Luminescent Lanthanide Metal Organic Frameworks for cis-Selective Isoprene Polymerization Catalysis

Directory of Open Access Journals (Sweden)

Samantha Russell

2015-11-01

Full Text Available In this study, we are combining two areas of chemistry; solid-state coordination polymers (or Metal-Organic Framework—MOF and polymerization catalysis. MOF compounds combining two sets of different lanthanide elements (Nd3+, Eu3+/Tb3+ were used for that purpose: the use of neodymium was required due to its well-known catalytic properties in dienes polymerization. A second lanthanide, europium or terbium, was included in the MOF structure with the aim to provide luminescent properties. Several lanthanides-based MOF meeting these criteria were prepared according to different approaches, and they were further used as catalysts for the polymerization of isoprene. Stereoregular cis-polyisoprene was received, which in some cases exhibited luminescent properties in the UV-visible range.

Dynamics of anion exchange of lanthanides in aqueous-organic complexing media

International Nuclear Information System (INIS)

Sheveleva, I.V.; Bogatyrev, I.O.

1987-01-01

Effect of organic solvents (ethanol, acetone, acetonitrile) on change in kinetic parameters of the anion exchange process (anion-exchange column chromatography) of r.e.e. (europium and gadolinium) in complexing nitric acid media has been studied. It is established that complex LnA 4 anion is the only sorbing form of europium and gadolinium on anionite. When the organic component content of the solution being the same, the dynamic parameters of lanthanide exchange have higher values in aqueous-acetonitrile and aqueous-acetone media in comparison with aqueous-enthanol solutions of nitric acid. Lesser mobility of complex lanthanide anions in aqueous-alcoholic solutions can be explained by stronger solvation in the presence of solvents with higher acceptor properties

Effect of drying method on properties of vanadium-molybdenum oxide catalysts

International Nuclear Information System (INIS)

Gorshkova, T.P.; Savchenko, L.A.; Tarasova, D.V.; Tret'yakov, Yu.D.; Olen'kova, I.P.; Nikoro, T.A.; Maksimov, N.G.

1981-01-01

Effect of drying method of molybdenum and vanadium salt solutions on physicochemical and catalytical properties of vanadium-molybdenum catalysts is studied. It is shown that the drying method of solutions determines the completeness of vanadium binding into oxide vanadium-molybdenum compounds and thus effects the activity and selectivity of catalysts in acrolein oxidation into acrylic acid. Besides the drying method determines the porous structure of catalysts [ru

Vanadium in organic fossils as determined by nuclear-physical methods of analysis

International Nuclear Information System (INIS)

Nadirov, N.N.; Solodukhin, V.P.

1998-01-01

Results are presented of several year investigation to study possibilities of the NPMA for the determination of vanadium in organic fossils and applications of these methods to scientific and practical tasks. For these purposes, various versions of activation analysis (AA), X-ray fluorescence analysis (XRFA), electron spin resonance (ESR) spectroscopy and atomic emission with inductively coupled plasma spectroscopy (AES-ICP). Advantages and pitfalls of individual methods are discussed. The techniques developed can be used for estimation and calculation of stocks of vanadium in organic fossils at the territories of Kazakstan, Tatarstan and along the Volga-river. Analysis results helped in discovering new, industrially important deposits of this valuable metal. Quantitative determination of vanadium was carried out at different stages of technological processes of its extraction from high-viscous oils and oil-bitumen rocks. Results of analyses allowed to reveal the most effective versions of technologies of demetallization of these fossils. Content of vanadium was also studied in different locations of high-viscous oil deposits being explored by the method of inside-stratum burning. Results of analyses showed that the concentration of vanadium in oil decreases considerably with increasing temperature, that is, a considerable part of vanadium (up to 60 percent) may be lost irretrievably. Thus, for the exploration of these deposits a method of vapor-thermal influence onto the stratum was recommended, by using of which the loss of vanadium is insignificant

Porous Hydrogen-Bonded Organic Frameworks

Directory of Open Access Journals (Sweden)

Yi-Fei Han

2017-02-01

Full Text Available Ordered porous solid-state architectures constructed via non-covalent supramolecular self-assembly have attracted increasing interest due to their unique advantages and potential applications. Porous metal-coordination organic frameworks (MOFs are generated by the assembly of metal coordination centers and organic linkers. Compared to MOFs, porous hydrogen-bonded organic frameworks (HOFs are readily purified and recovered via simple recrystallization. However, due to lacking of sufficiently ability to orientate self-aggregation of building motifs in predictable manners, rational design and preparation of porous HOFs are still challenging. Herein, we summarize recent developments about porous HOFs and attempt to gain deeper insights into the design strategies of basic building motifs.

Nanoscale luminescent lanthanide-based metal–organic frameworks: properties, synthesis, and applications

Energy Technology Data Exchange (ETDEWEB)

Hu, Dongqin; Song, Yonghai; Wang, Li, E-mail: lwanggroup@aliyun.com [Jiangxi Normal University, Key Laboratory of Functional Small Organic Molecule, Ministry of Education, Key Laboratory of Chemical Biology, Jiangxi Province, College of Chemistry and Chemical Engineering (China)

2015-07-15

Nanoscale luminescent lanthanide-based metal–organic frameworks (NLLn-MOFs) possess superior optical and physical properties such as higher luminescent lifetime, quantum yield, high stability, high surface area, high agent loading, and intrinsic biodegradability, and therefore are regarded as a novel generation of luminescent material compared with bulk lanthanide-based metal–organic frameworks (Ln-MOFs). Traditional luminescent Ln-MOFs have been well studied; however, NLLn-MOFs taking the advantages of nanomaterials have attracted extensive investigations for applications in optical imaging in living cells, light-harvesting, and sensing. In this review, we provide a survey of the latest progresses made in developing NLLn-MOFs, which contains the fundamental optical features, synthesis, and their potential applications. Finally, the future prospects and challenges of the rapidly growing field are summarized.

A General Model of Sensitized Luminescence in Lanthanide-Based Coordination Polymers and Metal-Organic Framework Materials.

Science.gov (United States)

Einkauf, Jeffrey D; Clark, Jessica M; Paulive, Alec; Tanner, Garrett P; de Lill, Daniel T

2017-05-15

Luminescent lanthanides containing coordination polymers and metal-organic frameworks hold great potential in many applications due to their distinctive spectroscopic properties. While the ability to design coordination polymers for specific functions is often mentioned as a major benefit bestowed on these compounds, the lack of a meaningful understanding of the luminescence in lanthanide coordination polymers remains a significant challenge toward functional design. Currently, the study of these compounds is based on the antenna effect as derived from molecular systems, where organic antennae are used to facilitate lanthanide-centered luminescence. This molecular-based approach does not take into account the unique features of extended network solids, particularly the formation of band structure. While guidelines for the antenna effect are well established, they require modification before being applied to coordination polymers. A series of nine coordination polymers with varying topologies and organic linkers were studied to investigate the accuracy of the antenna effect in coordination polymer systems. By comparing a molecular-based approach to a band-based one, it was determined that the band structure that occurs in aggregated organic solids needs to be considered when evaluating the luminescence of lanthanide coordination polymers.

Advanced porous electrodes with flow channels for vanadium redox flow battery

Science.gov (United States)

Bhattarai, Arjun; Wai, Nyunt; Schweiss, Ruediger; Whitehead, Adam; Lim, Tuti M.; Hng, Huey Hoon

2017-02-01

Improving the overall energy efficiency by reducing pumping power and improving flow distribution of electrolyte, is a major challenge for developers of flow batteries. The use of suitable channels can improve flow distribution through the electrodes and reduce flow resistance, hence reducing the energy consumption of the pumps. Although several studies of vanadium redox flow battery have proposed the use of bipolar plates with flow channels, similar to fuel cell designs, this paper presents the use of flow channels in the porous electrode as an alternative approach. Four types of electrodes with channels: rectangular open channel, interdigitated open cut channel, interdigitated circular poked channel and cross poked circular channels, are studied and compared with a conventional electrode without channels. Our study shows that interdigitated open channels can improve the overall energy efficiency up to 2.7% due to improvement in flow distribution and pump power reduction while interdigitated poked channel can improve up to 2.5% due to improvement in flow distribution.

Extraction of Lanthanide and Actinide Ions from Aqueous Mixtures Using a Carboxylic Acid-Functionalized Porous Aromatic Framework

Science.gov (United States)

2016-01-01

Porous aromatic frameworks (PAFs) incorporating a high concentration of acid functional groups possess characteristics that are promising for use in separating lanthanide and actinide metal ions, as required in the treatment of radioactive waste. These materials have been shown to be indefinitely stable to concentrated acids and bases, potentially allowing for multiple adsorption/stripping cycles. Additionally, the PAFs combine exceptional features from MOFs and inorganic/activated carbons giving rise to tunable pore surfaces and maximum chemical stability. Herein, we present a study of the adsorption of selected metal ions, Sr2+, Fe3+, Nd3+, and Am3+, from aqueous solutions employing a carbon-based porous aromatic framework, BPP-7 (Berkeley Porous Polymer-7). This material displays high metal loading capacities together with excellent adsorption selectivity for neodymium over strontium based on Langmuir adsorption isotherms and ideal adsorbed solution theory (IAST) calculations. Based in part upon X-ray absorption spectroscopy studies, the stronger adsorption of neodymium is attributed to multiple metal ion and binding site interactions resulting from the densely functionalized and highly interpenetrated structure of BPP-7. Recyclability and combustibility experiments demonstrate that multiple adsorption/stripping cycles can be completed with minimal degradation of the polymer adsorption capacity. PMID:27163056

Compaction of lanthanide oxide porous microspheres: experimental approach and numerical simulation

International Nuclear Information System (INIS)

Parant, Paul

2016-01-01

One option envisioned for the future management of high level nuclear waste is the transmutation of minor actinides into short-lived fission products in sodium fast reactor. This route requires the development of pellet fabrication processes to prepare Minor Actinide Bearing Blanket (MABB) for the transmutation of americium. Currently, those ceramic pellets are produced by powder metallurgy processes involving numerous grinding and milling steps that generate very fine and highly contaminating and irradiating particles. a viable option for reducing the amount of those fine particles would be to develop a dustless process by working on much coarser particles. In this context, this study is concerned with the pelletizing of porous and spherical lanthanides oxide precursors (surrogates of actinides). The present work uses both experimental data and numerical simulations to optimize the pelletizing step. The final aim is to obtain, after sintering, homogeneous, dense and undistorted ceramic pellets. Firstly, this study concerns the synthesis and characterization of these oxide microspheres precursors by the Weak acid Resin process, which consists in loading beads of ion exchange resin with lanthanides cations and mineralizing the metal loaded resin leads into sub-millimetric-sized oxide microspheres. Comprehensive characterizations of the microstructure were carried out in function of the synthesis parameters such as calcination temperature, metal nature and diameter size /distribution of the resin beads starting materials to better understand their behaviour into the matrix when producing pellets. Secondly, the mechanical properties of a single microsphere were investigated in order to better understand its behaviour during compaction steps. They were also analysed using multi-scale simulations based on the Discrete Element Method (DEM), which is well suited for such particulate materials. In a second approach, compaction studies were carried out in a three parts die

Effect of organic additives on positive electrolyte for vanadium redox battery

International Nuclear Information System (INIS)

Li Sha; Huang Kelong; Liu Suqin; Fang Dong; Wu Xiongwei; Lu Dan; Wu Tao

2011-01-01

Highlights: → Four organics as electrolyte additives of vanadium redox battery. → Changes are examined in the electrochemical properties of vanadium redox battery. → D-sorbitol is a suitable additive to the electrolyte for the vanadium redox battery. → The mechanism of improvement is discussed in detail. - Abstract: Fructose, mannitol, glucose, D-sorbitol are explored as additives in electrolyte for vanadium redox battery (VRB), respectively. The effects of additives on electrolyte are studied by cyclic voltammetry (CV), charge-discharge technique, electrochemical impedance spectroscopy (EIS) and Raman spectroscopy. The results indicate that the vanadium redox cell using the electrolyte with the additive of D-sorbitol exhibits the best electrochemical performance (the energy efficiency 81.8%). The EIS results indicate that the electrochemical activity of the electrolyte is improved by adding D-sorbitol, which can be interpreted as the increase of available (-OH) groups providing active sites for electron transfer. The Raman spectra show that VO 2+ ions take part in forming a complex with the D-sorbitol, which not only improve solubility of V(V) electrolyte, but also provide more activity sites for the V(IV)/V(V) redox reaction.

Effect of organic additives on positive electrolyte for vanadium redox battery

Energy Technology Data Exchange (ETDEWEB)

Li Sha [Department of Functional Materials and Chemistry, School of Chemistry and Chemical Engineering, Central South University, Changsha 410083 (China); Huang Kelong, E-mail: lisha_csu@163.com [Department of Functional Materials and Chemistry, School of Chemistry and Chemical Engineering, Central South University, Changsha 410083 (China); Liu Suqin; Fang Dong; Wu Xiongwei; Lu Dan; Wu Tao [Department of Functional Materials and Chemistry, School of Chemistry and Chemical Engineering, Central South University, Changsha 410083 (China)

2011-06-30

Highlights: > Four organics as electrolyte additives of vanadium redox battery. > Changes are examined in the electrochemical properties of vanadium redox battery. > D-sorbitol is a suitable additive to the electrolyte for the vanadium redox battery. > The mechanism of improvement is discussed in detail. - Abstract: Fructose, mannitol, glucose, D-sorbitol are explored as additives in electrolyte for vanadium redox battery (VRB), respectively. The effects of additives on electrolyte are studied by cyclic voltammetry (CV), charge-discharge technique, electrochemical impedance spectroscopy (EIS) and Raman spectroscopy. The results indicate that the vanadium redox cell using the electrolyte with the additive of D-sorbitol exhibits the best electrochemical performance (the energy efficiency 81.8%). The EIS results indicate that the electrochemical activity of the electrolyte is improved by adding D-sorbitol, which can be interpreted as the increase of available (-OH) groups providing active sites for electron transfer. The Raman spectra show that VO{sup 2+} ions take part in forming a complex with the D-sorbitol, which not only improve solubility of V(V) electrolyte, but also provide more activity sites for the V(IV)/V(V) redox reaction.

Versatile Organic Chemistry on Vanadium-Based Multi-Electron Reservoirs.

Science.gov (United States)

Nachtigall, Olaf; Spandl, Johann

2018-02-21

We report the synthesis, post-functionalization, and redox behavior of two organically functionalized aggregates, [V 6 O 7 (OMe) 9 {(OCH 2 ) 3 C-CH 2 N 3 }] and [V 6 O 7 (OMe) 9 {(OCH 2 ) 3 C-NH 2 }]. All twelve μ 2 -oxo groups on the edges of the Lindqvist-type {V 6 O 19 } core were replaced by alkoxo ligands. The absence of a negative charge and the closed organic shell make these neutral mixed-valence compounds very stable towards hydrolysis and well soluble in almost all common organic solvents. These are important advantages over classical POMs. By post-functionalization through copper(I)-catalyzed Huisgen cycloaddition or imine formation, various organic moieties could be introduced. Even a well-soluble trimer composed of three hexanuclear vanadium units connected through an aromatic triimino core was synthesized and studied. The diverse redox behavior, the versatile reactivity, the good stability, and the excellent solubility make our vanadium compounds highly interesting for applications as building blocks in macromolecular chemistry as well as redox labels in biochemistry. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

A high-performance dual-scale porous electrode for vanadium redox flow batteries

Science.gov (United States)

Zhou, X. L.; Zeng, Y. K.; Zhu, X. B.; Wei, L.; Zhao, T. S.

2016-09-01

In this work, we present a simple and cost-effective method to form a dual-scale porous electrode by KOH activation of the fibers of carbon papers. The large pores (∼10 μm), formed between carbon fibers, serve as the macroscopic pathways for high electrolyte flow rates, while the small pores (∼5 nm), formed on carbon fiber surfaces, act as active sites for rapid electrochemical reactions. It is shown that the Brunauer-Emmett-Teller specific surface area of the carbon paper is increased by a factor of 16 while maintaining the same hydraulic permeability as that of the original carbon paper electrode. We then apply the dual-scale electrode to a vanadium redox flow battery (VRFB) and demonstrate an energy efficiency ranging from 82% to 88% at current densities of 200-400 mA cm-2, which is record breaking as the highest performance of VRFB in the open literature.

Redes metalorgânicas e suas aplicações em catálise

Directory of Open Access Journals (Sweden)

André Luis Dantas Ramos

2014-01-01

Full Text Available Metal-organic frameworks (MOFs form a new class of materials with well-defined yet tunable properties. These are crystalline, highly porous and exhibit strong metal-ligand interactions. Importantly, their physical and chemical properties, including pore size, pore structure, acidity, and magnetic and optical characteristics, can be tailored by choosing the appropriate ligands and metal precursors. Here we review the key aspects of synthesis and characterization of MOFs, focusing on lanthanide-based and vanadium-based materials. We also outline some of their applications in catalysis and materials science.

Lanthanide-doped luminescent ionogels

OpenAIRE

Lunstroot, Kyra; Driesen, Kris; Nockemann, Peter; Van Hecke, Kristof; Van Meervelt, Luc; Görller-Walrand, Christiane; Binnemans, Koen; Bellayer, Séverine; Viau, Lydie; Le Bideau, Jean; Vioux, André

2009-01-01

Ionogels are solid oxide host networks confining at a meso-scale ionic liquids, and retaining their liquid nature. Ionogels were obtained by dissolving anthanide(III) complexes in the ionic liquid 1-hexyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide, [C6mim][Tf2N], followed by confinement of the lanthanide-doped ionic liquid mixtures in the pores of a nano-porous silica network. [C6mim][Ln(tta)4], where tta is 2-thenoyltrifluoroacetonate and Ln = Nd, Sm, Eu, Ho, Er, Yb, and [choli...

Some aspects of synergistic extraction of actinides and lanthanides from mixed aqueous-organic media

International Nuclear Information System (INIS)

Shukla, J.P.; Subramanian, M.S.

1981-01-01

Various aspects of the synergistic extraction and separation of actinides and lanthanides from mixed aqueous-organic solutions (polar media) have been reviewed. Notable recent developments as well as its current status in solvent extraction systems where the aqueous acidic phase contains an organic solvent which is completely miscible with water, are presented briefly. In general, extraction increases in the presence of an organic component. The less polar the additive, the higher is the tendency to form neutral metal complexes which ultimately brings about an increase in the extraction. In a polar media, synergism has mostly been observed, though antagonism is not uncommon. An attempt has been made to classify the factors that play an important role in polar phase extractions. Also, their influence particularly on the extractability of actinides and lanthanides is discussed. The discussion is limited to the factors affecting the extraction equilibria, effect of dielectric constant of the polar medium, solvation of the extracting agent and to the composition and stability of the metal complex in the organic phase. Hydroxyl (OHsup(-)) bearing organic additives, e.g. alcohols, and solvents not containing the hydroxyl group such as acetone, dimethylsulphoxide, tetrahydrofuran, amides and acetonitrile etc. are the two major classes of organic additives considered in these studies. Generally, synergistic effect in extraction of the ion-association (TBP, TOPO, sulphoxides etc.) or anion exchange (amines etc.) type is relatively more pronounced compared to other extractions. A tabular summary concerning extraction of actinides and lanthanides from polar media is appended for ready reference. (author)

Vanadium recovery process

International Nuclear Information System (INIS)

Pyrih, R.Z.; Rickard, R.S.

1978-01-01

A process for recovering vanadium values from carbonaceous type vanadium ores, and vanadium scrap, such as vanadium contaminated spent catalyst, is disclosed which comprises roasting the vanadium containing material in air at a temperature less than about 600 0 C to produce a material substantially devoid of organic matter, subjecting said roasted material to a further oxidizing roast in an oxygen atmosphere at a temperature of at least about 800 0 C for a period sufficient to convert substantially all of the vanadium to the soluble form, leaching the calcine with a suitable dilute mineral acid or water at a pH of neutral to about 2 to recover vanadium values, precipitating vanadium values as iron vanadate from the leach solution with a soluble iron compound at a pH from neutral to about 1, and recovering ferrovanadium from the iron vanadate by a reduction vacuum smelting operation. The conversion of vanadium in the ore to the soluble form by the oxidizing roast is accomplished without the addition of an alkaline salt during calcining

Vanadium - 1977

International Nuclear Information System (INIS)

Broderick, G.N.

