for several [Ru(L)(4)bpy](2+) complexes in which the emission process is nominally [uIII,bpy-] --> [RuII,bpy]. The perdeuteration of the 2,2'-bipyridine (bpy) ligand is found to increase the zero-point energy differences between the ground states and MLCT excited states by amounts that vary from 0 +/- 10 to 70 +/- 10 cm(-1) depending on the ligands L. This indicates that there are some vibrational modes with smaller force constants in the excited states than in the ground states for most of these complexes. These blue shifts increase approximately as the energy difference between the excited and ground states decreases, but they are otherwise not strongly correlated with the number of bipyridine ligands in the complex. Careful comparisons of the [Ru(L)(4)(d(8)-bpy)](2+) and [Ru(L)(4)(h(8)-bpy](2+) emission spectra are used to resolve the very weak vibronic contributions of the C-H stretching modes as the composite contributions of the corresponding vibrational reorganizational energies. The largest of these, 25 +/- 10 cm(-1), is found for the complexes with L = py or bpy/2 and smaller when L = NH(3). Perdeuteration of the am(m)ine ligands (NH(3), en, or [14]aneN(4)) has no significant effect on the zero-point energy difference, and the contributions of the NH stretching vibrational modes to the emission band shape are too weak to resolve. Ligand perdeuteration does increase the excited-state lifetimes by a factor that is roughly proportional to the excited-state-ground-state energy difference, even though the CH and NH vibrational reorganizational energies are too small for nuclear tunneling involving these modes to dominate the relaxation process. It is proposed that metal-ligand skeletal vibrational modes and configurational mixing between metal-centered, bpy-ligand-centered, and MLCT excited states are important in