1977-01-01

This report, with pertinent references, is a comprehensive description and analysis of the vanadium industry. Included is information on industry structure, size and organization; definitions, grades, and specifications; reserves and resources; geology; production and capacity; uses; technology; byproducts and coproducts; strategic considerations; economic and operating factors and problems; supply-demand relationships; and forecasts of supply and demand. Vanadium is used principally as an alloy in steel. Other important uses are in titanium alloys and in various chemical catalytic processes. The world supply of vanadium is sufficient to last far beyond the year 2000 at the present and projected rates of consumption. Almost all of the resources will economically yield vanadium only in conjunction with a coproduct

Superior lithium storage performance of hierarchical porous vanadium pentoxide nanofibers for lithium ion battery cathodes

Energy Technology Data Exchange (ETDEWEB)

Yan, Bo [Beijing Key Laboratory of Materials Utilization of Nonmetallic Minerals and Solid Wastes, National Laboratory of Mineral Materials, School of Materials Science and Technology, China University of Geosciences, Beijing 100083 (China); Energy & Materials Engineering Centre, College of Physics and Materials Science, Tianjin Normal University, Tianjin 300387 (China); National Key Laboratory of Power Sources, Tianjin Institute of Power Sources, Tianjin 300381 (China); Li, Xifei, E-mail: xfli2011@hotmail.com [Energy & Materials Engineering Centre, College of Physics and Materials Science, Tianjin Normal University, Tianjin 300387 (China); Bai, Zhimin, E-mail: zhimibai@cugb.edu.cn [Beijing Key Laboratory of Materials Utilization of Nonmetallic Minerals and Solid Wastes, National Laboratory of Mineral Materials, School of Materials Science and Technology, China University of Geosciences, Beijing 100083 (China); Li, Minsi [Department of Chemistry, University of Science and Technology of China, Hefei, Anhui 230026 (China); Dong, Lei; Xiong, Dongbin [Energy & Materials Engineering Centre, College of Physics and Materials Science, Tianjin Normal University, Tianjin 300387 (China); Li, Dejun, E-mail: dejunli@mail.tjnu.edu.cn [Energy & Materials Engineering Centre, College of Physics and Materials Science, Tianjin Normal University, Tianjin 300387 (China)

2015-06-15

Highlights: • Hierarchical porous vanadium pentoxide nanofibers were synthesized by electrospinning. • V{sub 2}O{sub 5} nanofibers showed much enhanced lithium storage performance. • Kinetics process of electrospinning V{sub 2}O{sub 5} nanofibers was studied by means of EIS for the first time. • Strategies to enhance the electrochemical performance of V{sub 2}O{sub 5} electrode were concluded. - Abstract: The hierarchical V{sub 2}O{sub 5} nanofibers cathode materials with diameter of 200–400 nm are successfully synthesized via an electrospinning followed by annealing. Powder X-ray diffraction (XRD) pattern confirms the formation of phase-pure product. Scanning electron microscopy (SEM) and transmission electron microscopy (TEM) obviously display the hierarchical porous nanofibers constructed by attached tiny vanadium oxide nanoplates. Electrochemical behavior of the as-prepared product is systematically studied using galvanostatic charge/discharge testing, cyclic voltammetry (CV), and electrochemical impedance spectroscopy (EIS). It turns out that in comparison to the commercial V{sub 2}O{sub 5} and other unique nanostructured materials in the literature, our V{sub 2}O{sub 5} nanofibers show much enhanced lithium storage capacity, improved cyclic stability, and higher rate capability. After 100 cycles at a current density of 800 mA g{sup −1}, the specific capacity of the V{sub 2}O{sub 5} nanofibers retain 133.9 mAh g{sup −1}, corresponding to high capacity retention of 96.05%. More importantly, the EIS at various discharge depths clearly reveal the kinetics process of the V{sub 2}O{sub 5} cathode reaction with lithium. Based on our results, the possible approach to improve the specific capacity and rate capability of the V{sub 2}O{sub 5} cathode material is proposed. It is expected that this study could accelerate the development of V{sub 2}O{sub 5} cathode in rechargeable lithium ion batteries.

Cooperative loading of multisite receptors with lanthanide containers: an approach for organized luminescent metallopolymers.

Science.gov (United States)

Babel, Lucille; Guénée, Laure; Besnard, Céline; Eliseeva, Svetlana V; Petoud, Stéphane; Piguet, Claude

2018-01-14

Metal-containing (bio)organic polymers are materials of continuously increasing importance for applications in energy storage and conversion, drug delivery, shape-memory items, supported catalysts, organic conductors and smart photonic devices. The embodiment of luminescent components provides a revolution in lighting and signaling with the ever-increasing development of polymeric light-emitting devices. Despite the unique properties expected from the introduction of optically and magnetically active lanthanides into organic polymers, the deficient control of the metal loading currently limits their design to empirical and poorly reproducible materials. We show here that the synthetic efforts required for producing soluble multi-site host systems L k are largely overcome by the virtue of reversible thermodynamics for mastering the metal loading with the help of only two parameters: (1) the affinity of the luminescent lanthanide container for a single binding site and (2) the cooperative effect which modulates the successive fixation of metallic units to adjacent sites. When unsymmetrical perfluorobenzene-trifluoroacetylacetonate co-ligands (pbta - ) are selected for balancing the charge of the trivalent lanthanide cations, Ln 3+ , in six-coordinate [Ln(pbta) 3 ] containers, the explored anti-cooperative complexation processes induce nearest-neighbor intermetallic interactions twice as large as thermal energy at room temperature ( RT = 2.5 kJ mol -1 ). These values have no precedent when using standard symmetrical containers and they pave the way for programming metal alternation in luminescent lanthanidopolymers.

Studies of Lanthanide Transport in Metallic Fuel

Energy Technology Data Exchange (ETDEWEB)

Zhang, Jinsuo; Taylor, Christopher

2018-04-02

result, Ln could transport to the fuel surface through pores filled with liquid cesium fission products. At the fuel slug surface, the lanthanides would undergo rapid precipitation when swamped with the large increase in liquid sodium content and cooler temperatures, which would lead to the observed sludge-like deposit. Prior PIE data also show that lanthanide deposits were found on the cold sides of closed and isolated pores, i.e., on pore surfaces directed away from the center, which can also be explained by the liquid-like transport theory. Since the total amount of lanthanides exceeds their solubility limit in liquid cesium, the small temperature gradient across a pore combined with the long durations is sufficient to drive cesium-mediated transport of lanthanides to the cold side of the pore. The liquid-like transport mechanism can qualitatively account for the migration and redistribution of lanthanides fission products in metallic fuels. The present project studied the mechanisms of lanthanide transport in metallic fuels based on the novel interpretation of ‘liquid-like’ transport mechanism experimentally and analytically. The project completed all the proposed research tasks by using an integral approach: (1) experimental studies for measurements of key parameters and first principles calculations to determine, for example, lanthanide solubility and diffusion coefficient in liquid cesium, sodium and cesium-sodium alloy; (2) theoretical model development for lanthanide transport in a non-isothermal single pore and porous medium to understand the observed behavior (deposition, dissolution and migration) in a single closed or open pore and porous medium; (3) further development of the multi-phase/physics BISON model. The key goal of the project is to develop fundamental understanding of the lanthanide fission product migration and redistribution in advanced metallic nuclear fuels, and then to provide fundamental theory/data for mitigating FCCI of advanced

Lanthanide co-ordination frameworks: Opportunities and diversity

International Nuclear Information System (INIS)

Hill, Robert J.; Long, De-Liang; Hubberstey, Peter; Schroeder, Martin; Champness, Neil R.

2005-01-01

Significant successes have been made over recent years in preparing co-ordination framework polymers that show macroscopic material properties, but in the vast majority of cases this has been achieved with d-block metal-based systems. Lanthanide co-ordination frameworks also offer attractive properties in terms of their potential applications as luminescent, non-linear optical and porous materials. However, lanthanide-based systems have been far less studied to date than their d-block counterparts. One possible reason for this is that the co-ordination spheres of lanthanide cations are more difficult to control and, in the absence of design strategies for lanthanide co-ordination frameworks, it is significantly more difficult to target materials with specific properties. However, this article highlights some of the exciting possibilities that have emerged from the earliest investigations in this field with new topological families of compounds being discovered from relatively simple framework components, including unusual eight, seven and five-connected framework systems. Our own research, as well as others, is leading to a much greater appreciation of the factors that control framework formation and the resultant observed topologies of these polymers. As this understanding develops targeting particular framework types will become more straightforward and the development of designed polyfunctional materials more accessible. Thus, it can be seen that lanthanide co-ordination frameworks have the potential to open up previously unexplored directions for materials chemistry. This article focuses on the underlying concepts for the construction of these enticing and potentially highly important materials

Vanadium levels in marine organisms of Onagawa Bay in Japan

International Nuclear Information System (INIS)

Fukushima, M.; Suzuki, H.; Saito, K.; Chatt, A.

2009-01-01

Vanadium in marine organisms from Onagawa Bay in Miyagi, Japan, was determined by an instrumental neutron activation analysis (INAA) method using anticoincidence gamma-ray spectrometry at the Dalhousie University SLOWPOKE-2 Reactor (DUSR) facility in Canada. Seaweeds, cultivated oysters, plankton, and four different species of sea squirt were collected from Onagawa Bay during 2005-2008. Vanadium levels around 20 μg g -1 (dry weight) were found in Japanese tangle and hijiki seaweeds. One species of sea squirt (Ciona savignyi) contained 160-500 ppm of V and it was highest among the four species of sea squirts studied. Protein-bound V species were separated by gel permeation chromatography (GPC) and the element determined by inductively coupled plasma atomic emission spectrometry (ICP-AES). (author)

Lanthanide-doped nanoparticles as the active optical medium in polymer-based devices

NARCIS (Netherlands)

Stouwdam, J.W.

2004-01-01

The luminescence of lanthanide ions in organic environment is greatly reduced compared to inorganic materials. This thesis describes the doping of the lanthanide ions in the core of inorganic nanoparticles that are soluble in organic solvents as a way to shield the lanthanide ions from the organic

Vanadium

Science.gov (United States)

Kelley, Karen D.; Scott, Clinton T.; Polyak, Désirée E.; Kimball, Bryn E.; Schulz, Klaus J.; DeYoung,, John H.; Seal, Robert R.; Bradley, Dwight C.

2017-12-19

per day. Vanadium is essential for some biological processes and organisms. For example, some nitrogen-fixing bacteria require vanadium for producing enzymes necessary to convert nitrogen from the atmosphere into ammonia, which is a more biologically accessible form of nitrogen.

Luminescent lanthanide reporters: new concepts for use in bioanalytical applications

International Nuclear Information System (INIS)

Vuojola, Johanna; Soukka, Tero

2014-01-01

Lanthanides represent the chemical elements from lanthanum to lutetium. They intrinsically exhibit some very exciting photophysical properties, which can be further enhanced by incorporating the lanthanide ion into organic or inorganic sensitizing structures. A very popular approach is to conjugate the lanthanide ion to an organic chromophore structure forming lanthanide chelates. Another approach, which has quickly gained interest, is to incorporate the lanthanide ions into nanoparticle structures, thus attaining improved specific activity and a large surface area for biomolecule immobilization. Lanthanide-based reporters, when properly shielded from the quenching effects of water, usually express strong luminescence emission, multiple narrow emission lines covering a wide wavelength range, and exceptionally long excited state lifetimes enabling time-gated luminescence detection. Because of these properties, lanthanide-based reporters have found widespread applications in various fields of life. This review focuses on the field of bioanalytical applications. Luminescent lanthanide reporters and assay formats utilizing these reporters pave the way for increasingly sensitive, simple, and easily automated bioanalytical applications. (topical review)

Biological toxicity of lanthanide elements on algae.

Science.gov (United States)

Tai, Peidong; Zhao, Qing; Su, Dan; Li, Peijun; Stagnitti, Frank

2010-08-01

The biological toxicity of lanthanides on marine monocellular algae was investigated. The specific objective of this research was to establish the relationship between the abundance in the seawater of lanthanides and their biological toxicities on marine monocellular algae. The results showed that all single lanthanides had similar toxic effects on Skeletonema costatum. High concentrations of lanthanides (29.04+/-0.61 micromol L(-1)) resulted in 50% reduction in growth of algae compared to the controls (0 micromol L(-1)) after 96 h (96 h-EC50). The biological toxicity of 13 lanthanides on marine monocellular algae was unrelated with the abundance of different lanthanide elements in nature, and the "Harkins rule" was not appropriate for the lanthanides. A mixed solution that contained equivalent concentrations of each lanthanide element had the same inhibition effect on algae cells as each individual lanthanide element at the same total concentration. This phenomenon is unique compared to the groups of other elements in the periodic table. Hence, we speculate that the monocellular organisms might not be able to sufficiently differentiate between the almost chemically identical lanthanide elements. Copyright (c) 2010 Elsevier Ltd. All rights reserved.

Lanthanide single molecule magnets

CERN Document Server

Tang, Jinkui

2015-01-01

This book begins by providing basic information on single-molecule magnets (SMMs), covering the magnetism of lanthanide, the characterization and relaxation dynamics of SMMs, and advanced means of studying lanthanide SMMs. It then systematically introduces lanthanide SMMs ranging from mononuclear and dinuclear to polynuclear complexes, classifying them and highlighting those SMMs with high barrier and blocking temperatures – an approach that provides some very valuable indicators for the structural features needed to optimize the contribution of an Ising type spin to a molecular magnet. The final chapter presents some of the newest developments in the lanthanide SMM field, such as the design of multifunctional and stimuli-responsive magnetic materials as well as the anchoring and organization of the SMMs on surfaces. In addition, the crystal structure and magnetic data are clearly presented with a wealth of illustrations in each chapter, helping newcomers and experts alike to better grasp ongoing trends and...

The oxidation of organic additives in the positive vanadium electrolyte and its effect on the performance of vanadium redox flow battery

Science.gov (United States)

Nguyen, Tam D.; Whitehead, Adam; Scherer, Günther G.; Wai, Nyunt; Oo, Moe O.; Bhattarai, Arjun; Chandra, Ghimire P.; Xu, Zhichuan J.

2016-12-01

Despite many desirable properties, the vanadium redox flow battery is limited, in the maximum operation temperature that can be continuously endured, before precipitation begins in the positive electrolyte. Many additives have been proposed to improve the thermal stability of the charged positive electrolyte. However, we have found that the apparent stability, revealed in laboratory testing, is often simply an artifact of the test method and arises from the oxidation of the additive, with corresponding partial reduction of V(V) to V(IV). This does not improve the stability of the electrolyte in an operating system. Here, we examined the oxidation of some typical organic additives with carboxyl, alcohol, and multi-functional groups, in sulfuric acid solutions containing V(V). The UV-vis measurements and titration results showed that many compounds reduced the state-of-charge (SOC) of vanadium electrolyte, for example, by 27.8, 88.5, and 81.9% with the addition of 1%wt of EDTA disodium salt, pyrogallol, and ascorbic acid, respectively. The cell cycling also indicated the effect of organic additives on the cell performance, with significant reduction in the usable charge capacity. In addition, a standard screening method for thermally stable additives was introduced, to quickly screen suitable additives for the positive vanadium electrolyte.

Lanthanide single molecule magnets

Energy Technology Data Exchange (ETDEWEB)

Tang, Jinkui; Zhang, Peng [Chinese Academy of Sciences, Changchun (China). Changchun Inst. of Applied Chemistry

2015-10-01

This book begins by providing basic information on single-molecule magnets (SMMs), covering the magnetism of lanthanide, the characterization and relaxation dynamics of SMMs and advanced means of studying lanthanide SMMs. It then systematically introduces lanthanide SMMs ranging from mononuclear and dinuclear to polynuclear complexes, classifying them and highlighting those SMMs with high barrier and blocking temperatures - an approach that provides some very valuable indicators for the structural features needed to optimize the contribution of an Ising type spin to a molecular magnet. The final chapter presents some of the newest developments in the lanthanide SMM field, such as the design of multifunctional and stimuli-responsive magnetic materials as well as the anchoring and organization of the SMMs on surfaces. In addition, the crystal structure and magnetic data are clearly presented with a wealth of illustrations in each chapter, helping newcomers and experts alike to better grasp ongoing trends and explore new directions.

A multifunctional chemical sensor based on a three-dimensional lanthanide metal-organic framework

International Nuclear Information System (INIS)

Du, Pei-Yao; Liao, Sheng-Yun; Gu, Wen; Liu, Xin

2016-01-01

A 3D lanthanide MOF with formula [Sm 2 (abtc) 1.5 (H 2 O) 3 (DMA)]·H 2 O·DMA (1) has been successfully synthesized via solvothermal method. Luminescence studies reveal that 1 exhibits dual functional detection benzyl alcohol and benzaldehyde among different aromatic molecules. In addition, 1 displays a turn-on luminescence sensing with respect to ethanol among different alcohol molecules, which suggests that 1 is also a promising luminescent probe for high selective sensing of ethanol. - Highlights: • A three-dimensional lanthanide metal-organic framework has been synthesized. • Complex 1 exhibits dual functional detection benzyl alcohol and benzaldehyde among different aromatic molecules. • Complex 1 displays a turn-on luminescence sensing with respect to ethanol among different alcohol molecules.

Modularity in developmental biology and artificial organs: a missing concept in tissue engineering.

Science.gov (United States)

Lenas, Petros; Luyten, Frank P; Doblare, Manuel; Nicodemou-Lena, Eleni; Lanzara, Andreina Elena

2011-06-01

Tissue engineering is reviving itself, adopting the concept of biomimetics of in vivo tissue development. A basic concept of developmental biology is the modularity of the tissue architecture according to which intermediates in tissue development constitute semiautonomous entities. Both engineering and nature have chosen the modular architecture to optimize the product or organism development and evolution. Bioartificial tissues do not have a modular architecture. On the contrary, artificial organs of modular architecture have been already developed in the field of artificial organs. Therefore the conceptual support of tissue engineering by the field of artificial organs becomes critical in its new endeavor of recapitulating in vitro the in vivo tissue development. © 2011, Copyright the Authors. Artificial Organs © 2011, International Center for Artificial Organs and Transplantation and Wiley Periodicals, Inc.

Exploring electrolyte preference of vanadium nitride supercapacitor electrodes

Energy Technology Data Exchange (ETDEWEB)

Wang, Bo; Chen, Zhaohui; Lu, Gang [Department of Electrical Engineering and Automation, Luoyang Institute of Science and Technology, Luoyang 471023 (China); Wang, Tianhu [School of Electrical Information and Engineering, Jiangsu University of Technology, Changzhou 213001 (China); Ge, Yunwang, E-mail: ywgelit@126.com [Department of Electrical Engineering and Automation, Luoyang Institute of Science and Technology, Luoyang 471023 (China)

2016-04-15

Highlights: • Hierarchical VN nanostructures were prepared on graphite foam. • Electrolyte preference of VN supercapacitor electrodes was explored. • VN showed better capacitive property in organic and alkaline electrolytes than LiCl. - Abstract: Vanadium nitride hierarchical nanostructures were prepared through an ammonia annealing procedure utilizing vanadium pentoxide nanostructures grown on graphite foam. The electrochemical properties of hierarchical vanadium nitride was tested in aqueous and organic electrolytes. As a result, the vanadium nitride showed better capacitive energy storage property in organic and alkaline electrolytes. This work provides insight into the charge storage process of vanadium nitride and our findings can shed light on other transition metal nitride-based electrochemical energy storage systems.

A multifunctional chemical sensor based on a three-dimensional lanthanide metal-organic framework

Energy Technology Data Exchange (ETDEWEB)

Du, Pei-Yao [College of Chemistry and Key Laboratory of Advanced Energy Materials Chemistry (MOE), Collaborative Innovation Center of Chemical Science and Engineering, Nankai University, Tianjin 300071 (China); Liao, Sheng-Yun [Department of Applied Chemistry, Tianjin University of Technology, Tianjin 300384 (China); Gu, Wen, E-mail: guwen68@nankai.edu.cn [College of Chemistry and Key Laboratory of Advanced Energy Materials Chemistry (MOE), Collaborative Innovation Center of Chemical Science and Engineering, Nankai University, Tianjin 300071 (China); Liu, Xin, E-mail: liuxin64@nankai.edu.cn [College of Chemistry and Key Laboratory of Advanced Energy Materials Chemistry (MOE), Collaborative Innovation Center of Chemical Science and Engineering, Nankai University, Tianjin 300071 (China)

2016-12-15

A 3D lanthanide MOF with formula [Sm{sub 2}(abtc){sub 1.5}(H{sub 2}O){sub 3}(DMA)]·H{sub 2}O·DMA (1) has been successfully synthesized via solvothermal method. Luminescence studies reveal that 1 exhibits dual functional detection benzyl alcohol and benzaldehyde among different aromatic molecules. In addition, 1 displays a turn-on luminescence sensing with respect to ethanol among different alcohol molecules, which suggests that 1 is also a promising luminescent probe for high selective sensing of ethanol. - Highlights: • A three-dimensional lanthanide metal-organic framework has been synthesized. • Complex 1 exhibits dual functional detection benzyl alcohol and benzaldehyde among different aromatic molecules. • Complex 1 displays a turn-on luminescence sensing with respect to ethanol among different alcohol molecules.

Amphoteric Ion-Exchange Membranes with Significantly Improved Vanadium Barrier Properties for All-Vanadium Redox Flow Batteries.

Science.gov (United States)

Nibel, Olga; Rojek, Tomasz; Schmidt, Thomas J; Gubler, Lorenz

2017-07-10

All-vanadium redox flow batteries (VRBs) have attracted considerable interest as promising energy-storage devices that can allow the efficient utilization of renewable energy sources. The membrane, which separates the porous electrodes in a redox flow cell, is one of the key components in VRBs. High rates of crossover of vanadium ions and water through the membrane impair the efficiency and capacity of a VRB. Thus, membranes with low permeation rate of vanadium species and water are required, also characterized by low resistance and stability in the VRB environment. Here, we present a new design concept for amphoteric ion-exchange membranes, based on radiation-induced grafting of vinylpyridine into an ethylene tetrafluoroethylene base film and a two-step functionalization to introduce cationic and anionic exchange sites, respectively. During long-term cycling, redox flow cells containing these membranes showed higher efficiency, less pronounced electrolyte imbalance, and significantly reduced capacity decay compared to the cells with the benchmark material Nafion 117. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Lanthanide-organic frameworks constructed from multi-functional ligands: Syntheses, structures, near-infrared and visible photoluminescence properties

International Nuclear Information System (INIS)

Li Xinfa; Xie Zailai; Lin Jingxiang; Cao Rong

2009-01-01

A series of multi-functional ligands supported lanthanide-organic frameworks, formulated as [Ln(HL 1 )(H 2 L 2 ) 0.5 (H 4 L 2 ) 0.5 (H 2 O)].(H 2 O) 1.5 .{Ln=La (1), Pr (2), Nd (3), Sm (4), Eu (5); H 3 L 1 =5-Sulfosaclicylic acid; H 4 L 2 =N,N'-piperazine (bis-methylene phosphonic acid)}, have been synthesized by hydrothermal reactions. Single crystal X-ray diffractions and powder XRD patterns confirm they are isostructural. They feature 3D framework structures based on extension of a 'zigzag' inorganic chain by organic linkers. Moreover, the photoluminescence properties of 5 and 3 have been investigated, and they show strong solid-state emissions in the visible and near-infrared (IR) regions at room temperature. - Graphical abstract: Five multi-functional ligands supported 3D lanthanide-organic frameworks have been synthesized and structurally characterized. Compounds 5 and 3 displayed strong solid-state emissions in the visible and near-infrared region at room temperature.

Synthesis and luminescence properties of hybrid organic-inorganic transparent titania thin film activated by in-situ formed lanthanide complexes

International Nuclear Information System (INIS)

Wang Yige; Wang Li; Li Huanrong; Liu Peng; Qin Dashan; Liu Binyuan; Zhang Wenjun; Deng Ruiping; Zhang Hongjie

2008-01-01

Stable transparent titania thin films were fabricated at room temperature by combining thenoyltrifluoroacetone (TTFA)-modified titanium precursors with amphiphilic triblock poly(ethylene oxide)-poly(propylene oxide)-poly(ethylene oxide) (PEO-PPO-PEO, P123) copolymers. The obtained transparent titania thin films were systematically investigated by IR spectroscopy, PL emission and excitation spectroscopy and transmission electron microscopy. IR spectroscopy indicates that TTFA coordinates the titanium center during the process of hydrolysis and condensation. Luminescence spectroscopy confirms the in-situ formation of lanthanide complexes in the transparent titania thin film. TEM image shows that the in-situ formed lanthanide complexes were homogeneously distributed throughout the whole thin film. The quantum yield and the number of water coordinated to lanthanide metal center have been theoretically determined based on the luminescence data. - Graphical abstract: Novel stable luminescent organic-inorganic hybrid titania thin film with high transparency activated by in-situ formed lanthanide complexes have been obtained at room temperature via a simple one-pot synthesis approach by using TTFA-modified titanium precursor with amphiphilic triblock copolymer P123. The obtained hybrid thin film displays bright red (or green), near-monochromatic luminescence due to the in-situ formed lanthanide complex

Self-sufficiency of an autonomous reconfigurable modular robotic organism

CERN Document Server

Qadir, Raja Humza

2015-01-01

This book describes how the principle of self-sufficiency can be applied to a reconfigurable modular robotic organism. It shows the design considerations for a novel REPLICATOR robotic platform, both hardware and software, featuring the behavioral characteristics of social insect colonies. Following a comprehensive overview of some of the bio-inspired techniques already available, and of the state-of-the-art in re-configurable modular robotic systems, the book presents a novel power management system with fault-tolerant energy sharing, as well as its implementation in the REPLICATOR robotic modules. In addition, the book discusses, for the first time, the concept of “artificial energy homeostasis” in the context of a modular robotic organism, and shows its verification on a custom-designed simulation framework in different dynamic power distribution and fault tolerance scenarios. This book offers an ideal reference guide for both hardware engineers and software developers involved in the design and implem...

The geochemistry and mobility of the lanthanides in marine sediments

International Nuclear Information System (INIS)

Elderfield, H.

1988-07-01

A study has been made to evaluate lanthanide mobility in sediments directly by measuring concentrations of 10 lanthanide elements in sediments and pore waters. Due to the very low concentrations of the lanthanides in sea water relative to marine sediments, evidence of lanthanide mobilization is usually difficult to detect from studies of solid-phase geochemistry. Results show that the lanthanides can be extremely mobile. Concentrations in pore waters up to 100 times sea water concentrations have been measured. The conclusions are tentative but the present data suggest that the lanthanides are mobilized during oxidation of organic-rich sediments and are relocated in part in association with secondary Fe-rich phases. The behaviour of Ce is, predictably, somewhat different from the other lanthanides and may be more mobile as a consequence of its redox chemistry. (author)

Intramolecular deactivation processes of electronically excited Lanthanide(III) complexes with organic acids of low molecular weight

Science.gov (United States)

Burek, Katja; Eidner, Sascha; Kuke, Stefanie; Kumke, Michael U.

2018-02-01

The luminescence of Lanthanide(III) complexes with different model ligands was studied under direct as well as sensitized excitation conditions. The research was performed in the context of studies dealing with deep-underground storages for high-level nuclear waste. Here, Lanthanide(III) ions served as natural analogues for Actinide(III) ions and the low-molecular weight organic ligands are present in clay minerals and furthermore, they were employed as proxies for building blocks of humic substances, which are important complexing molecules in the natural environment, e.g., in the far field of a repository site. Time-resolved luminescence spectroscopy was applied for a detailed characterization of Eu(III), Tb(III), Sm(III) and Dy(III) complexes in aqueous solutions. Based on the observed luminescence the ligands were tentatively divided into two groups (A, B). The luminescence of Lanthanide(III) complexes of group A was mainly influenced by an energy transfer to OH-vibrations. Lanthanide(III) complexes of group B showed ligand-related luminescence quenching, which was further investigated. To gain more information on the underlying quenching processes of group A and B ligands, measurements at different temperatures (77 K ≤ T ≤ 353 K) were performed and activation energies were determined based on an Arrhenius analysis. Moreover, the influence of the ionic strength between 0 M ≤ I ≤ 4 M on the Lanthanide(III) luminescence was monitored for different complexes, in order to evaluate the influence of specific conditions encountered in host rocks foreseen as potential repository sites.

Modular nuclear fuel element, modular capsule for a such element and fabrication process for a modular capsule

International Nuclear Information System (INIS)

Chotard, A.

1988-01-01

The nuclear fuel rod is made by a tubular casing closed at both ends and containing a series of modular capsules with little play with the casing and made by a jacket closed by porous plugs at both ends and containing a stack of fuel pellets [fr

Redefining the modular organization of the core Mediator complex.

Science.gov (United States)

Wang, Xuejuan; Sun, Qianqian; Ding, Zhenrui; Ji, Jinhua; Wang, Jianye; Kong, Xiao; Yang, Jianghong; Cai, Gang

2014-07-01

The Mediator complex plays an essential role in the regulation of eukaryotic transcription. The Saccharomyces cerevisiae core Mediator comprises 21 subunits, which are organized into Head, Middle and Tail modules. Previously, the Head module was assigned to a distinct dense domain at the base, and the Middle and Tail modules were identified to form a tight structure above the Head module, which apparently contradicted findings from many biochemical and functional studies. Here, we compared the structures of the core Mediator and its subcomplexes, especially the first 3D structure of the Head + Middle modules, which permitted an unambiguous assignment of the three modules. Furthermore, nanogold labeling pinpointing four Mediator subunits from different modules conclusively validated the modular assignment, in which the Head and Middle modules fold back on one another and form the upper portion of the core Mediator, while the Tail module forms a distinct dense domain at the base. The new modular model of the core Mediator has reconciled the previous inconsistencies between the structurally and functionally defined Mediator modules. Collectively, these analyses completely redefine the modular organization of the core Mediator, which allow us to integrate the structural and functional information into a coherent mechanism for the Mediator's modularity and regulation in transcription initiation.

Separation of lanthanides using micro solvent extraction system

International Nuclear Information System (INIS)

Nishihama, S.; Tajiri, Y.; Yoshizuka, K.

2006-01-01

A micro solvent extraction system for the separation of lanthanides has been investigated. The micro flow channel is fabricated on a poly(methyl methacrylate) (PMMA) plate, and solvent extraction progresses by feeding aqueous and organic solutions into the channel simultaneously. The extraction equilibrium is quickly achieved, without any mechanical mixing, when a narrow channel (100 μm width and 100 μm depth) is used. The results of solvent extraction from the Pr/Nd and Pr/Sm binary solutions revealed that both lanthanides are firstly extracted together, and then, the lighter lanthanide extracted in the organic solution alternatively exchanges to the heavier one in the aqueous solution to achieve the extraction equilibrium. The phase separation of the aqueous and organic phases after extraction can also be successively achieved by contriving the cross section of the flow channel, and the extractive separation of Pr/Sm is demonstrated. (authors)

Significance of porous structure on degradatin of 2 2' dichloro diethyl sulphide and 2 chloroethyl ethyl sulphide on the surface of vanadium oxide nanostructure

International Nuclear Information System (INIS)

Singh, Beer; Mahato, T.H.; Srivastava, A.K.; Prasad, G.K.; Ganesan, K.; Vijayaraghavan, R.; Jain, Rajeev

2011-01-01

Degradation of the king of chemical warfare agent, 2 2' dichloro diethyl sulphide (HD), and its simulant 2 chloroethyl ethyl sulphide (CEES) were investigated on the surface of porous vanadium oxide nanotubes at room temperature (30 ± 2 ° C ). Reaction kinetics was monitored by GC-FID technique and the reaction products were characterized by GC-MS. Data indicates that HD degraded faster relative to CEES inside the solid decontaminant compared to the reported liquid phase degradation of CEES and HD. Data explores the role of hydrolysis, elimination and oxidation reactions in the detoxification of HD and CEES and the first order rate constant and t 1/2 were calculated to be 0.026 h -1 , 26.6 h for CEES and 0.052 h -1 , 13.24 h for HD. In this report faster degradation of HD compared to CEES was explained on the basis of porous structure.

Vanadium

International Nuclear Information System (INIS)

Duke, V.W.A.

1983-07-01

Although a relatively abundant element, vanadium occurs only rarely in sufficient concentration to be worked commercially. In most cases, vanadium is produced as a co-product of some other element, most commonly iron. The principal ore deposits of vanadium occur in titaniferous magnetites that have been formed by magnetic segregation. Important commercial deposits of vanadium also occur associated with uranium, and with phosphate deposits. The principal uses of vanadium are in the production of special purpose, particularly high-strength low-alloy steels, in the manufacture of titanium alloys, and as a catalyst, notably in the manufacture of sulphuric acid. Small quantities of vanadium, often in combination with niobium, are added to steel to bring about toughening through grain refinement, and increased tensile strength through precipitation hardening. Known world reserves of vanadium are very large and fully adequate to meet any foreseeable demand. By far the largest known deposits of vanadium occur in South Africa. Many other similar deposits are known, but are only exploited in the USSR and China. The present total world demand for vanadium amounts to about 40 000 tons of metal annually and this is produced primarily in four countries, South Africa, the USSR, the People's Republic of China and the United States of America, in that order. South Africa is the principal vanadium producing country in the world, supplying vanadium in various forms. Vanadium has a very low and non-accumulative toxicity; recovery plants can be operated in such a manner to ensure no air or steam pollution results

Enrichment, Distribution of Vanadium-Containing Protein in Vanadium-Enriched Sea Cucumber Apostichopus japonicus and the Ameliorative Effect on Insulin Resistance.

Science.gov (United States)

Liu, Yanjun; Zhou, Qingxin; Zhao, Yanlei; Wang, Yiming; Wang, Yuming; Wang, Jingfeng; Xu, Jie; Xue, Changhu

2016-05-01

Sea cucumbers are a potential source of natural organic vanadium that may improve insulin resistance. In this work, vanadium was accumulated rapidly in blood, body wall, and intestine by sea cucumber Apostichopus japonicus. Furthermore, water-soluble vanadium-containing proteins, the main form of the organic vanadium, were tentatively accumulated and isolated by a bioaccumulation experiment. It was also designed to evaluate the beneficial effect of vanadium-containing proteins (VCPs) from sea cucumber rich in vanadium on the development of hyperglycemia and insulin resistance in C57BL/6J mice fed with a high-fat high-sucrose diet (HFSD). HFSD mice treated with VCPs significantly decreased fasting blood glucose, serum insulin, and HOMA-IR values as compared to HFSD mice, respectively. Serum adiponectin, resistin, TNF-α, and leptin levels in insulin-resistant mice were dramatically reduced by a VCP supplement. These results show an ameliorative effect on insulin resistance by treatment with VCPs. Such compound seems to be a valuable therapy to achieve and/or maintain glycemic control and therapeutic agents in the treatment arsenal for insulin resistance and type 2 diabetes.

IT PROJECT PORTFOLIO MANAGEMENT: MODULARITY PROBLEMS IN A PUBLIC ORGANIZATION

DEFF Research Database (Denmark)

Hansen, Lars Kristian; Mengiste, Shegaw Anagaw

2012-01-01

As today’s public and private sector organizations heavily rely on Information Technology (IT) to provide faster cycle times and better services, IT Project Portfolio Management (IT PPM) has become a high priority issue. This research adopts engaged scholarship to investigate IT PPM practices...... within a large local government. The investigation applies Modularity theory to analyze rich data from the local government covering several units with quite diverse functions to address the following two questions (1) which modularity problems does a public organization have in its IT PPM practices...... suggest a model addressing the identified problems by organizing IT PPM in three modules connected by three gateways. These results may be used to inform further research into IT PPM and to help managers improve IT PPM practices in public organizations. Keywords: IT Project Portfolio Management (IT PPM...

Luminescent hybrid lanthanide sulfates and lanthanide sulfonate-carboxylates with 1,10-phenanthroline involving in-situ oxidation of 2-mercaptonbenzoic acid

Science.gov (United States)

Zhong, Jie-Cen; Wan, Fang; Sun, Yan-Qiong; Chen, Yi-Ping

2015-01-01

A series of lanthanide sulfates and lanthanide sulfonate-carboxylates, [Ln2(phen)2(SO4)3(H2O)2]n (I:Ln=Nd(1a), Sm(1b), Eu(1c), phen=1,10-phenanthroline) and [Ln(phen)(2-SBA)(BZA)]n (II: Ln=Sm(2a), Eu(2b), Dy(2c), 2-SBA=2-sulfobenzoate, BZA=benzoate) have been hydrothermally synthesized from lanthanide oxide, 2-mercaptonbenzoic acid with phen as auxiliary ligand and characterized by single-crystal X-ray diffraction, elemental analyses, IR spectra, TG analyses and luminescence spectroscopy. Interestingly, SO4 2 - anions in I came from the in situ deep oxidation of thiol groups of 2-mercaptonbenzoic acid while 2-sulfobenzoate and benzoate ligands in II from the middle oxidation and desulfuration reactions of 2-mercaptonbenzoic acid. Compounds I are organic-inorganic hybrid lanthanide sulfates, which have rare one-dimensional column-like structures. Complexes II are binuclear lanthanide sulfonate-carboxylates with 2-sulfobenzoate and benzoate as bridges and 1,10-phenanthroline as terminal. Photoluminescence studies reveal that complexes I and II exhibit strong lanthanide characteristic emission bands in the solid state at room temperature.

Citrate-based open-quotes Talspeakclose quotes actinide-lanthanide separation process

International Nuclear Information System (INIS)

Del Cul, G.D.; Toth, L.M.; Bond, W.D.

1997-01-01

Lanthanide elements are produced in relatively high yield by fission of 235 U. Almost all the lanthanide isotopes decay to stable nonradioactive lanthanide isotopes in a relatively short time. Consequently, it is highly advantageous to separate the relatively small actinide fraction from the relatively large quantities of lanthanide isotopes. The TALSPEAK process (Trivalent Actinide Lanthanide Separations by Phosphorus-reagent Extraction from Aqueous Complexes) is one of the few means available to separate the trivalent actinides from the lanthanides. Previous work based on the use of lactic or glycolic acid has shown deleterious effects of some impurity ions such as zirconium(IV), even at concentrations on the order of 10 -4 M. Other perceived problems were the need to maintain the pH and reagent concentrations within a narrow range and a significant solubility of the organic phase at high carboxylic acid concentrations. The authors' cold experiments showed that replacing the traditional extractants glycolic or lactic acid with citric acid eliminates or greatly reduces the deleterious effects produced by impurities such as zirconium. An extensive series of batch tests was done using a wide range of reagent concentrations at different pH values, temperatures, and contact times. The results demonstrated that the citrate-based TALSPEAK can tolerate appreciable changes in pH and reagent concentrations while maintaining an adequate lanthanide extraction. Experiments using a three-stage glass mixer-settler showed a good lanthanide extraction, appropriate phase disengagement, no appreciable deleterious effects due to the presence of impurities such as zirconium, excellent pH buffering, and no significant loss of organic phase

Lanthanide Cofactors for Triphosphorylation Ribozymes

Science.gov (United States)

Sweeney, K. J.; Müller, U. F.

2017-07-01

RNA world organisms could have used trimetaphosphate as energy source for thermodynamically unfavorable RNA polymerization. Using in vitro selection we show here that Lanthanides can serve as cofactors for ribozyme-catalyzed RNA triphosphorylation.

Evaluation of radiation heat transfer in porous medial: Application for a pebble bed modular reactor cooled by CO2 gas

Directory of Open Access Journals (Sweden)

Sidi-Ali Kamel

2013-01-01

Full Text Available This work analyses the contribution of radiation heat transfer in the cooling of a pebble bed modular reactor. The mathematical model, developed for a porous medium, is based on a set of equations applied to an annular geometry. Previous major works dealing with the subject have considered the forced convection mode and often did not take into account the radiation heat transfer. In this work, only free convection and radiation heat transfer are considered. This can occur during the removal of residual heat after shutdown or during an emergency situation. In order to derive the governing equations of radiation heat transfer, a steady-state in an isotropic and emissive porous medium (CO2 is considered. The obtained system of equations is written in a dimensionless form and then solved. In order to evaluate the effect of radiation heat transfer on the total heat removed, an analytical method for solving the system of equations is used. The results allow quantifying both radiation and free convection heat transfer. For the studied situation, they show that, in a pebble bed modular reactor, more than 70% of heat is removed by radiation heat transfer when CO2 is used as the coolant gas.

Organic derivatives of lanthanides containing metal in cycle

International Nuclear Information System (INIS)

Syutkina, O.P.; Rybakova, L.F.; Egorova, E.N.; Sigalov, A.B.; Beletskaya, I.P.

1983-01-01

The reaction of 2.2'-dilithium biphenyl with LnBr 3 (Ln=Pr, Sm, Gd, Ho, Yb here bromium atoms are comparatively easily replaced. Previously unknown organic derivatives of lanthanides containing metal in the cycle are obtained. It is established that a successful extraction of the compound requires reaction conditions, such as the use of ether as a solvent with the followinq addition of TGP, the order of addition of reagents. Compounds are extracted in the form of solvates containing TGP melecules. The complexes prepared are coloured, depending on the metal, beige (Pr, Sm) brown (Gd, Yb) and red-brown (Ho). They dissolve readily in TGP moderately in benzen toluene, CCl 4 . When stored their solubility in benzene and CCl 4 decreases considerably, and after 3-2 days, they are practically insoluhle. The compounds prepared are characterized by the elementary analysis, IR and PMR spectra

Triheterometallic Lanthanide Complexes Prepared from Kinetically Inert Lanthanide Building Blocks

DEFF Research Database (Denmark)

Sørensen, Thomas Just; Tropiano, Manuel; Kenwright, Alan M.

2017-01-01

Three molecular structures, each containing three different lanthanide(III) centres, have been prepared by coupling three kinetically inert lanthanide(III) complexes in an Ugi reaction. These 2 kDa molecules were purified by dialysis and characterised by NMR and luminescence techniques. The photo...... and lanthanide(III) centres in these molecules inhibits the efficient sensitisation of europium. We conclude that the intramolecular collisions required for efficient Dexter energy transfer from the sensitiser to the lanthanide(III) centre can be prevented by steric congestion....

Luminescent Lanthanide Reporters for High-Sensitivity Novel Bioassays

Energy Technology Data Exchange (ETDEWEB)

Anstey, Mitchell R. [Sandia National Lab. (SNL-CA), Livermore, CA (United States); Fruetel, Julia A. [Sandia National Lab. (SNL-CA), Livermore, CA (United States); Foster, Michael E. [Sandia National Lab. (SNL-CA), Livermore, CA (United States); Hayden, Carl C. [Sandia National Lab. (SNL-CA), Livermore, CA (United States); Buckley, Heather L. [Sandia National Lab. (SNL-CA), Livermore, CA (United States); Arnold, John [Sandia National Lab. (SNL-CA), Livermore, CA (United States)

2013-09-01

Biological imaging and assay technologies rely on fluorescent organic dyes as reporters for a number of interesting targets and processes. However, limitations of organic dyes such as small Stokes shifts, spectral overlap of emission signals with native biological fluorescence background, and photobleaching have all inhibited the development of highly sensitive assays. To overcome the limitations of organic dyes for bioassays, we propose to develop lanthanide-based luminescent dyes and demonstrate them for molecular reporting applications. This relatively new family of dyes was selected for their attractive spectral and chemical properties. Luminescence is imparted by the lanthanide atom and allows for relatively simple chemical structures that can be tailored to the application. The photophysical properties offer unique features such as narrow and non-overlapping emission bands, long luminescent lifetimes, and long wavelength emission, which enable significant sensitivity improvements over organic dyes through spectral and temporal gating of the luminescent signal.Growth in this field has been hindered due to the necessary advanced synthetic chemistry techniques and access to experts in biological assay development. Our strategy for the development of a new lanthanide-based fluorescent reporter system is based on chelation of the lanthanide metal center using absorbing chromophores. Our first strategy involves "Click" chemistry to develop 3-fold symmetric chelators and the other involves use of a new class of tetrapyrrole ligands called corroles. This two-pronged approach is geared towards the optimization of chromophores to enhance light output.

Photocytotoxic lanthanide complexes

Indian Academy of Sciences (India)

Among many applications of lanthanides, gadolinium complexes are used as magnetic resonance imaging (MRI) contrast agents in clinical radiology and luminescent lanthanides for bioanalysis, imaging and sensing. The chemistry of photoactive lanthanide complexes showing biological applications is of recent origin.

Inverted organic solar cells with solvothermal synthesized vanadium-doped TiO2 thin films as efficient electron transport layer

Institute of Scientific and Technical Information of China (English)

Mehdi Ahmadi; Sajjad Rashidi Dafeh; Samaneh Ghazanfarpour; Mohammad Khanzadeh

2017-01-01

We investigated the effects of using different thicknesses of pure and vanadium-doped thin films of TiO2 as the electron transport layer in the inverted configuration of organic photovoltaic cells based on poly (3-hexylthiophene) P3HT:[6-6] phenyl-(6) butyric acid methyl ester (PCBM).1％ vanadium-doped TiO2 nanoparticles were synthesized via the solvothermal method.Crystalline structure,morphology,and optical properties of pure and vanadium-doped TiO2 thin films were studied by different techniques such as x-ray diffraction,scanning electron microscopy,transmittance electron microscopy,and UV-visible transmission spectrum.The doctor blade method which is compatible with roll-2-roll printing was used for deposition of pure and vanadium-doped TiO2 thin films with thicknesses of 30 nm and 60 nm.The final results revealed that the best thickness of TiO2 thin films for our fabricated cells was 30 nm.The cell with vanadium-doped TiO2 thin film showed slightly higher power conversion efficiency and great Jsc of 10.7 mA/cm2 compared with its pure counterpart.In the cells using 60 nm pure and vanadium-doped TiO2 layers,the cell using the doped layer showed much higher efficiency.It is remarkable that the extemal quantum efficiency of vanadium-doped TiO2 thin film was better in all wavelengths.

Sustained activity in hierarchical modular neural networks: self-organized criticality and oscillations

Directory of Open Access Journals (Sweden)

Sheng-Jun Wang

2011-06-01

Full Text Available Cerebral cortical brain networks possess a number of conspicuous features of structure and dynamics. First, these networks have an intricate, non-random organization. They are structured in a hierarchical modular fashion, from large-scale regions of the whole brain, via cortical areas and area subcompartments organized as structural and functional maps to cortical columns, and finally circuits made up of individual neurons. Second, the networks display self-organized sustained activity, which is persistent in the absence of external stimuli. At the systems level, such activity is characterized by complex rhythmical oscillations over a broadband background, while at the cellular level, neuronal discharges have been observed to display avalanches, indicating that cortical networks are at the state of self-organized criticality. We explored the relationship between hierarchical neural network organization and sustained dynamics using large-scale network modeling. It was shown that sparse random networks with balanced excitation and inhibition can sustain neural activity without external stimulation. We find that a hierarchical modular architecture can generate sustained activity better than random networks. Moreover, the system can simultaneously support rhythmical oscillations and self-organized criticality, which are not present in the respective random networks. The underlying mechanism is that each dense module cannot sustain activity on its own, but displays self-organized criticality in the presence of weak perturbations. The hierarchical modular networks provide the coupling among subsystems with self-organized criticality. These results imply that the hierarchical modular architecture of cortical networks plays an important role in shaping the ongoing spontaneous activity of the brain, potentially allowing the system to take advantage of both the sensitivityof critical state and predictability and timing of oscillations for efficient

Secret lanthanides.

Science.gov (United States)

Sturza, C M

2014-09-15

Lanthanides are a group of 15 chemical elements which, together with their salts, have come to be used in the last decade as homoeopathic remedies. The effective introduction of lanthanides and their salts into the clinical use, as homoeopathic remedies was based on the idea of Jan Scholten, MD to relate their physicochemical properties shown in the periodic table of elements to their homoeopathic potential. The lanthanides and their salts were prepared as homoeopathic remedies by Pharmacist Robert Münz.

Disrupted modular organization of primary sensory brain areas in schizophrenia

Directory of Open Access Journals (Sweden)

Cécile Bordier

Full Text Available Abnormal brain resting-state functional connectivity has been consistently observed in patients affected by schizophrenia (SCZ using functional MRI and other neuroimaging techniques. Graph theoretical methods provide a framework to investigate these defective functional interactions and their effects on the organization of brain connectivity networks. A few studies have shown altered distribution of connectivity within and between functional modules in SCZ patients, an indication of imbalanced functional segregation ad integration. However, no major alterations of modular organization have been reported in patients, and unambiguous identification of the neural substrates affected remains elusive. Recently, it has been demonstrated that current modularity analysis methods suffer from a fundamental and severe resolution limit, as they fail to detect features that are smaller than a scale determined by the size of the entire connectivity network. This resolution limit is likely to have hampered the ability to resolve differences between patients and controls in previous studies. Here, we apply Surprise, a novel resolution limit-free approach, to study the modular organization of resting state functional connectivity networks in a large cohort of SCZ patients and in matched healthy controls. Leveraging these important methodological advances we find new evidence of substantial fragmentation and reorganization involving primary sensory, auditory and visual areas in SCZ patients. Conversely, frontal and prefrontal areas, typically associated with higher cognitive functions, appear to be largely unaffected, with changes selectively involving language and speech processing areas. Our findings support the hypothesis that cognitive dysfunction in SCZ may involve deficits occurring already at early stages of sensory processing. Keywords: Schizophrenia, Surprise, Asymptotical surprise, Functional connectivity, Community detection, Modularity, Graph theory

Significance of porous structure on degradatin of 2 2' dichloro diethyl sulphide and 2 chloroethyl ethyl sulphide on the surface of vanadium oxide nanostructure

Energy Technology Data Exchange (ETDEWEB)

Singh, Beer, E-mail: beerbs5@rediffmail.com [Defence R and D Establishment, Jhansi Road, Gwalior, M.P 474002 (India); Mahato, T.H.; Srivastava, A.K.; Prasad, G.K.; Ganesan, K.; Vijayaraghavan, R. [Defence R and D Establishment, Jhansi Road, Gwalior, M.P 474002 (India); Jain, Rajeev [School of Studies in Chemistry, Jiwaji University, Gwalior, M.P. 474011 (India)

2011-06-15

Degradation of the king of chemical warfare agent, 2 2' dichloro diethyl sulphide (HD), and its simulant 2 chloroethyl ethyl sulphide (CEES) were investigated on the surface of porous vanadium oxide nanotubes at room temperature (30 {+-} 2{sup Degree-Sign }C ). Reaction kinetics was monitored by GC-FID technique and the reaction products were characterized by GC-MS. Data indicates that HD degraded faster relative to CEES inside the solid decontaminant compared to the reported liquid phase degradation of CEES and HD. Data explores the role of hydrolysis, elimination and oxidation reactions in the detoxification of HD and CEES and the first order rate constant and t{sub 1/2} were calculated to be 0.026 h{sup -1}, 26.6 h for CEES and 0.052 h{sup -1}, 13.24 h for HD. In this report faster degradation of HD compared to CEES was explained on the basis of porous structure.

Nitrogen-Doped Carbon Nanotube/Graphite Felts as Advanced Electrode Materials for Vanadium Redox Flow Batteries.

Science.gov (United States)

Wang, Shuangyin; Zhao, Xinsheng; Cochell, Thomas; Manthiram, Arumugam

2012-08-16

Nitrogen-doped carbon nanotubes have been grown, for the first time, on graphite felt (N-CNT/GF) by a chemical vapor deposition approach and examined as an advanced electrode for vanadium redox flow batteries (VRFBs). The unique porous structure and nitrogen doping of N-CNT/GF with increased surface area enhances the battery performance significantly. The enriched porous structure of N-CNTs on graphite felt could potentially facilitate the diffusion of electrolyte, while the N-doping could significantly contribute to the enhanced electrode performance. Specifically, the N-doping (i) modifies the electronic properties of CNT and thereby alters the chemisorption characteristics of the vanadium ions, (ii) generates defect sites that are electrochemically more active, (iii) increases the oxygen species on CNT surface, which is a key factor influencing the VRFB performance, and (iv) makes the N-CNT electrochemically more accessible than the CNT.

Tuning surface porosity on vanadium surface by low energy He{sup +} ion irradiation

Energy Technology Data Exchange (ETDEWEB)

Tripathi, J.K., E-mail: jtripat@purdue.edu; Novakowski, T.J.; Hassanein, A.

2016-08-15

Highlights: • Surface nanostructuring on vanadium surface using novel He{sup +} ion irradiation process. • Tuning surface-porosity using high-flux, low-energy He{sup +} ion irradiation at constant elevated sample temperature (823–173 K). • Presented top-down approach guarantees good contact between different crystallites. • Sequential significant enhancement in surface-pore edge size (and corresponding reduction in surface-pore density) with increasing sample temperature. - Abstract: In the present study, we report on tuning the surface porosity on vanadium surfaces using high-flux, low-energy He{sup +} ion irradiation as function of sample temperature. Polished, mirror-finished vanadium samples were irradiated with 100 eV He{sup +} ions at a constant ion-flux of 7.2 × 10{sup 20} ions m{sup −2} s{sup −1} for 1 h duration at constant sample temperatures in the wide range of 823–1173 K. Our results show that the surface porosity of V{sub 2}O{sub 5} (naturally oxidized vanadium porous structure, after taking out from UHV) is strongly correlated to the sample temperature and is highly tunable. In fact, the surface porosity significantly increases with reducing sample temperature and reaches up to ∼87%. Optical reflectivity on these highly porous V{sub 2}O{sub 5} surfaces show ∼0% optical reflectivity at 670 nm wavelength, which is very similar to that of “black metal”. Combined with the naturally high melting point of V{sub 2}O{sub 5}, this very low optical reflectivity suggests potential application in solar power concentration technology. Additionally, this top-down approach guarantees relatively good contact between the different crystallites and avoids electrical conductivity limitations (if required). Since V{sub 2}O{sub 5} is naturally a potential photocatalytic material, the resulting sub-micron-sized cube-shaped porous structures could be used in solar water splitting for hydrogen production in energy applications.

Pepspectives of chlorine application in metallurgy of vanadium

International Nuclear Information System (INIS)

Korshunov, B.G.; Kutsenko, S.A.

1983-01-01

The most expedient variants of reprocessing of vanadium technical oxide (5), ferrovanadium and converter slags by chlorine technology with production of pure metal are considered. It is shown that production of vanadium by the way of electro- or metallothermal reduction of chlorides provides more plastic metal in comparison with reduction from oxides. The methods of production of VOCl 3 , VCl 4 and vanadium lowest chlorides are considered. Necessity of expansion of production of vanadium chlorine derivatives is dictated as well by their increasing application in different areas of national economy, in particular, as catalysts in organic synthesis

Series of mixed uranyl-lanthanide (Ce, Nd) organic coordination polymers with aromatic polycarboxylates linkers.

Science.gov (United States)

Mihalcea, Ionut; Volkringer, Christophe; Henry, Natacha; Loiseau, Thierry

2012-09-17

Three series of mixed uranyl-lanthanide (Ce or Nd) carboxylate coordination polymers have been successfully synthesized by means of a hydrothermal route using either conventional or microwave heating methods. These compounds have been prepared from mixtures of uranyl nitrate, lanthanide nitrate together with phthalic acid (1,2), pyromellitic acid (3,4), or mellitic acid (5,6) in aqueous solution. The X-ray diffraction (XRD) single-crystal revealed that the phthalate complex (UO(2))(4)O(2)Ln(H(2)O)(7)(1,2-bdc)(4)·NH(4)·xH(2)O (Ln = Ce(1), Nd(2); x = 1 for 1, x = 0 for 2), is based on the connection of tetranuclear uranyl-centered building blocks linked to discrete monomeric units LnO(2)(H(2)O)(7) via the organic species to generate infinite chains, intercalated by free ammonium cations. The pyromellitate phase (UO(2))(3)Ln(2)(H(2)O)(12)(btec)(3)·5H(2)O (Ce(3), Nd(4)) contains layers of monomeric uranyl-centered hexagonal and pentagonal bipyramids linked via the carboxylate arms of the organic molecules. The three-dimensionality of the structure is ensured by the connection of remaining free carboxylate groups with isolated monomeric units LnO(2)(H(2)O)(7). The network of the third series (UO(2))(2)(OH)Ln(H(2)O)(7)(mel)·5H(2)O (Ce(5), Nd(6)) is built up from dinuclear uranyl units forming layers through connection with the mellitate ligands, which are further linked to each other through discrete monomers LnO(3)(H(2)O)(6). The thermal decomposition of the various coordination complexes led to the formation of mixed uranium-lanthanide oxide, with the fluorite-type structure at 1500 °C (for 1, 2) or 1400 °C for 3-6. Expected U/Ln ratio from the crystal structures were observed for compounds 1-6.

Responsive hybrid inorganic-organic system derived from lanthanide luminescence

Energy Technology Data Exchange (ETDEWEB)

Zhou, Zhan [School of Chemistry and Environment, South China Normal University, Guangzhou 510006 (China); Zheng, Yuhui, E-mail: yhzheng78@scnu.edu.cn [School of Chemistry and Environment, South China Normal University, Guangzhou 510006 (China); Jiang, Lasheng; Yang, Jinglian [School of Chemistry and Environment, South China Normal University, Guangzhou 510006 (China); Wang, Qianming, E-mail: qmwang@scnu.edu.cn [Key Laboratory of Theoretical Chemistry of Environment, Ministry of Education, School of Chemistry and Environment, South China Normal University, Guangzhou 510006 (China); School of Chemistry and Environment, South China Normal University, Guangzhou 510006 (China); Guangzhou Key Laboratory of Materials for Energy Conversion and Storage, Guangzhou 510006 (China)

2016-05-15

Highlights: • A novel covalent hybrid material was used to detect hemoglobin. • All the recognition experiments were performed in buffer solution. • Porous nano-structures was extensively studied for the recognition. - Abstract: Terbium ions were incorporated into new organic-inorganic matrices to achieve intense green emissions. Hemoglobin (HB) interactions lead to dramatic changes in the luminescence emission intensities. Infrared spectra, morphological studies and photoluminescence give information for the speciation and process of hemoglobin additions. The porous material has a large specific surface area of 351 cm{sup 2}/g and the detection limit for HB (0.7 μM) was much lower than its physical doped material (8 μM). This promising hybrid material will lead to the design of versatile optical probes that are efficiently responding to the external targets.

Exploring Trianglamine Derivatives and Trianglamine Coordination Complexes as Porous Organic Materials

KAUST Repository

Eziashi, Magdalene

2018-05-01

Trianglamines are triangular chiral macrocycles that were first synthesized by Gawronski’s group in Poland in the year 2000.1 Despite their unique properties; triangular pore shape, chirality, symmetric structure and tunable pore size, they are still a poorly researched class of macrocycles today. Trianglamines have yet a role to play as porous organic molecules for separation processes, as macrocyclic precursors to build increasingly complex supramolecular assemblies and as building blocks for caged porous organic structures. The aim of the Thesis work is to explore trianglamine, its derivatives, and assemblies as viable porous organic molecules for potential gas capture and separation.

Lanthanide extraction with 2,5-dimethyl-2-hydroxyhexanoic acid

International Nuclear Information System (INIS)

Miller, J.H.

1977-12-01

This research is concerned with the solvent extraction into chloroform of the lanthanides, using 2,5-dimethyl-2-hydroxyhexanoic acid (DMHHA). This acid is the first α-hydroxy aliphatic acid to be studied as an extracting agent for the lanthanides. The chloroform-water DMHHA partition constant was determined to be 1.0 (at 0.1 M ionic strength and 25 0 C). The acid dimerizes in chloroform with a constant of 56. The light lanthanides can be extracted into chloroform by forming complexes with the DMHHA anions. The extracted metal species is highly aggregated. This extraction has a solubility limit which increases with the addition of unionized acid. The resultant extract is also highly aggregated. At unionized acid-to-metal ratios greater than one, extractions first occur followed by the slow precipitation of the lanthanide. At the tracer level, neodymium is extracted primarily as NdA 3 (HA) 5 and (NdA 3 ) 2 (HA)/sub q/. Very small amounts of (NdA 3 ) 2 and other metal aggregates are also present. The heavy lanthanides do not extract from solutions of DMHHA and its potassium salt, but form aqueous emulsions and precipitates. In the presence of the organic soluble tetrabutylammonium ion the heavy lanthanides can be extracted, presumably as ion pairs. The stability constants of the light lanthanides and DMHHA were determined. The separation factors obtained from DMHHA extractions of the light lanthanides were also investigated and found to be comparable to those obtained employing normal aliphatic carboxylic acid

Modular organization of the white spruce (Picea glauca) transcriptome reveals functional organization and evolutionary signatures.

Science.gov (United States)

Raherison, Elie S M; Giguère, Isabelle; Caron, Sébastien; Lamara, Mebarek; MacKay, John J

2015-07-01

Transcript profiling has shown the molecular bases of several biological processes in plants but few studies have developed an understanding of overall transcriptome variation. We investigated transcriptome structure in white spruce (Picea glauca), aiming to delineate its modular organization and associated functional and evolutionary attributes. Microarray analyses were used to: identify and functionally characterize groups of co-expressed genes; investigate expressional and functional diversity of vascular tissue preferential genes which were conserved among Picea species, and identify expression networks underlying wood formation. We classified 22 857 genes as variable (79%; 22 coexpression groups) or invariant (21%) by profiling across several vegetative tissues. Modular organization and complex transcriptome restructuring among vascular tissue preferential genes was revealed by their assignment to coexpression groups with partially overlapping profiles and partially distinct functions. Integrated analyses of tissue-based and temporally variable profiles identified secondary xylem gene networks, showed their remodelling over a growing season and identified PgNAC-7 (no apical meristerm (NAM), Arabidopsis transcription activation factor (ATAF) and cup-shaped cotyledon (CUC) transcription factor 007 in Picea glauca) as a major hub gene specific to earlywood formation. Reference profiling identified comprehensive, statistically robust coexpressed groups, revealing that modular organization underpins the evolutionary conservation of the transcriptome structure. © 2015 The Authors. New Phytologist © 2015 New Phytologist Trust.

Understanding Socio Technical Modularity

DEFF Research Database (Denmark)

Thuesen, Christian Langhoff; Kudsk, Anders; Hvam, Lars

2011-01-01

Modularity has gained an increasing popularity as a central concept for exploring product structure, process structure, organization structure and supply chain structure. With the offset in system theory the predominant understanding of modularity however faces difficulties in explaining the social...... dimension of modularity like irrational behaviors, cultural differences, learning processes, social organization and institutional influences on modularity. The paper addresses this gab offering a reinterpretation of the modularity concept from a socio-technical perspective in general and Actor Network...... Theory in particular. By formulating modularity from an ANT perspective covering social, material and process aspects, the modularity of a socio-technical system can be understood as an entanglement of product, process, organizational and institutional modularity. The theoretical framework is illustrated...

Luminescence stability of porous Si terminated by hydrophilic organic molecules

Science.gov (United States)

Matsumoto, Kimihisa; Kamiguchi, Masao; Kamiya, Kazuhide; Nomura, Takashi; Suzuki, Shinya

2016-02-01

The effects of the surface termination of a porous Si surface by propionic acid and by undecylenic acid on their hydrophilicity and luminescence stability were studied. In the measurements of the contact angle of water droplets on porous Si films, the hydrophilicity of porous Si is improved by the surface termination each types of organic molecule. The PL intensity of as-prepared porous Si decreased with increasing aging time in ambient air. As PL quenching involves PL blue shift and increasing Si-O bonds density, nonradiative recombination centers are formed in the surface oxide. After the hydrosilylation process of propionic acid and undecylenic acid, PL intensity decreased and became 30% that of as-prepared porous Si film. However, the PL intensity was stable and exceeded that of the as-prepared film after 1000 min of aging in the ambient air. The PL stabilities are contributed to the termination by organic molecules that inhibits surface oxidation.

Sustained Activity in Hierarchical Modular Neural Networks: Self-Organized Criticality and Oscillations

Science.gov (United States)

Wang, Sheng-Jun; Hilgetag, Claus C.; Zhou, Changsong

2010-01-01

Cerebral cortical brain networks possess a number of conspicuous features of structure and dynamics. First, these networks have an intricate, non-random organization. In particular, they are structured in a hierarchical modular fashion, from large-scale regions of the whole brain, via cortical areas and area subcompartments organized as structural and functional maps to cortical columns, and finally circuits made up of individual neurons. Second, the networks display self-organized sustained activity, which is persistent in the absence of external stimuli. At the systems level, such activity is characterized by complex rhythmical oscillations over a broadband background, while at the cellular level, neuronal discharges have been observed to display avalanches, indicating that cortical networks are at the state of self-organized criticality (SOC). We explored the relationship between hierarchical neural network organization and sustained dynamics using large-scale network modeling. Previously, it was shown that sparse random networks with balanced excitation and inhibition can sustain neural activity without external stimulation. We found that a hierarchical modular architecture can generate sustained activity better than random networks. Moreover, the system can simultaneously support rhythmical oscillations and SOC, which are not present in the respective random networks. The mechanism underlying the sustained activity is that each dense module cannot sustain activity on its own, but displays SOC in the presence of weak perturbations. Therefore, the hierarchical modular networks provide the coupling among subsystems with SOC. These results imply that the hierarchical modular architecture of cortical networks plays an important role in shaping the ongoing spontaneous activity of the brain, potentially allowing the system to take advantage of both the sensitivity of critical states and the predictability and timing of oscillations for efficient information

Electrodeposition of Vanadium Oxides at Room Temperature as Cathodes in Lithium-Ion Batteries

Directory of Open Access Journals (Sweden)

Michalis Rasoulis

2017-07-01

Full Text Available Electrodeposition of vanadium pentoxide coatings was performed at room temperature and a short growth period of 15 min based on an alkaline solution of methanol and vanadyl (III acetyl acetonate. All samples were characterized by X-ray diffraction, Raman spectroscopy, field-emission scanning electron microscopy, cyclic voltammetry, and electrochemical impedance spectroscopy. The current density and electrolyte concentration were found to affect the characteristics of the as-grown coatings presenting enhanced crystallinity and porous structure at the highest values employed in both cases. The as-grown vanadium pentoxide at current density of 1.3 mA·cm−2 and electrolyte concentration of 0.5 M indicated the easiest charge transfer of Li+ across the vanadium pentoxide/electrolyte interface presenting a specific discharge capacity of 417 mAh·g−1, excellent capacitance retention of 95%, and coulombic efficiency of 94% after 1000 continuous Li+ intercalation/deintercalation scans. One may then suggest that this route is promising to prepare large area vanadium pentoxide electrodes with excellent stability and efficiency at very mild conditions.

Coordination symmetry determination of some lanthanide complexes by x-ray diffraction

International Nuclear Information System (INIS)

Oliveira Paiva Santos, C. de.

1983-01-01

The x-ray determination of the crystal and molecular structures of three lanthanide complexes is described. The work is a contribution to the study of the coordination chemistry of lanthanide ions with organic ligands and in particular, it aims to compare the observed point symmetry of the ion environment with spectroscopic predictions. (author)

Synthesis, structural characterization and selectively catalytic properties of metal-organic frameworks with nano-sized channels: A modular design strategy

International Nuclear Information System (INIS)

Qiu Lingguang; Gu Lina; Hu Gang; Zhang Lide

2009-01-01

Modular design method for designing and synthesizing microporous metal-organic frameworks (MOFs) with selective catalytical activity was described. MOFs with both nano-sized channels and potential catalytic activities could be obtained through self-assembly of a framework unit and a catalyst unit. By selecting hexaaquo metal complexes and the ligand BTC (BTC=1,3,5-benzenetricarboxylate) as framework-building blocks and using the metal complex [M(phen) 2 (H 2 O) 2 ] 2+ (phen=1,10-phenanthroline) as a catalyst unit, a series of supramolecular MOFs 1-7 with three-dimensional nano-sized channels, i.e. [M 1 (H 2 O) 6 ].[M 2 (phen) 2 (H 2 O) 2 ] 2 .2(BTC).xH 2 O (M 1 , M 2 =Co(II), Ni(II), Cu(II), Zn(II), or Mn(II), phen=1,10-phenanthroline, BTC=1,3,5-benzenetricarboxylate, x=22-24), were synthesized through self-assembly, and their structures were characterized by IR, elemental analysis, and single-crystal X-ray diffraction. These supramolecular microporous MOFs showed significant size and shape selectivity in the catalyzed oxidation of phenols, which is due to catalytic reactions taking place in the channels of the framework. Design strategy, synthesis, and self-assembly mechanism for the construction of these porous MOFs were discussed. - Grapical abstract: A modular design strategy has been developed to synthesize microporous metal-organic frameworks with potential catalytic activity by self-assembly of the framework-building blocks and the catalyst unit

Organic-soluble lanthanide nuclear magnetic resonance shift reagents for sulfonium and isothiouronium salts

International Nuclear Information System (INIS)

Wenzel, T.J.; Zaia, J.

1987-01-01

Lanthanide complexes of the formula [Ln(fod) 4 ] - (FOD, 6,6,7,7,8,8,8-heptafluoro-2,2-dimethyl-3,5-octanedione) are effective organic-soluble nuclear magnetic resonance shift reagents for sulfonium and isothiouronium salts. The shift reagent is formed in solution from Ln(fod) 3 and Ag(fod) or K(fod). The selection of Ag(fod) or K(fod) in forming the shift reagent is dependent on the anion of the organic salt. Ag(fod) is more effective with halide salts, whereas K(fod) is preferred with tetrafluoroborate salts. Resolution of diastereotopic hydrogen atoms was observed in the shifted spectra of certain substrates. Enantiomeric resolution was obtained in the spectrum of sec-butylisothiouronium chloride with a chiral shift reagent. The reagents can be employed in solvents such as chloroform and benzene

The Lanthanide Contraction Revisited

Energy Technology Data Exchange (ETDEWEB)

Seitz, Michael; Oliver, Allen G.; Raymond, Kenneth N.

2007-04-19

A complete, isostructural series of lanthanide complexes (except Pm) with the ligand TREN-1,2-HOIQO has been synthesized and structurally characterized by means of single-crystal X-ray analysis. All complexes are 1D-polymeric species in the solid state, with the lanthanide being in an eight-coordinate, distorted trigonal-dodecahedral environment with a donor set of eight unique oxygen atoms. This series constitutes the first complete set of isostructural lanthanide complexes with a ligand of denticity greater than two. The geometric arrangement of the chelating moieties slightly deviates across the lanthanide series, as analyzed by a shape parameter metric based on the comparison of the dihedral angles along all edges of the coordination polyhedron. The apparent lanthanide contraction in the individual Ln-O bond lengths deviates considerably from the expected quadratic decrease that was found previously in a number of complexes with ligands of low denticity. The sum of all bond lengths around the trivalent metal cation, however, is more regular, showing an almost ideal quadratic behavior across the entire series. The quadratic nature of the lanthanide contraction is derived theoretically from Slater's model for the calculation of ionic radii. In addition, the sum of all distances along the edges of the coordination polyhedron show exactly the same quadratic dependency as the Ln-X bond lengths. The universal validity of this coordination sphere contraction, concomitant with the quadratic decrease in Ln-X bond lengths, was confirmed by reexamination of four other, previously published, almost complete series of lanthanide complexes. Due to the importance of multidentate ligands for the chelation of rare-earth metals, this result provides a significant advance for the prediction and rationalization of the geometric features of the corresponding lanthanide complexes, with great potential impact for all aspects of lanthanide coordination.

Photoluminescence properties of lanthanide-organic frameworks (LnOFs) with thiophene-2,5-dicarboxylate and acetate

Energy Technology Data Exchange (ETDEWEB)

Han, Jing; Wei, Qing; Xie, Gang; Chen, Sanping [Key Lab. of Synthetic and Natural Functional Molecule Chemistry of Ministry of Education, College of Chemistry and Materials Science, Northwest Univ., Xi' an, Shaanxi (China); Zhang, Sheng [Key Lab. of Synthetic and Natural Functional Molecule Chemistry of Ministry of Education, College of Chemistry and Materials Science, Northwest Univ., Xi' an, Shaanxi (China); College of Chemistry and Chemical Engineering, Baoji Univ. of Arts and Science, Baoji, Shaanxi (China)

2017-07-17

S-heterocyclic dicarboxylic acid, thiophene-2,5-dicarboxylic acid (H{sub 2}TDC), was employed to construct a series of lanthanide-organic frameworks (LnOFs) with coligand acetate, formulated as [Ln(TDC)(OAc)(H{sub 2}O)]{sub n} [Ln = Eu (1), Tb (2), Gd (3), Dy (4), Sm (5)] under hydrothermal conditions. Structure analysis reveals that 1-5 have dinuclear 3D metal organic frameworks (MOFs), in which TDC{sup 2-} and OAc{sup -} display (κ{sup 1}-κ{sup 1})-(κ{sup 1}-κ{sup 1})-μ{sub 4} and (κ{sup 2}-κ{sup 1})-μ{sub 2} coordination fashions, respectively. The dehydrated products of all compounds show high thermal stability above 410 C. As for 1, 2, 4, and 5, the photoluminescence analyses exhibit characteristic luminescence emission bands of the corresponding lanthanide ions in the visible region. In particular, compound 2 displays bright green luminescence in the solid state with {sup 5}D{sub 4} lifetime of 0.510 ms and relative high overall quantum yield of 16 %, based on an ideal energy gap between the lowest triplet state energy level of H{sub 2}TDC ligand and the {sup 5}D{sub 4} state energy level of Tb{sup 3+}. The energy transfer mechanisms in compounds 1 and 2 were also discussed. (copyright 2017 WILEY-VCH Verlag GmbH and Co. KGaA, Weinheim)

Vanadium and titanium determination by resorcinalhydrazide of salicylic acid

Energy Technology Data Exchange (ETDEWEB)

Karpova, O I; Pilipenko, A T; Lukachina, V V [AN Ukrainskoj SSR, Kiev. Inst. Kolloidnoj Khimii i Khimii Vody

1979-02-01

The complexing of titanium and vanadium with resorcinalhydrazyl of salicylic acid (RHSA) in water-organic media is studied. Titanium (4) forms a complex at pH 0.8-1.8, vanadium - at pH 2.5-5.6, and at pH 7.6-9.8. The complexes are well extracted by polar and nonpolar solvents from acid solutions. The techniques are developed for the determination of titanium and vanadium by the RHSA agent in nickel alloys.

Vanadium Bioleaching Behavior by Acidithiobacillus ferrooxidans from a Vanadium-Bearing Shale

Directory of Open Access Journals (Sweden)

Dunpei Wei

2018-01-01

Full Text Available This study investigated bioleaching behavior of vanadium from a vanadium-bearing shale using Acidithiobacillus ferrooxidans (A. ferrooxidans. Results showed a maximum recovery of 62% vanadium in 1.2-day bioleaching, which was 22.45% higher than the controls. Then, the vanadium leaching efficiency decreased significantly, only 24% of that was obtained on the tenth day. The vanadium extraction in 1.2 days was mainly attributed to the dissolution of vanadium in free oxides of shale. Fe3+ produced by A. ferrooxidans promoted the dissolution process. X-ray diffraction (XRD patterns of the leached residues confirmed the generation of jarosite. SEM-EDS analysis of the residues indicated that jarosite adsorbed on the shale and inhibited the further dissolution of vanadium. The relevance of V, Fe, S, O was quite good in the energy disperse X-ray spectrometry (EDS element mapping of jarosite, and acid-washing of the jarosite resulted in 31.6% of the vanadium in the precipitates desorption, indicating that the decrease of vanadium leaching efficiency in bioleaching process was caused by both adsorption and co-precipitation with jarosite.

Recovery of lanthanides

International Nuclear Information System (INIS)

Tilley, G.L.; Doyle, W.E.

1990-01-01

This paper discusses a method for recovering a lanthanide and thorium from a material containing a fluorine compound and the lanthanide and thorium. It comprises a. obtaining the material from a roasted, acid-leached bastnasite ore; b. forming a mixture of the material with at least about ten weight percent of silica; c. contacting the mixture with sulfuric acid; d. heating the mixture and sulfuric acid to a temperature of at least about 150 degrees C for at least about 3 hours to cause most of the fluorine to be released as a volatile material containing silicon and fluorine; e. contacting the reacted mixture with an aqueous medium consisting essentially of water to solubilize the lanthanide and thorium while leaving an insoluble residue; and f. separating the aqueous solution of the lanthanide and thorium from the insoluble residue

Efficient Construction of Well-Defined Multicompartment Porous Systems in a Modular and Chemically Orthogonal Fashion.

Science.gov (United States)

Gao, Ning; Tian, Tian; Cui, Jiecheng; Zhang, Wanlin; Yin, Xianpeng; Wang, Shiqiang; Ji, Jingwei; Li, Guangtao

2017-03-27

A microfluidic assembly approach was developed for efficiently producing hydrogel spheres with reactive multidomains that can be employed as an advantageous platform to create spherical porous networks in a facile manner with well-defined multicompartments and spatiotemporally controlled functions. This strategy allows for not only large scale fabrication of various robust hydrogel microspheres with controlled size and porosity, but also the domains embedded in hydrogel network could be introduced in a modular manner. Additionally, the number of different domains and their ratio could be widely variable on demand. More importantly, the reactive groups distributed in individual domains could be used as anchor sites to further incorporate functional units in an orthogonal fashion, leading to well-defined multicompartment systems. The strategy provides a new and efficient route to construct well-defined functional multicompartment systems with great flexibility and extendibility. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Anthracene-Based Lanthanide Metal-Organic Frameworks: Synthesis, Structure, Photoluminescence, and Radioluminescence Properties

Directory of Open Access Journals (Sweden)

Stephan R. Mathis

2018-01-01

Full Text Available Four anthracene-based lanthanide metal-organic framework structures (MOFs were synthesized from the combination of the lanthanide ions, Eu3+, Tb3+, Er3+, and Tm3+, with 9,10-anthracenedicarboxylic acid (H2ADC in dimethylformamide (DMF under hydrothermal conditions. The 3-D networks crystalize in the triclinic system with P-1 space group with the following compositions: (i {{[Ln2(ADC3(DMF4·DMF]}n, Ln = Eu (1 and Tb (2} and (ii {{[Ln2(ADC3(DMF2(OH22·2DMF·H2O]}n, Ln = Er (3 and Tm (4}. The metal centers exist in various coordination environments; nine coordinate in (i, while seven and eight coordinate in (ii. The deprotonated ligand, ADC, assumes multiple coordination modes, with its carboxylate functional groups severely twisted away from the plane of the anthracene moiety. The structures show ligand-based photoluminescence, which appears to be significantly quenched when compared with that of the parent H2ADC solid powder. Structure 2 is the least quenched and showed an average photoluminescence lifetime from bi-exponential decay of 0.3 ns. On exposure to ionizing radiation, the structures show radioluminescence spectral features that are consistent with the isolation of the ligand units in its 3-D network. The spectral features vary among the 3-D networks and appear to suggest that the latter undergo significant changes in their molecular and/or electronic structure in the presence of the ionizing radiation.

Extraction of lanthanides and actinides (III) by DI-2 ethyl dithiophosphoric acid and DI-2 ethyl hexyl monothiophosphoric acid. Structure of the complexes in the organic phase

International Nuclear Information System (INIS)

Pattee, D.; Musikas, C.; Faure, A.; Chachaty, C.

1986-09-01

To operate a trivalent actinide-lanthanide (III) group chemical separation from low pH nitric solutions we studied the extractive properties of the di-2 ethyl hexyl dithiophosphoric acid (HDEHDTP); this bidentate ligand which possesses a sulfur donor atom is a good extractant of soft acids. We so expect a better selectivity for the actinides (III) extraction. We also have investigated extractive properties of di-2 ethyl hexyl monothiophosphoric acid (HDEHTP) for trivalent actinides and lanthanides; HDEHDTP is a bidentate ligand with one oxygen donor atom and so is a better extractant for hard acids like actinides and lanthanides (III); but its selectivity is weak. The addition of TBP (tri-n butyl phosphate) to HDEHDTP deals to strong synergistic organic complexes with a great selectivity for Am(III). We explicited this phenomenon. When the metal is macroconcentrated the organic complexes aggregate and form inverted micelles

Vanadium bioavailability and toxicity to soil microorganisms and plants

OpenAIRE

Larsson, Maja A; Baken, Stijn; Gustafsson, Jon Petter; Hadialhejazi, Golshid; Smolders, Erik

2013-01-01

Vanadium, V, is a redox-sensitive metal that in solution, under aerobic conditions, prevails as the oxyanion vanadate(V). There is little known regarding vanadium toxicity to soil biota, and the present study was set up to determine the toxicity of added vanadate to soil organisms and to investigate the relationship between toxicity and vanadium sorption in soils. Five soils with contrasting properties were spiked with 7 different doses (3.2-3200mgVkg(-1)) of dissolved vanadate, and toxicity ...

Syntheses, structures and characterizations of three novel vanadium selenites with organically bonded copper/nickel complex

Science.gov (United States)

Qian, Cheng; Kong, Fang; Mao, Jiang-Gao

2016-06-01

A series of vanadium selenites covalently bonded with metal-organic complex, namely, Ni(2,2-bipy)2V2O4(SeO3)2 (1), Cu(2,2-bipy)V2O4(SeO3)2·0.5H2O (2) and Cu2(2,2-bipy)2V5O12(SeO3)2 (3) (2,2-bipy=2,2-bipyridine) have been hydrothermally synthesized and structurally characterized. They exhibit three different structural dimensions, from 0D cluster, 1D chain to 2D layer. Compound 1 features a 0D {Ni(2,2-bipy)2V2O4(SeO3)2}2 dimeric cluster composed of two {Ni(2,2-bipy)2}2+ moieties connected by the {V4O8(SeO3)4}4- cluster. Compound 2 shows a 1D {Cu(2,2-bipy)V2O4(SeO3)2}n chain in which the {Cu2(2,2-bipy)2}4+ moieties are bridged by the {V4O8(SeO3)4}4- clusters. Compound 3 displays a 2D structure consisted of mixed valence vanadium selenites layers {VIVVV4SeIV2O18}n4- and {Cu(2,2-bipy)}2+ complex moieties. The adjacent layers are further interconnected via π-π interactions between the 2,2-bipy ligands exhibiting an interesting 3D supramolecular architecture. Both compound 1 and 2 contain a new {V4O8(SeO3)4}4- cluster and compound 3 exhibits the first 2D vanadate polyhedral layer in vanadium selenites/tellurites with organic moieties.

Researches on vanadium and its compounds; Recherches sur le Vanadium et ses composes

Energy Technology Data Exchange (ETDEWEB)

Morette, Andre

1937-06-03

In this research thesis, the author proposes a new study of the action of some reduction agents on two groups of vanadium compounds, oxides and chlorides. Thus, he reports the study of the circumstances of reduction of vanadium oxides by carbon and of vanadium carburization from these compounds. He also reports the determination of the composition of vanadium melts obtained at high temperatures (either in a vacuum furnace or with an electric arc furnace). In order to determine in which conditions the processing of vanadium oxides could produce the pure metal, the author studied the action of calcium and magnesium on the vanadium pentoxide and trioxide. The second part of the thesis addresses the preparation of pure vanadium from vanadium anhydride chlorides. Then, the author reports the development of processes which could easily produce powdered vanadium [French] Nous nous sommes propose de reprendre l'etude de l'action de quelques reducteurs sur les deux groupes de composes du vanadium, oxydes et chlorures. Nous avons ete ainsi amene a preciser les circonstances de la reduction des oxydes de vanadium par le carbone et de la carburation du vanadium a partir de ceux-ci, puis a determiner la constitution des fontes de vanadium obtenues a haute temperature, soit au four a vide, soit au four a arc. D'autre part, en vue de determiner dans quelles conditions le traitement des oxydes de vanadium pourrait conduire au metal pur, nous avons repris et complete des travaux anterieurs concernant l'action du calcium et du magnesium sur le pentoxyde ou eventuellement le trioxyde de vanadium. Une seconde partie de notre these a ete consacree a la preparation du vanadium pur a partir des chlorures anhydres de vanadium. Nous nous sommes attache a trouver le mode operatoire le plus favorable pour l'obtention de chacun d'eux. Il nous a ete donne ainsi l'occasion de preciser certaines de leurs proprietes physiques et chimiques. Puis, a la suite d'essais systematiques, nous avons

Vanadium contents in Kazakhstan fossils hydrocarbons by data of nuclear-physical analysis methods

International Nuclear Information System (INIS)

Nadirov, N.K.; Solodukhin, V.P.

1998-01-01

Investigation of nuclear physical methods possibilities of vanadium determination analysis in organic fossils and an application of these methods for solution of scientific and practical tasks are presented. Vanadium contents in high viscous petroleums and petroleum bituminous rock of different deposits of Western Kazakhstan and carbonaceous shales of Dzhangariya are studied. Presented data evidence that organic fossils of numerous deposits of Kazakhstan have industrial interest because of high vanadium concentration in its contents

Porous Organic Polymers for CO2 Capture

KAUST Repository

Teng, Baiyang

2013-01-01

to reduce the emission of CO2 to atmosphere. Porous organic polymers (POPs) are promising candidates for this application due to their readily tunable textual properties and surface functionalities. The objective of this thesis work is to develop new POPs

Calorimetric approach of lanthanides (3) complexation and extraction by malonamides

International Nuclear Information System (INIS)

Flandin, J.L.

2001-01-01

In the field of long lived radionuclides separation, diamides are interesting extractants because of their ability to co-extract trivalent lanthanides and actinides, which is a preliminary and essential step in high level radioactive waste reprocessing. The research carried out contributes to a better understanding of the mechanisms and the aim is the determination of thermodynamics properties (Δ r G, Δ r H et Δ r S) related to the complexation and the extraction of lanthanides(III) by malonamides. The first part of the document deals with the complexation of lanthanides(III) by an hydrosoluble diamide. The experimental results obtained by UV-visible spectrometry, TRLIF, NMR and microcalorimetric titration proved that lanthanides(III)-TEMA interactions in aqueous medium are very weak and that the complexation reaction is endothermic. The TEMA ligand still stays in the second coordination sphere of coordination of the lanthanide ion. The second part of this study focuses on the extraction of neodymium(III) nitrate by a lipophilic diamide which is an exothermic reaction. The influence of the composition of aqueous and organic phases on the thermodynamics properties Δ r G et Δ r H has been studied by microcalorimetric titration. The most influent parameter is the total concentration in extractant. As a consequence, thermodynamic values are very dependent on the organic phase organisation before and alter extraction. At the same time, this study showed the interest of the calorimetric approach for the analysis of basic reactions like diamide dilution and their organisation as oligomeric aggregates. (author)

Episodic Memory Retrieval Benefits from a Less Modular Brain Network Organization.

Science.gov (United States)

Westphal, Andrew J; Wang, Siliang; Rissman, Jesse

2017-03-29

Most complex cognitive tasks require the coordinated interplay of multiple brain networks, but the act of retrieving an episodic memory may place especially heavy demands for communication between the frontoparietal control network (FPCN) and the default mode network (DMN), two networks that do not strongly interact with one another in many task contexts. We applied graph theoretical analysis to task-related fMRI functional connectivity data from 20 human participants and found that global brain modularity-a measure of network segregation-is markedly reduced during episodic memory retrieval relative to closely matched analogical reasoning and visuospatial perception tasks. Individual differences in modularity were correlated with memory task performance, such that lower modularity levels were associated with a lower false alarm rate. Moreover, the FPCN and DMN showed significantly elevated coupling with each other during the memory task, which correlated with the global reduction in brain modularity. Both networks also strengthened their functional connectivity with the hippocampus during the memory task. Together, these results provide a novel demonstration that reduced modularity is conducive to effective episodic retrieval, which requires close collaboration between goal-directed control processes supported by the FPCN and internally oriented self-referential processing supported by the DMN. SIGNIFICANCE STATEMENT Modularity, an index of the degree to which nodes of a complex system are organized into discrete communities, has emerged as an important construct in the characterization of brain connectivity dynamics. We provide novel evidence that the modularity of the human brain is reduced when individuals engage in episodic memory retrieval, relative to other cognitive tasks, and that this state of lower modularity is associated with improved memory performance. We propose a neural systems mechanism for this finding where the nodes of the frontoparietal control

Electric double layer capacitance on hierarchical porous carbons in an organic electrolyte

OpenAIRE

Yamada, Hirotoshi; Moriguchi, Isamu; Kudo, Tetsuichi

2008-01-01

Nanoporous carbons were prepared by using colloidal crystal as a template. Nitrogen adsorption/desorption isotherms and transmission electron microscope images revealed that the porous carbons exhibit hierarchical porous structures with meso/macropores and micropores. Electric double layer capacitor performance of the porous carbons was investigated in an organic electrolyte of 1 M LiClO4 in propylene carbonate and dimethoxy ethane. The hierarchical porous carbons exhibited large specific dou...

Modular assembly of metal-organic super-containers incorporating calixarenes

Science.gov (United States)

Wang, Zhenqiang; Dai, Feng-Rong

2018-01-16

A new strategy to design container molecules is presented. Sulfonylcalix[4]arenes, which are synthetic macrocyclic containers, are used as building blocks that are combined with various metal ions and tricarboxylate ligands to construct metal-organic `super-containers` (MOSCs). These MOSCs possess both endo and exo cavities and thus mimic the structure of viruses. The synthesis of MOSCs is highly modular, robust, and predictable.

APS- and XPS-investigations of vanadium, vanadium carbide and graphite

Energy Technology Data Exchange (ETDEWEB)

Bradshaw, A M; Krause, U [Technische Univ. Muenchen (F.R. Germany). Inst. fuer Physikalische Chemie und Theoretische Chemie

1975-11-01

Soft X-ray appearance potential spectroscopy (APS) and X-ray photoelectron spectroscopy (XPS) have been used to study vanadium, vanadium carbide, and graphite. The chemical shifts for vanadium carbide with respect to metallic vanadium and graphite are compared for the two methods. The Csub(K) structure in APS and the valence band in XPS for vanadium carbide show good agreement with the band structure calculations of Neckel and co-workers. Using the band structure calculations of Painter et al. it is also shown how the multi-peak structure in the APS spectrum of graphite is possibly due to density of states effects. It would therefore appear that plasmon coupling plays only a minor role.

Ordered microporous layered lanthanide 1,3,5-benzenetriphosphonates pillared with cationic organic molecules.

Science.gov (United States)

Araki, Takahiro; Kondo, Atsushi; Maeda, Kazuyuki

2015-04-13

Novel isomorphous pillared-layer-type crystalline lanthanide 1,3,5-benzenetriphosphonates were prepared with bpy and dbo as organic pillars (LnBP-bpy and LnBP-dbo; Ln: Ce, Pr, and Nd). Ab initio crystal structure solution using synchrotron X-ray powder diffraction data revealed that the organic pillars do not exist as neutral coordinating ligands but as cationic molecules. Especially the LnBP-dbo phases have ordered interlayer space filled with water molecules between the dbo pillars, and the interlayer water is successfully removed by heating under vacuum with slightly distorted but basically retained pillared layer structures. Microporosity of the materials is confirmed by adsorption of nitrogen, carbon dioxide, and hydrogen gases. Such microporous layered metal phosphonates pillared with cationic molecules should be unprecedented and should offer new strategies to design ordered microporous materials. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Syntheses, structures and characterizations of three novel vanadium selenites with organically bonded copper/nickel complex

International Nuclear Information System (INIS)

Qian, Cheng; Kong, Fang; Mao, Jiang-Gao

2016-01-01

A series of vanadium selenites covalently bonded with metal-organic complex, namely, Ni(2,2-bipy) 2 V 2 O 4 (SeO 3 ) 2 (1), Cu(2,2-bipy)V 2 O 4 (SeO 3 ) 2 ·0.5H 2 O (2) and Cu 2 (2,2-bipy) 2 V 5 O 12 (SeO 3 ) 2 (3) (2,2-bipy=2,2-bipyridine) have been hydrothermally synthesized and structurally characterized. They exhibit three different structural dimensions, from 0D cluster, 1D chain to 2D layer. Compound 1 features a 0D {Ni(2,2-bipy) 2 V 2 O 4 (SeO 3 ) 2 } 2 dimeric cluster composed of two {Ni(2,2-bipy) 2 } 2+ moieties connected by the {V 4 O 8 (SeO 3 ) 4 } 4- cluster. Compound 2 shows a 1D {Cu(2,2-bipy)V 2 O 4 (SeO 3 ) 2 } n chain in which the {Cu 2 (2,2-bipy) 2 } 4+ moieties are bridged by the {V 4 O 8 (SeO 3 ) 4 } 4− clusters. Compound 3 displays a 2D structure consisted of mixed valence vanadium selenites layers {V IV V V 4 Se IV 2 O 18 } n 4− and {Cu(2,2-bipy)} 2+ complex moieties. The adjacent layers are further interconnected via π-π interactions between the 2,2-bipy ligands exhibiting an interesting 3D supramolecular architecture. Both compound 1 and 2 contain a new {V 4 O 8 (SeO 3 ) 4 } 4− cluster and compound 3 exhibits the first 2D vanadate polyhedral layer in vanadium selenites/tellurites with organic moieties. - Graphical abstract: We got three new vanadium selenites with organically linked copper/nickel complex, namely, Ni(2,2-bipy) 2 V 2 O 4 (SeO 3 ) 2 (1), Cu(2,2-bipy)V 2 O 4 (SeO 3 ) 2 ·0.5H 2 O (2) and Cu 2 (2,2-bipy) 2 V 5 O 12 (SeO 3 ) 2 (3) by hydrothermally syntheses. They display three different structural dimensions, from 0D cluster, to 1D chain and 2D layer. Display Omitted - Highlights: • Three new compounds display three different structural dimensions, from 0D cluster, to 1D chain and 2D layer. • The Tetranuclear {V 4 O 8 (SeO 3 ) 4 } 4− cluster and the vanadate {V 5 O 17 } n 2D layer are observed firstly. • Optical Properties and Magnetic Properties of three compounds are reported.

Vanadium Electrolyte Studies for the Vanadium Redox Battery-A Review.

Science.gov (United States)

Skyllas-Kazacos, Maria; Cao, Liuyue; Kazacos, Michael; Kausar, Nadeem; Mousa, Asem

2016-07-07

The electrolyte is one of the most important components of the vanadium redox flow battery and its properties will affect cell performance and behavior in addition to the overall battery cost. Vanadium exists in several oxidation states with significantly different half-cell potentials that can produce practical cell voltages. It is thus possible to use the same element in both half-cells and thereby eliminate problems of cross-contamination inherent in all other flow battery chemistries. Electrolyte properties vary with supporting electrolyte composition, state-of-charge, and temperature and this will impact on the characteristics, behavior, and performance of the vanadium battery in practical applications. This Review provides a broad overview of the physical properties and characteristics of the vanadium battery electrolyte under different conditions, together with a description of some of the processing methods that have been developed to produce vanadium electrolytes for vanadium redox flow battery applications. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Expanded Organic Building Units for the Construction of Highly Porous Metal-Organic Frameworks

NARCIS (Netherlands)

Kong, G.Q.; Han, Z.D.; He, Y.; Qu, S.; Zhou, W.; Yildirim, T.; Krishna, R.; Zou, C.; Chen, B.; Wu, C.D.

2013-01-01

wo new organic building units that contain dicarboxylate sites for their self-assembly with paddlewheel [Cu2(CO2)4] units have been successfully developed to construct two isoreticular porous metal-organic frameworks (MOFs), ZJU-35 and ZJU-36, which have the same tbo topologies (Reticular Chemistry

Calorimetric approach of lanthanides (3) complexation and extraction by malonamides; Approche calorimetrique de la complexation et de l'extraction des lanthanides (3) par les malonamides

Energy Technology Data Exchange (ETDEWEB)

Flandin, J.L

2001-07-01

In the field of long lived radionuclides separation, diamides are interesting extractants because of their ability to co-extract trivalent lanthanides and actinides, which is a preliminary and essential step in high level radioactive waste reprocessing. The research carried out contributes to a better understanding of the mechanisms and the aim is the determination of thermodynamics properties ({delta}{sub r}G, {delta}{sub r}H et {delta}{sub r}S) related to the complexation and the extraction of lanthanides(III) by malonamides. The first part of the document deals with the complexation of lanthanides(III) by an hydrosoluble diamide. The experimental results obtained by UV-visible spectrometry, TRLIF, NMR and microcalorimetric titration proved that lanthanides(III)-TEMA interactions in aqueous medium are very weak and that the complexation reaction is endothermic. The TEMA ligand still stays in the second coordination sphere of coordination of the lanthanide ion. The second part of this study focuses on the extraction of neodymium(III) nitrate by a lipophilic diamide which is an exothermic reaction. The influence of the composition of aqueous and organic phases on the thermodynamics properties {delta}{sub r}G et {delta}{sub r}H has been studied by microcalorimetric titration. The most influent parameter is the total concentration in extractant. As a consequence, thermodynamic values are very dependent on the organic phase organisation before and alter extraction. At the same time, this study showed the interest of the calorimetric approach for the analysis of basic reactions like diamide dilution and their organisation as oligomeric aggregates. (author)

'Americium(III)/trivalent lanthanides' separation using organothiophosphinic acids

International Nuclear Information System (INIS)

Hill, C.; Madic, C.; Baron, P.; Ozawa, Masaki; Tanaka, Yasumasa.

1997-01-01

The present paper describes the extraction of neodymium and other lanthanides by saponified Cyanex 301 acid. The saponification of commercial Cyanex 301 acid favoured the extraction of macro concentrations of neodymium from sodium nitrate aqueous solutions (pH eq ∼ 4). The amount of lanthanide extracted in the organic phase always reached the third of the initial concentration of saponified Cyanex 301 acid, which assumed a cation exchange mechanism to occur during the extraction. No nitrate anion took part in the complex formation. This paper also compares the abilities of purified Cyanex 301, Cyanex 302 and Cyanex 272 acids to extract and separate 241 Am(III) from 152 Eu(III). Very high separation factors S.F. Am/Eu were observed in the case of purified Cyanex 301 acid. Finally some studies are presented herein using tri-n-butylphosphate (TBP) as a synergistic extractant with Cyanex 301 acid to separate actinides from trivalent lanthanide. (author)

Vanadium Compounds as PTP Inhibitors

Directory of Open Access Journals (Sweden)

Elsa Irving

2017-12-01

Full Text Available Phosphotyrosine signaling is regulated by the opposing actions of protein tyrosine kinases (PTKs and protein tyrosine phosphatases (PTPs. Here we discuss the potential of vanadium derivatives as PTP enzyme inhibitors and metallotherapeutics. We describe how vanadate in the V oxidized state is thought to inhibit PTPs, thus acting as a pan-inhibitor of this enzyme superfamily. We discuss recent developments in the biological and biochemical actions of more complex vanadium derivatives, including decavanadate and in particular the growing number of oxidovanadium compounds with organic ligands. Pre-clinical studies involving these compounds are discussed in the anti-diabetic and anti-cancer contexts. Although in many cases PTP inhibition has been implicated, it is also clear that many such compounds have further biochemical effects in cells. There also remain concerns surrounding off-target toxicities and long-term use of vanadium compounds in vivo in humans, hindering their progress through clinical trials. Despite these current misgivings, interest in these chemicals continues and many believe they could still have therapeutic potential. If so, we argue that this field would benefit from greater focus on improving the delivery and tissue targeting of vanadium compounds in order to minimize off-target toxicities. This may then harness their full therapeutic potential.

Analytical chemistry of lanthanides

International Nuclear Information System (INIS)

Al-Sowdani, K.H.

1986-12-01

Candoluminescence of the lanthanides and the development of instruments for monitoring the phenomenon are described. The use of fluorescence spectroscopy, spectrofluorometry and spectrophotometry for the quantitative chemical analysis of the lanthanides is described. (U.K.)

Episodic Memory Retrieval Benefits from a Less Modular Brain Network Organization

Science.gov (United States)

2017-01-01

Most complex cognitive tasks require the coordinated interplay of multiple brain networks, but the act of retrieving an episodic memory may place especially heavy demands for communication between the frontoparietal control network (FPCN) and the default mode network (DMN), two networks that do not strongly interact with one another in many task contexts. We applied graph theoretical analysis to task-related fMRI functional connectivity data from 20 human participants and found that global brain modularity—a measure of network segregation—is markedly reduced during episodic memory retrieval relative to closely matched analogical reasoning and visuospatial perception tasks. Individual differences in modularity were correlated with memory task performance, such that lower modularity levels were associated with a lower false alarm rate. Moreover, the FPCN and DMN showed significantly elevated coupling with each other during the memory task, which correlated with the global reduction in brain modularity. Both networks also strengthened their functional connectivity with the hippocampus during the memory task. Together, these results provide a novel demonstration that reduced modularity is conducive to effective episodic retrieval, which requires close collaboration between goal-directed control processes supported by the FPCN and internally oriented self-referential processing supported by the DMN. SIGNIFICANCE STATEMENT Modularity, an index of the degree to which nodes of a complex system are organized into discrete communities, has emerged as an important construct in the characterization of brain connectivity dynamics. We provide novel evidence that the modularity of the human brain is reduced when individuals engage in episodic memory retrieval, relative to other cognitive tasks, and that this state of lower modularity is associated with improved memory performance. We propose a neural systems mechanism for this finding where the nodes of the frontoparietal

Extraction of lanthanide(III) nitrates from water-salt solutions with n.-octanol

International Nuclear Information System (INIS)

Keskinov, V.A.; Kudrova, A.V.; Valueva, O.V.; Pyartman, A.K.

2004-01-01

Extraction of lanthanide(III) nitrates (Ln=La-Nd, Sm-Gd) from aqueous-salt solutions at 298.15 K was studied using solution of n.-octanol, its concentration 6.31 mol/l. It was ascertained that at Ln(NO 3 ) 3 concentration in aqueous phase below 0.6 mol/l, there is actually no extraction. At higher concentrations of nitrates in aqueous phase the content of lanthanides(III) in organic phase increases in the series La-Gd. Isotherms of extraction were ascertained, its phase equilibria being described mathematically. It is shown that extraction of lanthanide(III) nitrates with n.-octanol should be realized from concentrated aqueous solutions [ru

Geochemistry of vanadium in an epigenetic, sandstone-hosted vanadium- uranium deposit, Henry Basin, Utah

Science.gov (United States)

Wanty, R.B.; Goldhaber, M.B.; Northrop, H.R.

1990-01-01

The epigenetic Tony M vanadium-uranium orebody in south-central Utah is hosted in fluvial sandstones of the Morrison Formation (Upper Jurassic). Measurements of the relative amounts of V+3 and V +4 in ore minerals show that V+3 is more abundant. Thermodynamic calculations show that vanadium was more likely transported to the site of mineralization as V+4. The ore formed as V+4 was reduced by hydrogen sulfide, followed by hydrolysis and precipitation of V+3 in oxide minerals or chlorite. Uranium was transported as uranyl ion (U+6), or some complex thereof, and reduced by hydrogen sulfide, forming coffinite. Detrital organic matter in the rocks served as the carbon source for sulfate-reducing bacteria. Vanadium most likely was derived from the dissolution of iron-titanium oxides. Uranium probably was derived from the overlying Brushy Basin Member of the Morrison Formation. Previous studies have shown that the ore formed at the density-stratified interface between a basinal brine and dilute meteoric water. The mineralization processes described above occurred within the mixing zone between these two fluids. -from Authors

Scandium, yttrium and the lanthanides

International Nuclear Information System (INIS)

Hart, F.A.

1987-01-01

This chapter on the chemistry of the coordination complexes of scandium, yttrium and the lanthanides includes sections on the nitrogen and oxygen donor ligands and complex halides of scandium, and the phosphorus and sulfur donor ligands of yttrium and the lanthanides. Complexes with the macrocylic ligands and with halides are also discussed. Sections on the NMR and electronic spectra of the lanthanides are also included. (UK)

Vanadium bioavailability and toxicity to soil microorganisms and plants.

Science.gov (United States)

Larsson, Maja A; Baken, Stijn; Gustafsson, Jon Petter; Hadialhejazi, Golshid; Smolders, Erik

2013-10-01

Vanadium, V, is a redox-sensitive metal that in solution, under aerobic conditions, prevails as the oxyanion vanadate(V). There is little known regarding vanadium toxicity to soil biota, and the present study was set up to determine the toxicity of added vanadate to soil organisms and to investigate the relationship between toxicity and vanadium sorption in soils. Five soils with contrasting properties were spiked with 7 different doses (3.2-3200 mg V kg(-1)) of dissolved vanadate, and toxicity was measured with 2 microbial and 3 plant assays. The median effective concentration (EC50) thresholds of the microbial assays ranged from 28 mg added V kg(-1) to 690 mg added V kg(-1), and the EC50s in the plant assays ranged from 18 mg added V kg(-1) to 510 mg added V kg(-1). The lower thresholds were in the concentration range of the background vanadium in the untreated control soils (15-58 mg V kg(-1)). The vanadium toxicity to plants decreased with a stronger soil vanadium sorption strength. The EC50 values for plants expressed on a soil solution basis ranged from 0.8 mg V L(-1) to 15 mg V L(-1) and were less variable among soils than corresponding values based on total vanadium in soil. It is concluded that sorption decreases the toxicity of added vanadate and that soil solution vanadium is a more robust measure to determine critical vanadium concentrations across soils. © 2013 SETAC.

Leaching characteristics of vanadium in mine tailings and soils near a vanadium titanomagnetite mining site

Energy Technology Data Exchange (ETDEWEB)

Yang, Jinyan; Tang, Ya; Yang, Kai [College of Architecture and Environment, Sichuan University, Chengdu 610065 (China); Rouff, Ashaki A. [School of Earth and Environmental Sciences, Queens College City University of New York, 65-30 Kissena Boulevard, Flushing, NY 11367 (United States); Elzinga, Evert J. [Department of Earth and Environmental Sciences, Rutgers University, Newark, NJ (United States); Huang, Jen-How, E-mail: jen-how.huang@unibas.ch [Institute of Environmental Geosciences, University of Basel, CH-4056 Basel (Switzerland)

2014-01-15

Highlights: • Vanadium in the soil and mine tailings has low solubility. • The leachability of vanadium in the mine tailings is lower than in the soil. • Low risk of vanadium migrating from the soil and mine tailings into the surrounding environment. • Drought and rewetting increase vanadium release from the soil and mine tailings. • Soil leaching processes control vanadium transport in soils overlain with mine tailings. -- Abstract: A series of column leaching experiments were performed to understand the leaching behaviour and the potential environmental risk of vanadium in a Panzhihua soil and vanadium titanomagnetite mine tailings. Results from sequential extraction experiments indicated that the mobility of vanadium in both the soil and the mine tailings was low, with <1% of the total vanadium readily mobilised. Column experiments revealed that only <0.1% of vanadium in the soil and mine tailing was leachable. The vanadium concentrations in the soil leachates did not vary considerably, but decreased with the leachate volume in the mine tailing leachates. This suggests that there was a smaller pool of leachable vanadium in the mine tailings compared to that in the soil. Drought and rewetting increased the vanadium concentrations in the soil and mine tailing leachates from 20 μg L{sup −1} to 50–90 μg L{sup −1}, indicating the potential for high vanadium release following periods of drought. Experiments with soil columns overlain with 4, 8 and 20% volume mine tailings/volume soil exhibited very similar vanadium leaching behaviour. These results suggest that the transport of vanadium to the subsurface is controlled primarily by the leaching processes occurring in soils.

Pressure-induced polyamorphism in lanthanide-solute metallic glasses

Energy Technology Data Exchange (ETDEWEB)

Li, Liangliang; Li, Renfeng; Liu, Haozhe [Harbin Institute of Technology, Harbin (China); Center for High Pressure Science Technology Advanced Research, Changchun (China); Wang, Luhong [Harbin Institute of Technology, Harbin (China); Qu, Dongdong [School of Mechanical and Mining Engineering, The University of Queensland, Brisbane, QLD (Australia); Zhao, Haiyan [X-ray Science Division, Advanced Photon Source, Argonne National Laboratory, Argonne, IL (United States); Center for Advanced Energy Studies, University of Idaho, Idaho Falls, ID (United States); Chapman, Karena W.; Chupas, Peter J. [X-ray Science Division, Advanced Photon Source, Argonne National Laboratory, Argonne, IL (United States)

2017-06-15

The electronic structure inheritance of lanthanide-solvent atoms in lanthanide-based metallic glasses has been proposed. Is a polyamorphism possible in lanthanide-solute metallic glasses? So far, polyamorphic phase transitions in metallic glass containing lanthanide have been observed only in lanthanide-solvent metallic glasses. Here, a pressure-induced transition between two distinct amorphous states, accompanied by a 7% volume collapse at ambient pressure, was observed in La{sub 43.4}Pr{sub 18.6}Al{sub 14}Cu{sub 24} metallic glass, with low lanthanide content, by using in situ X-ray total scattering method. The transformation also indicated by changes in short range and medium range order. Thus, it is proposed that the lanthanide-solute metallic glasses also inherit 4f electronic transition from pure lanthanide element in polyamorphic transition. This discovery offers a supplement to research on lanthanide-based metallic glasses, which further provides a new perspective of the polyamorphic transformation in metallic glasses containing lanthanide element. (copyright 2017 WILEY-VCH Verlag GmbH and Co. KGaA, Weinheim)

Extraction chromatography of lanthanides, ch. 8

International Nuclear Information System (INIS)

Siekierski, S.; Fidelis, I.

1975-01-01

The extraction of lanthanides by chelate formation with acidic organophosphorous extractants, by solvation of salts, and in the form of ion pairs is reviewed. The double-double effect and its significance for the lanthanide as well as the actinide separation is discussed. A short survey of the existing data on the enthalpies of lanthanide extraction and on the influence of temperature on their separation factor is given. The resolution ability of columns used for the separation of lanthanides is briefly surveyed

Investigation on the fates of vanadium and nickel during co-gasification of petroleum coke with biomass.

Science.gov (United States)

Li, Jiazhou; Wang, Xiaoyu; Wang, Bing; Zhao, Jiantao; Fang, Yitian

2018-06-01

This study investigates the volatilization behaviors and mineral transformation of vanadium and nickel during co-gasification of petroleum coke with biomass. Moreover, the evolution of occurrence modes of vanadium and nickel was also determined by the method of sequential chemical extraction. The results show that the volatilities of vanadium and nickel in petroleum coke have a certain level of growth with an increase in the temperature. With the addition of biomass, their volatilities both show an obvious decrease. Organic matter and stable forms are the dominant chemical forms of vanadium and nickel. After gasification, organic-bound vanadium and nickel decompose completely and convert into other chemical forms. The crystalline phases of vanadium trioxide, coulsonite, nickel sulfide, and elemental nickel are clearly present in petroleum coke and biomass gasification ashes. When the addition of biomass reaches 60 wt%, the diffraction peaks of orthovanadate are found while that of vanadium trioxide disappear. Copyright © 2018 Elsevier Ltd. All rights reserved.

Organometallic complex chemistry of plutonium and selected lanthanides

International Nuclear Information System (INIS)

Seemann, U.

1987-01-01

This study deals with the metallo-organic chemistry of plutonium and also with that of some lanthanides. For plutonium, the conversion of Cs 2 PuCl 6 with four equivalents KCp is investigated. In the series Sm, Gd, Dy and Er, compounds of the type Cp 2 LnX and the base adducts with acetonitrile are analysed. The ligand X passes the series Cl, N 3 , NCS and NCO. Both, the thermal and the vibrational spectroscopic behaviour is investigated. In addition, the effect of a changed ligand sphere on the optical spectrum is discussed. The adduct-free compounds are described by a ternary reaction not yet known from literature. For the first time, force constant calculations are carried out on metallo-organic compounds of lanthanides. With the exception of Cp 2 LnCl compounds, all compouds are presented for the first time in the framework of this study. (orig.) [de

SOLVENT EXTRACTION PROCESS FOR SEPARATING ACTINIDE AND LANTHANIDE METAL VALUES

Science.gov (United States)

Hildebrandt, R.A.; Hyman, H.H.; Vogler, S.

1962-08-14

A process of countercurrently extracting an aqueous mineral acid feed solution for the separation of actinides from lanthanides dissolved therern is described. The feed solution is made acid-defrcient with alkali metal hydroxide prior to.contact with acid extractant; during extraction, however, acid is transferred from organic to aqueous solution and the aqueous solution gradually becomes acid. The acid-deficient phase ' of the process promotes the extraction of the actinides, while the latter acid phase'' of the process improves retention of the lanthanides in the aqueous solution. This provides for an improved separation. (AEC)

Complexing of vanadium(3) with chromotropic acid derivatives

International Nuclear Information System (INIS)

Babenko, N.L.; Busev, A.I.; Sukhorukova, N.V.; Frolova, O.S.

1976-01-01

A spectrophotometric study has been made of the complex formation of vanadium (3) with arsenazo(1), arsenazo(3) and some monosubstituted derivatives of chromotropic acid and sulphanylamides. In acid medium vanadium (3) reacts with each of these reagents to produce a 1:1 complex. Optimum conditions of the complex formation was found. The effect of H + on the complex formation of vanadium (3) with chromotropic acid derivatives was established. It was found by the graphical method that the formation of the complex is accompanied by the elimination of one proton. Patterns were found of the influence of the nature of substituents in the organic compound on the ionization constants of acid groups and stability of complexes. Molar extinction coefficients, equilibrium constants of the formation reactions and instability constants for the complexes were calculated. The structure of complexes was suggested. Similar behaviour of all the reagents was established in the complex formation with vanadium (3)

Neural modularity helps organisms evolve to learn new skills without forgetting old skills.

Science.gov (United States)

Ellefsen, Kai Olav; Mouret, Jean-Baptiste; Clune, Jeff

2015-04-01

A long-standing goal in artificial intelligence is creating agents that can learn a variety of different skills for different problems. In the artificial intelligence subfield of neural networks, a barrier to that goal is that when agents learn a new skill they typically do so by losing previously acquired skills, a problem called catastrophic forgetting. That occurs because, to learn the new task, neural learning algorithms change connections that encode previously acquired skills. How networks are organized critically affects their learning dynamics. In this paper, we test whether catastrophic forgetting can be reduced by evolving modular neural networks. Modularity intuitively should reduce learning interference between tasks by separating functionality into physically distinct modules in which learning can be selectively turned on or off. Modularity can further improve learning by having a reinforcement learning module separate from sensory processing modules, allowing learning to happen only in response to a positive or negative reward. In this paper, learning takes place via neuromodulation, which allows agents to selectively change the rate of learning for each neural connection based on environmental stimuli (e.g. to alter learning in specific locations based on the task at hand). To produce modularity, we evolve neural networks with a cost for neural connections. We show that this connection cost technique causes modularity, confirming a previous result, and that such sparsely connected, modular networks have higher overall performance because they learn new skills faster while retaining old skills more and because they have a separate reinforcement learning module. Our results suggest (1) that encouraging modularity in neural networks may help us overcome the long-standing barrier of networks that cannot learn new skills without forgetting old ones, and (2) that one benefit of the modularity ubiquitous in the brains of natural animals might be to

Neural modularity helps organisms evolve to learn new skills without forgetting old skills.

Directory of Open Access Journals (Sweden)

Kai Olav Ellefsen

2015-04-01

Full Text Available A long-standing goal in artificial intelligence is creating agents that can learn a variety of different skills for different problems. In the artificial intelligence subfield of neural networks, a barrier to that goal is that when agents learn a new skill they typically do so by losing previously acquired skills, a problem called catastrophic forgetting. That occurs because, to learn the new task, neural learning algorithms change connections that encode previously acquired skills. How networks are organized critically affects their learning dynamics. In this paper, we test whether catastrophic forgetting can be reduced by evolving modular neural networks. Modularity intuitively should reduce learning interference between tasks by separating functionality into physically distinct modules in which learning can be selectively turned on or off. Modularity can further improve learning by having a reinforcement learning module separate from sensory processing modules, allowing learning to happen only in response to a positive or negative reward. In this paper, learning takes place via neuromodulation, which allows agents to selectively change the rate of learning for each neural connection based on environmental stimuli (e.g. to alter learning in specific locations based on the task at hand. To produce modularity, we evolve neural networks with a cost for neural connections. We show that this connection cost technique causes modularity, confirming a previous result, and that such sparsely connected, modular networks have higher overall performance because they learn new skills faster while retaining old skills more and because they have a separate reinforcement learning module. Our results suggest (1 that encouraging modularity in neural networks may help us overcome the long-standing barrier of networks that cannot learn new skills without forgetting old ones, and (2 that one benefit of the modularity ubiquitous in the brains of natural animals

Neural Modularity Helps Organisms Evolve to Learn New Skills without Forgetting Old Skills

Science.gov (United States)

Ellefsen, Kai Olav; Mouret, Jean-Baptiste; Clune, Jeff

2015-01-01

A long-standing goal in artificial intelligence is creating agents that can learn a variety of different skills for different problems. In the artificial intelligence subfield of neural networks, a barrier to that goal is that when agents learn a new skill they typically do so by losing previously acquired skills, a problem called catastrophic forgetting. That occurs because, to learn the new task, neural learning algorithms change connections that encode previously acquired skills. How networks are organized critically affects their learning dynamics. In this paper, we test whether catastrophic forgetting can be reduced by evolving modular neural networks. Modularity intuitively should reduce learning interference between tasks by separating functionality into physically distinct modules in which learning can be selectively turned on or off. Modularity can further improve learning by having a reinforcement learning module separate from sensory processing modules, allowing learning to happen only in response to a positive or negative reward. In this paper, learning takes place via neuromodulation, which allows agents to selectively change the rate of learning for each neural connection based on environmental stimuli (e.g. to alter learning in specific locations based on the task at hand). To produce modularity, we evolve neural networks with a cost for neural connections. We show that this connection cost technique causes modularity, confirming a previous result, and that such sparsely connected, modular networks have higher overall performance because they learn new skills faster while retaining old skills more and because they have a separate reinforcement learning module. Our results suggest (1) that encouraging modularity in neural networks may help us overcome the long-standing barrier of networks that cannot learn new skills without forgetting old ones, and (2) that one benefit of the modularity ubiquitous in the brains of natural animals might be to

Numerical study of the effects of carbon felt electrode compression in all-vanadium redox flow batteries

International Nuclear Information System (INIS)

Oh, Kyeongmin; Won, Seongyeon; Ju, Hyunchul

2015-01-01

Highlights: • The effects of electrode compression on VRFB are examined. • The electronic conductivity is improved when the compression is increased. • The kinetic losses are similar regardless of the electrode compression level. • The vanadium distribution is more uniform within highly compressed electrode. - Abstract: The porous carbon felt electrode is one of the major components of all-vanadium redox flow batteries (VRFBs). These electrodes are necessarily compressed during stack assembly to prevent liquid electrolyte leakage and diminish the interfacial contact resistance among VRFB stack components. The porous structure and properties of carbon felt electrodes have a considerable influence on the electrochemical reactions, transport features, and cell performance. Thus, a numerical study was performed herein to investigate the effects of electrode compression on the charge and discharge behavior of VRFBs. A three-dimensional, transient VRFB model developed in a previous study was employed to simulate VRFBs under two degrees of electrode compression (10% vs. 20%). The effects of electrode compression were precisely evaluated by analysis of the solid/electrolyte potential profiles, transfer current density, and vanadium concentration distributions, as well as the overall charge and discharge performance. The model predictions highlight the beneficial impact of electrode compression; the electronic conductivity of the carbon felt electrode is the main parameter improved by electrode compression, leading to reduction in ohmic loss through the electrodes. In contrast, the kinetics of the redox reactions and transport of vanadium species are not significantly altered by the degree of electrode compression (10% to 20%). This study enhances the understanding of electrode compression effects and demonstrates that the present VRFB model is a valuable tool for determining the optimal design and compression of carbon felt electrodes in VRFBs.

Thermodynamic modelling of the extraction of nitrates of lanthanides by CMPO and by CMPO-like calixarene in concentrated nitric acid medium. Application in the optimization of the separation of lanthanides and actinides/lanthanides; Modelisation thermodynamique de l'extraction de nitrates de lanthanides par le CMPO et par un calixarene-CMPO en milieu acide nitrique concentre. Application a l'optimisation de la separation des lanthanides et des actinides/lanthanides

Energy Technology Data Exchange (ETDEWEB)

Belair, S

2003-07-01

The separation minor actinides / lanthanides in nitric acid medium is as one of problems of separative chemistry the most delicate within the framework of the processes allowing the recovery of long life radioelements present in the solutions of fission products. Previous studies showed that CMPO-substituted calix[4]arenes presents a better affinity for actinides than for lanthanides. To optimize the operating conditions of separation and to take into account the degree of non-ideality for the concentrated nitric solutions, we adopted a thermodynamic approach. The methodology taken to determine the number and the stoichiometry of the complexes formed in organic phase base on MIKULIN-SERGIEVSKII's model used through a software of data processing of experimental extraction isotherms. These tools are exploited at first on an extraction system engaging the CMPO, extractant reagent of actinides and lanthanides in concentrated nitric medium. The modelling of the system Ln(NO{sub 3}){sub 3}-HNO{sub 3}-H{sub 2}O/CMPO comes to confirm the results of several studies. At the same time, they allow to establish working hypotheses aiming at limiting the investigations of our researches towards the most stable complexes formed between lanthanides and CMPO-like calixarene to which the same method is then applied. An analytical expression of the selectivity of separation by the calixarene is established to determine the parameters and physico-chemical variables on which it depends. So, the ratio of the constants of extraction and the value of the activity of water of the system fixes the selectivity of separation of 2 elements. The exploitation of this relation allows to preview the influence of a variation of the concentration of nitric acid. Experiments of extraction confirm these forecasts and inform about the affinity of the calixarene with respect to lanthanides elements and to the americium. (author)

Analysis of vanadium slags, roasted and leached products. Determination of contents of total vanadium, chromium, sodium, and soluble vanadium

International Nuclear Information System (INIS)

Hasek, Z.

1975-01-01

Accurate, rapid and simple methods were elaborated of determining total vanadium, chromium, and sodium in vanadium slags, and in roasted and leached products in one sample batch. The analysis was conducted in a teflon vial using inorganic acids. A method od determining soluble vanadium in similar materials was also elaborated and verified. (B.S.)

Reticular Chemistry and Metal-Organic Frameworks: Design and Synthesis of Functional Materials for Clean Energy Applications

KAUST Repository

Alezi, Dalal

2017-01-01

Gaining control over the assembly of crystalline solid-state materials has been significantly advanced through the field of reticular chemistry and metal organic frameworks (MOFs). MOFs have emerged as a unique modular class of porous materials

Porous Organic Polymers for CO2 Capture

KAUST Repository

Teng, Baiyang

2013-05-01

Carbon dioxide (CO2) has long been regarded as the major greenhouse gas, which leads to numerous negative effects on global environment. The capture and separation of CO2 by selective adsorption using porous materials proves to be an effective way to reduce the emission of CO2 to atmosphere. Porous organic polymers (POPs) are promising candidates for this application due to their readily tunable textual properties and surface functionalities. The objective of this thesis work is to develop new POPs with high CO2 adsorption capacities and CO2/N2 selectivities for post-combustion effluent (e.g. flue gas) treatment. We will also exploit the correlation between the CO2 capture performance of POPs and their textual properties/functionalities. Chapters Two focuses on the study of a group of porous phenolic-aldehyde polymers (PPAPs) synthesized by a catalyst-free method, the CO2 capture capacities of these PPAPs exceed 2.0 mmol/g at 298 K and 1 bar, while keeping CO2/N2 selectivity of more than 30 at the same time. Chapter Three reports the gas adsorption results of different hyper-cross-linked polymers (HCPs), which indicate that heterocyclo aromatic monomers can greatly enhance polymers’ CO2/N2 selectivities, and the N-H bond is proved to the active CO2 adsorption center in the N-contained (e.g. pyrrole) HCPs, which possess the highest selectivities of more than 40 at 273 K when compared with other HCPs. Chapter Four emphasizes on the chemical modification of a new designed polymer of intrinsic microporosity (PIM) with high CO2/N2 selectivity (50 at 273 K), whose experimental repeatability and chemical stability prove excellent. In Chapter Five, we demonstrate an improvement of both CO2 capture capacity and CO2/N2 selectivity by doping alkali metal ions into azo-polymers, which leads a promising method to the design of new porous organic polymers.

Anatomy-Based Organization of Modular Robots

DEFF Research Database (Denmark)

Christensen, David Johan; Campbell, Jason

2008-01-01

This paper presents a novel biologically inspired hierarchical approach to organizing and controlling modular robots. The purpose of our approach is to decompose the complexity of assembling and commanding a functional robot made of numerous simple modules (thousands to millions) by introducing...... a hierarchy of structure and control. The robots we describe incorporate anatomically inspired parts such as muscles, bones and joints, and these parts in turn are assembled from modules. Each of those parts encapsulates one or more functions, e.g. a muscle can contract. Control of the robot can then be cast...... as a problem of controlling its anatomical parts rather than each discrete module. We show simulation results from experiments using gradient-based primitives to control parts of increasingly complex robots, including snake, crawler, cilia-surface, arm-joint-muscle and grasping robots. We conclude...

Modularization and Flexibilization.

Science.gov (United States)

Van Meel, R. M.

Publications in the fields of educational science, organization theory, and project management were analyzed to identify the possibilities that modularization offers to institutions of higher professional education and to obtain background information for use in developing a method for modularization in higher professional education. It was…

Mesoporous stilbene-based lanthanide metal organic frameworks: synthesis, photoluminescence and radioluminescence characteristics.

Science.gov (United States)

Mathis Ii, Stephan R; Golafale, Saki T; Bacsa, John; Steiner, Alexander; Ingram, Conrad W; Doty, F Patrick; Auden, Elizabeth; Hattar, Khalid

2017-01-03

Ultra large pore isostructural metal organic frameworks (MOFs) which exhibit both photoluminescence and scintillation properties, were synthesized from trans-4,4'-stilbenedicarboxylic acid (H 2 L) and trivalent lanthanide (Ln) metal salts under solvothermal conditions (Ln = Er 3+ (1) and Tm 3+ (2)). This new class of mesoporous materials is a non-interpenetrating network that features ultra-large diamond shaped pores of dimensions with approximate cross-sectional dimensions of 28 Å × 12 Å. The fully deprotonated ligand, L, is isolated and rigidified as it serves as the organic linker component of the MOF structure. Its low density unit cells possess asymmetric units with two crystallographically independent Ln 3+ ions in seven coordinate arrangements. A distinct feature of the structure is the bis-bidentate carboxylate groups. They serve as a ligand that coordinates two Ln(iii) ions while each L connects four Ln(iii) ions yielding an exceptionally large diamond-shaped rectangular network. The structure exhibits ligand-based photoluminescence with increased lifetime compared to free stilbene molecules on exposure to UV radiation, and also exhibits strong scintillation characteristics, comprising of both prompt and delayed radioluminescence features, on exposure to ionizing radiation.

Thermodynamic modelling of the extraction of nitrates of lanthanides by CMPO and by CMPO-like calixarene in concentrated nitric acid medium. Application in the optimization of the separation of lanthanides and actinides/lanthanides

International Nuclear Information System (INIS)

Belair, S.

2003-01-01

The separation minor actinides / lanthanides in nitric acid medium is as one of problems of separative chemistry the most delicate within the framework of the processes allowing the recovery of long life radioelements present in the solutions of fission products. Previous studies showed that CMPO-substituted calix[4]arenes presents a better affinity for actinides than for lanthanides. To optimize the operating conditions of separation and to take into account the degree of non-ideality for the concentrated nitric solutions, we adopted a thermodynamic approach. The methodology taken to determine the number and the stoichiometry of the complexes formed in organic phase base on MIKULIN-SERGIEVSKII's model used through a software of data processing of experimental extraction isotherms. These tools are exploited at first on an extraction system engaging the CMPO, extractant reagent of actinides and lanthanides in concentrated nitric medium. The modelling of the system Ln(NO 3 ) 3 -HNO 3 -H 2 O/CMPO comes to confirm the results of several studies. At the same time, they allow to establish working hypotheses aiming at limiting the investigations of our researches towards the most stable complexes formed between lanthanides and CMPO-like calixarene to which the same method is then applied. An analytical expression of the selectivity of separation by the calixarene is established to determine the parameters and physico-chemical variables on which it depends. So, the ratio of the constants of extraction and the value of the activity of water of the system fixes the selectivity of separation of 2 elements. The exploitation of this relation allows to preview the influence of a variation of the concentration of nitric acid. Experiments of extraction confirm these forecasts and inform about the affinity of the calixarene with respect to lanthanides elements and to the americium. (author)

Syntheses, structures and characterizations of three novel vanadium selenites with organically bonded copper/nickel complex

Energy Technology Data Exchange (ETDEWEB)

Qian, Cheng [College of Chemistry, Fuzhou University, Fuzhou, Fujian 350002 (China); State Key Laboratory of Structural Chemistry, Fujian Institute of Research on the Structure of Matter, Chinese Academy of Sciences, Fuzhou 350002 (China); Kong, Fang [State Key Laboratory of Structural Chemistry, Fujian Institute of Research on the Structure of Matter, Chinese Academy of Sciences, Fuzhou 350002 (China); Mao, Jiang-Gao, E-mail: mjg@fjirsm.ac.cn [College of Chemistry, Fuzhou University, Fuzhou, Fujian 350002 (China); State Key Laboratory of Structural Chemistry, Fujian Institute of Research on the Structure of Matter, Chinese Academy of Sciences, Fuzhou 350002 (China)

2016-06-15

A series of vanadium selenites covalently bonded with metal-organic complex, namely, Ni(2,2-bipy){sub 2}V{sub 2}O{sub 4}(SeO{sub 3}){sub 2} (1), Cu(2,2-bipy)V{sub 2}O{sub 4}(SeO{sub 3}){sub 2}·0.5H{sub 2}O (2) and Cu{sub 2}(2,2-bipy){sub 2}V{sub 5}O{sub 12}(SeO{sub 3}){sub 2} (3) (2,2-bipy=2,2-bipyridine) have been hydrothermally synthesized and structurally characterized. They exhibit three different structural dimensions, from 0D cluster, 1D chain to 2D layer. Compound 1 features a 0D {Ni(2,2-bipy)_2V_2O_4(SeO_3)_2}{sub 2} dimeric cluster composed of two {Ni(2,2-bipy)_2}{sup 2+} moieties connected by the {V_4O_8(SeO_3)_4}{sup 4-} cluster. Compound 2 shows a 1D {Cu(2,2-bipy)V_2O_4(SeO_3)_2}{sub n} chain in which the {Cu_2(2,2-bipy)_2}{sup 4+} moieties are bridged by the {V_4O_8(SeO_3)_4}{sup 4−} clusters. Compound 3 displays a 2D structure consisted of mixed valence vanadium selenites layers {V"I"VV"V_4Se"I"V_2O_1_8}{sub n}{sup 4−} and {Cu(2,2-bipy)}{sup 2+} complex moieties. The adjacent layers are further interconnected via π-π interactions between the 2,2-bipy ligands exhibiting an interesting 3D supramolecular architecture. Both compound 1 and 2 contain a new {V_4O_8(SeO_3)_4}{sup 4−} cluster and compound 3 exhibits the first 2D vanadate polyhedral layer in vanadium selenites/tellurites with organic moieties. - Graphical abstract: We got three new vanadium selenites with organically linked copper/nickel complex, namely, Ni(2,2-bipy){sub 2}V{sub 2}O{sub 4}(SeO{sub 3}){sub 2} (1), Cu(2,2-bipy)V{sub 2}O{sub 4}(SeO{sub 3}){sub 2}·0.5H{sub 2}O (2) and Cu{sub 2}(2,2-bipy){sub 2}V{sub 5}O{sub 12}(SeO{sub 3}){sub 2} (3) by hydrothermally syntheses. They display three different structural dimensions, from 0D cluster, to 1D chain and 2D layer. Display Omitted - Highlights: • Three new compounds display three different structural dimensions, from 0D cluster, to 1D chain and 2D layer. • The Tetranuclear {V_4O_8(SeO_3)_4}{sup 4−} cluster and the vanadate {V

Thermodynamics of oxygen in solid solution in vanadium and niobium--vanadium alloys

International Nuclear Information System (INIS)

Steckel, G.L.

1977-01-01

A thermodynamic study was made of the vanadium-oxygen and niobium-vanadium-oxygen systems utilizing the solid state galvanic cell technique. Investigations were made with a ThO 2 /Y 2 O 3 electrolyte over the temperature ranges 700 to 1200 0 C (973 to 1473 K) for the binary system and 650 to 1150 0 C (923 to 1423 K) for the ternary system. The activity of oxygen in vanadium obeys Henry's law for the temperatures of this investigation for concentrations up to 3.2 at. percent oxygen. For higher concentrations the activity coefficient shows positive deviations from Henry's law. The terminal solubility of oxygen in vanadium was determined. The activity of oxygen in Nb--V alloys obeys Henry's law for the temperatures of this study for oxygen concentrations less than approximately 2 at. percent. For certain Nb/V ratios Henry's law is obeyed for concentrations as high as 6.5 at. percent oxygen. First order entropy and enthalpy interaction coefficients have been determined to describe the effect on the oxygen activity of niobium additions to vanadium-rich alloys with dilute oxygen concentrations. Niobium causes relatively small decreases in the oxygen activity of V-rich alloys and increases the oxygen solubility limit. Vanadium additions to Nb-rich alloys also increases the oxygen solubility and causes substantial decreases in the dilute solution oxygen activities. The change in the thermodynamic properties when molecular oxygen dissolves in vanadium and niobium--vanadium alloys and the equilibrium oxygen pressure over the binary and ternary systems were also determined

Scandium, yttrium and the lanthanide metals

International Nuclear Information System (INIS)

Brown, Paul L.; Ekberg, Christian

2016-01-01

The hydroxide and oxide phases that exist for scandium(III) include scandium hydroxide, which likely has both amorphous and crystalline forms, ScOOH(s), and scandium oxide. This chapter presents the data selected for the stability constants of the polymeric hydrolysis species of scandium at zero ionic strength. The behaviour of yttrium, and the lanthanide metals, in the environment is largely dependent on their solution equilibria. Hydrolysis and other complexation reactions of yttrium and the lanthanide metals are important in the disposal of nuclear waste. The trivalent lanthanide metals include lanthanum(III) through lutetium(III). A number of studies have reported a tetrad effect for the geochemical behaviour of the lanthanide series, including stability constants and distribution coefficients. The solubility of many of the lanthanide hydroxide phases has been studied at fixed ionic strength. In studying the hydrolysis of cerium(IV), a number of studies have utilised oxidation-reduction reactions in determining the relevant stability constants.

An extraction process to recover vanadium from low-grade vanadium-bearing titanomagnetite

Energy Technology Data Exchange (ETDEWEB)

Chen, Desheng; Zhao, Hongxin; Hu, Guoping [National Engineering Laboratory for Hydrometallurgical Cleaner Production Technology, Beijing 100190 (China); Key Laboratory of Green Process and Engineering, Institute of Process Engineering, Chinese Academy of Sciences, Beijing 100190 (China); Qi, Tao, E-mail: tqgreen@ipe.ac.cn [National Engineering Laboratory for Hydrometallurgical Cleaner Production Technology, Beijing 100190 (China); Key Laboratory of Green Process and Engineering, Institute of Process Engineering, Chinese Academy of Sciences, Beijing 100190 (China); Yu, Hongdong; Zhang, Guozhi [National Engineering Laboratory for Hydrometallurgical Cleaner Production Technology, Beijing 100190 (China); Key Laboratory of Green Process and Engineering, Institute of Process Engineering, Chinese Academy of Sciences, Beijing 100190 (China); Wang, Lina, E-mail: linawang@ipe.ac.cn [National Engineering Laboratory for Hydrometallurgical Cleaner Production Technology, Beijing 100190 (China); Key Laboratory of Green Process and Engineering, Institute of Process Engineering, Chinese Academy of Sciences, Beijing 100190 (China); Wang, Weijing [National Engineering Laboratory for Hydrometallurgical Cleaner Production Technology, Beijing 100190 (China); Key Laboratory of Green Process and Engineering, Institute of Process Engineering, Chinese Academy of Sciences, Beijing 100190 (China)

2015-08-30

Highlights: • The leaching solution contains high concentration of acid, iron, impurities and lower vanadium. • 99.4% of vanadium and 4.2% of iron were extracted by three-stage extraction process. • 99.6% of vanadium and 5.4% of iron were stripped by three-stage stripping process. • The stripping solution contains 40.16 g/L V{sub 2}O{sub 5}, 0.691 g/L Fe, 0.007 g/L TiO{sub 2} and 0.247 g/L CaO. • The vanadium product of V{sub 2}O{sub 5} with purity of 99.12%, 0.026% Fe and well crystallized. - Abstract: An extraction process to recover vanadium from low-grade vanadium-bearing titanomagnetite was developed. In this study, a mixed solvent system of di(2-ethylhexyl) phosphate (D2EHPA) and tri-n-butyl phosphate (TBP) diluted with kerosene was used for the selective extraction of vanadium from a hydrochloric acid leaching solution that contained low vanadium concentration with high concentrations of iron and impurities of Ca, Mg, and Al. In the extraction process, the initial solution pH and the phase ratio had considerable functions in the extraction of vanadium from the hydrochloric acid leaching solution. Under optimal extraction conditions (i.e., 30–40 °C for 10 min, 1:3 phase ratio (O/A), 20% D2EHPA concentration (v/v), and 0–0.8 initial solution pH), 99.4% vanadium and only 4.2% iron were extracted by the three-stage counter-current extraction process. In the stripping process with H{sub 2}SO{sub 4} as the stripping agent and under optimal stripping conditions (i.e., 20% H{sub 2}SO{sub 4} concentration, 5:1 phase ratio (O/A), 20 min stripping time, and 40 °C stripping temperature), 99.6% vanadium and only 5.4% iron were stripped by the three-stage counter-current stripping process. The stripping solution contained 40.16 g/L V{sub 2}O{sub 5}, 0.691g/L Fe, 0.007 g/L TiO{sub 2}, 0.006 g/L SiO{sub 2} and 0.247 g/L CaO. A V{sub 2}O{sub 5} product with a purity of 99.12% V{sub 2}O{sub 5} and only 0.026% Fe was obtained after the oxidation, precipitation

Determination of vanadium in Syrian commercial and raffinate phosphoric acid

International Nuclear Information System (INIS)

Al-Merey, R.

2002-04-01

This study presents two methods for vanadium determination in Syrian commercial phosphoric acid. The vanadium (V) in the oxidized commercial phosphoric acid by ammonium persulfate solution is extracted from 5-M hydrochloride acid medium using N-benzoyl-N-phenyl hydroxyl amine (BPHA) in chloroform as an extracting solution. The first method, the extract vanadium as VOL 2 Cl is changed to V 2 O 3 L 4 complex by the addition of benzimidazole in 1-butanol to the violet organic layer. The absorbance is then measured at 440 nm (the molar absorptivity was found to be 3865 M -1 cm -1 ), where Beer law is applicable up to 36-μg ml -1 . the accuracy, precision and detection limit were found to be 3.7%, 77 ppb and 37 ppb, respectively. the second method, the organic layer is heated to evaporate chloroform, the residue is digested using 20% ammonium persulfate and 2-M sulfuric acid solutions. The vanadium concentration is measured spectrophotometrically by oxidizing gallic acid with persulfate (S 2 O 8 2- ) anion in phosphoric acid medium, where the vanadium (V) acts as a catalyst in the oxidation reaction. This method has a high sensitivity (∼10 -12 ) with accuracy and precision 5% and 0.621 ppb, respectively. Also Beer law at λ m ax=415 nm (ε=∼2 x 10 6 M -1 ) is applicable in the range 2.58-33.3 ppb. (author)

Separation of lanthanides through hydroxyapatite

International Nuclear Information System (INIS)

Garcia M, F.G.

2006-01-01

With the objective of obtaining from an independent way to each one of the lanthanides 151 Pm, 161 Tb, 166 Ho and 177 Lu free of carrier and with high specific activities starting from the indirect irradiation via, it intends in this work to determine the viability of separation of the couples Nd/Pm, Dy/Ho, Gd/Tb and Yb/Lu, by means of ion exchange column chromatography, using hydroxyapatite (HAp) and fluorite like absorbent material in complexing media. It is important to mention that have registered separation studies among lanthanides of the heavy group with those of the slight group, using the same mass and, in comparison with this work, quantities different from the father were used and of the son, also, that the separation studies were carried out among neighboring lanthanides. In this investigation, it was determined the effect that its have the complexing media: KSCN, sodium tartrate, sodium citrate, EDTA and aluminon, their pH and concentration, in the adsorption of the lanthanides in both minerals, in order to determine the chromatographic conditions for separation of the couples Nd/Pm, Dy/Ho, Gd/Tb and Yb/Lu. The work consists of five chapters, in the first one they are presented a theoretical introduction of the characteristics more important of the lanthanides, the hydroxyapatite and the fluorite; in the second, it is deepened in the ion exchange, as well as the two techniques (XRD and High Vacuum Electron Microscopy) to make the characterization of LnCI 3 (Ln = Nd, Gd, Dy or Yb) synthesized. The third chapter, it describes the methodology continued in our experimental work; in the room, its are presented the obtained results of the static and dynamic method to determine the viability of separation of neighboring lanthanides; and finally, the five chapter shows the conclusions. In this study, it is concludes that the separation among neighboring lanthanides cannot be carried out in the minerals and used media; because practically these lanthanides

Potential of hybrid functionalized meso-porous materials for the separation and immobilization of radionuclides

International Nuclear Information System (INIS)

Luca, V.

2013-01-01

Functionalized meso-porous materials are a class of hybrid organic-inorganic material in which a meso-porous metal oxide framework is functionalized with multifunctional organic molecules. These molecules may contain one or more anchor groups that form strong bonds to the pore surfaces of the metal oxide framework and free functional groups that can impart and or modify the functionality of the material such as for binding metal ions in solution. Such materials have been extensively studied over the past decade and are of particular interest in absorption applications because of the tremendous versatility in choosing the composition and architecture of the metal oxide framework and the nature of the functional organic molecule as well as the efficient mass transfer that can occur through a well-designed hierarchically porous network. A sorbent for nuclear applications would have to be highly selective for particular radio nuclides, it would need to be hydrolytically and radiolytically stable, and it would have to possess reasonable capacity and fast kinetics. The sorbent would also have to be available in a form suitable for use in a column. Finally, it would also be desirable if once saturated with radio nuclides, the sorbent could be recycled or converted directly into a ceramic or glass waste form suitable for direct repository disposal or even converted directly into a material that could be used as a transmutation target. Such a cradle-to- grave strategy could have many benefits in so far as process efficiency and the generation of secondary wastes are concerned.This paper will provide an overview of work done on all of the above mentioned aspects of the development of functionalized meso-porous adsorbent materials for the selective separation of lanthanides and actinides and discuss the prospects for future implementation of a cradle-to-grave strategy with such materials. (author)

Luminescent hybrid lanthanide sulfates and lanthanide sulfonate-carboxylates with 1,10-phenanthroline involving in-situ oxidation of 2-mercaptonbenzoic acid

International Nuclear Information System (INIS)

Zhong, Jie-Cen; Wan, Fang; Sun, Yan-Qiong; Chen, Yi-Ping

2015-01-01

A series of lanthanide sulfates and lanthanide sulfonate-carboxylates, [Ln 2 (phen) 2 (SO 4 ) 3 (H 2 O) 2 ] n (I:Ln=Nd(1a), Sm(1b), Eu(1c), phen=1,10-phenanthroline) and [Ln(phen)(2-SBA)(BZA)] n (II: Ln=Sm(2a), Eu(2b), Dy(2c), 2-SBA=2-sulfobenzoate, BZA=benzoate) have been hydrothermally synthesized from lanthanide oxide, 2-mercaptonbenzoic acid with phen as auxiliary ligand and characterized by single-crystal X-ray diffraction, elemental analyses, IR spectra, TG analyses and luminescence spectroscopy. Interestingly, SO 4 2− anions in I came from the in situ deep oxidation of thiol groups of 2-mercaptonbenzoic acid while 2-sulfobenzoate and benzoate ligands in II from the middle oxidation and desulfuration reactions of 2-mercaptonbenzoic acid. Compounds I are organic–inorganic hybrid lanthanide sulfates, which have rare one-dimensional column-like structures. Complexes II are binuclear lanthanide sulfonate-carboxylates with 2-sulfobenzoate and benzoate as bridges and 1,10-phenanthroline as terminal. Photoluminescence studies reveal that complexes I and II exhibit strong lanthanide characteristic emission bands in the solid state at room temperature. - Graphical abstract: Lanthanide sulfates and lanthanide sulfonate-carboxylates have been hydrothermally synthesized. Interestingly, sulfate anions, 2-sulfobenzoate and benzoate ligands came from the in situ oxidation and desulfuration reactions of 2-mercaptonbenzoic acid. - Highlights: • In situ oxidation and desulfuration reactions of 2-mercaptonbenzoic acid. • The organic–inorganic hybrid lanthanide sulfates with one-dimensional column-like structure. • The dinuclear lanthanide sulfonate-carboxylates. • The emission spectra exhibit the characteristic transition of 5 D 0 → 7 F J (J=0–4) of the Eu(III)

Lanthanide contraction effect on crystal structures of lanthanide coordination polymers with cyclohexanocucurbit[6]uril ligand

Energy Technology Data Exchange (ETDEWEB)

Zheng, Li-Mei [College of Chemistry and Chemical Engineering, Henan University of Technology, Zhengzhou 450001 (China); Liu, Jing-Xin, E-mail: jxliu411@ahut.edu.cn [College of Chemistry and Chemical Engineering, Anhui University of Technology, Maanshan 243002 (China)

2017-01-15

A series of compounds based on the macrocyclic ligand cyclohexanocucurbit[6]uril (Cy6Q[6]) with formulas (Ln(H{sub 2}O){sub 6}Cy6Q[6])·2(CdCl{sub 4})·H{sub 3}O·xH{sub 2}O [isomorphous with Ln=La (1), Ce (2), Pr (3) and Nd (4), x=11 (1), 11 (2), 10 (3) and 11 (4)], (Sm(H{sub 2}O){sub 5}Cy6Q[6])·2(CdCl{sub 4})·H{sub 3}O·10H{sub 2}O (5) and (Ln(H{sub 2}O){sub 5}(NO{sub 3})@Cy6Q[6])·2(CdCl{sub 4})·2H{sub 3}O·xH{sub 2}O [isomorphous with Ln=Gd (6), Tb (7) and Dy (8), x=8 (6), 6 (7) and 6 (8)], have been successfully synthesized by the self-assembly of Cy6Q[6] with the corresponding lanthanide nitrate under hydrochloric acid aqueous solution in the presence of CdCl{sub 2}. Single-crystal X-ray diffraction analyses revealed that compounds 1–8 all crystallize in monoclinic space group P2{sub 1}/c, and display 1D coordination polymer structures. The lanthanide contraction effect on the structures of 1–8 has also been investigated and discussed in detail. In contrast, the reaction of Cy6Q[6] with the Ho(NO){sub 3}, Tm(NO){sub 3}, Yb(NO){sub 3} under the same conditions resulted in the compounds 9–11 with formulas Cy6Q[6]·2(CdCl{sub 4})·2H{sub 3}O·xH{sub 2}O [isomorphous with x=10 (9), 10 (10), and 9 (11)], in which no lanthanide cations are observed. The structural difference of these compounds indicates that the Cy6Q[6] may be used in the separation of lanthanide cations. - Graphical abstract: The reaction of cyclohexanocucurbit[6]uril with lanthanide ions (La{sup 3+}, Ce{sup 3+}, Pr{sup 3+}, Nd{sup 3+}, Sm{sup 3+}, Gd{sup 3+}, Tb{sup 3+}, Dy{sup 3+}, Ho{sup 3+}, Tm{sup 3+} and Yb{sup 3+}) under hydrochloric acid in the presence of CdCl{sub 2} resulted in eleven compounds, which demonstrate interesting lanthanide contraction effect and provide a means of separating lanthanide ions. - Highlights: • Eleven compounds of the Ln{sup 3+} with the Cy6Q[6] were synthesized and described. • Compounds 1-8 demonstrate interesting lanthanide contraction effect. �

Vanadium in South Africa

International Nuclear Information System (INIS)

Rohrman, B.

1985-01-01

This paper deals briefly with the history of vanadium and its uses, price movement, and world resources. It then describes the titanomagnetite ore of the Bushveld Complex, and the production of vanadium from this ore at Highveld Steel and Vanadium Corporation Limited, giving details of the various processes used, including the roast-leach, rotary-kiln, electric-smelting, shaking-ladle, and basic-oxygen-furnace operations. The paper concludes with a very brief account of the treatment of Highveld slags in Europe for the production of vanadium pentoxide and ferrovanadium

Comparative modular analysis of gene expression in vertebrate organs

Directory of Open Access Journals (Sweden)

Piasecka Barbara

2012-03-01

Full Text Available Abstract Background The degree of conservation of gene expression between homologous organs largely remains an open question. Several recent studies reported some evidence in favor of such conservation. Most studies compute organs' similarity across all orthologous genes, whereas the expression level of many genes are not informative about organ specificity. Results Here, we use a modularization algorithm to overcome this limitation through the identification of inter-species co-modules of organs and genes. We identify such co-modules using mouse and human microarray expression data. They are functionally coherent both in terms of genes and of organs from both organisms. We show that a large proportion of genes belonging to the same co-module are orthologous between mouse and human. Moreover, their zebrafish orthologs also tend to be expressed in the corresponding homologous organs. Notable exceptions to the general pattern of conservation are the testis and the olfactory bulb. Interestingly, some co-modules consist of single organs, while others combine several functionally related organs. For instance, amygdala, cerebral cortex, hypothalamus and spinal cord form a clearly discernible unit of expression, both in mouse and human. Conclusions Our study provides a new framework for comparative analysis which will be applicable also to other sets of large-scale phenotypic data collected across different species.

Comparative modular analysis of gene expression in vertebrate organs.

Science.gov (United States)

Piasecka, Barbara; Kutalik, Zoltán; Roux, Julien; Bergmann, Sven; Robinson-Rechavi, Marc

2012-03-29

The degree of conservation of gene expression between homologous organs largely remains an open question. Several recent studies reported some evidence in favor of such conservation. Most studies compute organs' similarity across all orthologous genes, whereas the expression level of many genes are not informative about organ specificity. Here, we use a modularization algorithm to overcome this limitation through the identification of inter-species co-modules of organs and genes. We identify such co-modules using mouse and human microarray expression data. They are functionally coherent both in terms of genes and of organs from both organisms. We show that a large proportion of genes belonging to the same co-module are orthologous between mouse and human. Moreover, their zebrafish orthologs also tend to be expressed in the corresponding homologous organs. Notable exceptions to the general pattern of conservation are the testis and the olfactory bulb. Interestingly, some co-modules consist of single organs, while others combine several functionally related organs. For instance, amygdala, cerebral cortex, hypothalamus and spinal cord form a clearly discernible unit of expression, both in mouse and human. Our study provides a new framework for comparative analysis which will be applicable also to other sets of large-scale phenotypic data collected across different species.

Low-voltage organic field-effect transistors based on novel high-κ organometallic lanthanide complex for gate insulating materials

Directory of Open Access Journals (Sweden)

Qi Liu

2014-08-01

Full Text Available A novel high-κ organometallic lanthanide complex, Eu(tta3L (tta=2-thenoyltrifluoroacetonate, L = 4,5-pinene bipyridine, is used as gate insulating material to fabricate low-voltage pentacene field-effect transistors (FETs. The optimized gate insulator exhibits the excellent properties such as low leakage current density, low surface roughness, and high dielectric constant. When operated under a low voltage of −5 V, the pentacene FET devices show the attractive electrical performance, e.g. carrier mobility (μFET of 0.17 cm2 V−1 s−1, threshold voltage (Vth of −0.9 V, on/off current ratio of 5 × 103, and subthreshold slope (SS of 1.0 V dec−1, which is much better than that of devices obtained on conventional 300 nm SiO2 substrate (0.13 cm2 V−1 s−1, −7.3 V and 3.1 V dec−1 for μFET, Vth and SS value when operated at −30 V. These results indicate that this kind of high-κ organometallic lanthanide complex becomes a promising candidate as gate insulator for low-voltage organic FETs.

Separation/preconcentration and determination of vanadium with dispersive liquid-liquid microextraction based on solidification of floating organic drop (DLLME-SFO) and electrothermal atomic absorption spectrometry.

Science.gov (United States)

Asadollahi, Tahereh; Dadfarnia, Shayessteh; Shabani, Ali Mohammad Haji

2010-06-30

A novel dispersive liquid-liquid microextraction based on solidification of floating organic drop (DLLME-SFO) for separation/preconcentration of ultra trace amount of vanadium and its determination with the electrothermal atomic absorption spectrometry (ETAAS) was developed. The DLLME-SFO behavior of vanadium (V) using N-benzoyl-N-phenylhydroxylamine (BPHA) as complexing agent was systematically investigated. The factors influencing the complex formation and extraction by DLLME-SFO method were optimized. Under the optimized conditions: 100 microL, 200 microL and 25 mL of extraction solvent (1-undecanol), disperser solvent (acetone) and sample volume, respectively, an enrichment factor of 184, a detection limit (based on 3S(b)/m) of 7 ng L(-1) and a relative standard deviation of 4.6% (at 500 ng L(-1)) were obtained. The calibration graph using the preconcentration system for vanadium was linear from 20 to 1000 ng L(-1) with a correlation coefficient of 0.9996. The method was successfully applied for the determination of vanadium in water and parsley. Copyright 2010 Elsevier B.V. All rights reserved.

Lanthanide complexation in aqueous solutions

International Nuclear Information System (INIS)

Choppin, G.R.

1984-01-01

The lanthanide elements form an extended series of cations with the same charge, slightly varying radii and useful magnetic and spectroscopic properties. Their use in technology is growing rapidly as their properties are more fully explored. The lanthanides also offer scientists valuable and often unique probes for investigating a variety of chemical and physical phenomena. This review has attempted to call attention to these latter uses without trying to provide a thorough discussion of all the relevant literature. Hopefully, awareness of the more interesting facets of present studies of lanthanide complexes in aqueous solution will spur even more advances in the use of these elements. (Auth.)

Melting technique for vanadium containing steels

Energy Technology Data Exchange (ETDEWEB)

Grishanov, M P; Gutovskij, I B; Vakhrushev, A S

1980-04-28

To descrease cost price of high-quality vanadium steels a method of their melting in open-hearth furnaces with acid lining using slag-metal fraction of vanadium, which is loaded in the content of 2.1-4.7% of melting mass, is suggested. Introduction of slag-metal fraction of vanadium ensures the formation of slag with composition that guarantees the necessary content of vanadium in steel and does not require introduction of expensive vanadium-containing ferroalloys into the melt.

Photoluminescent lanthanide-organic bilayer networks with 2,3-pyrazinedicarboxylate and oxalate.

Science.gov (United States)

Soares-Santos, Paula C R; Cunha-Silva, Luís; Paz, Filipe A Almeida; Ferreira, Rute A S; Rocha, João; Carlos, Luís D; Nogueira, Helena I S

2010-04-05

The hydrothermal reaction between lanthanide nitrates and 2,3-pyrazinedicarboxylic acid led to a new series of two-dimensional (2D) lanthanide-organic frameworks: [Ln(2)(2,3-pzdc)(2)(ox)(H(2)O)(2)](n) [where 2,3-pzdc(2-) = 2,3-pyrazinedicarboxylate, ox(2-) = oxalate, and Ln(III) = Ce, Nd, Sm, Eu, Gd, Tb, or Er]. The structural details of these materials were determined by single-crystal X-ray diffraction (for Ce(3+) and Nd(3+)) that revealed the formation of a layered structure. Cationic monolayers of {(infinity)(2)[Ln(2,3-pzdc)(H(2)O)](+)} are interconnected via the ox(2-) ligand leading to the formation of neutral (infinity)(2)[Ln(2)(2,3-pzdc)(2)(ox)(H(2)O)(2)] bilayer networks; structural cohesion of the crystalline packing is reinforced by the presence of highly directional O-H...O hydrogen bonds between adjacent bilayers. Under the employed hydrothermal conditions 2,3-pyrazinedicarboxylic acid can be decomposed into ox(2-) and 2-pyrazinecarboxylate (2-pzc(-)), as unequivocally proved by the isolation of the discrete complex [Tb(2)(2-pzc)(4)(ox)(H(2)O)(6)].10H(2)O. Single-crystal X-ray diffraction of this latter complex revealed its co-crystallization with an unprecedented (H(2)O)(16) water cluster. Photoluminescence measurements were performed for the Nd(3+), Sm(3+), Eu(3+), and Tb(3+) compounds which show, under UV excitation at room temperature, the Ln(3+) characteristic intra-4f(N) emission peaks. The energy level of the triplet states of 2,3-pyrazinedicarboxylic acid (18939 cm(-1)) and oxalic acid (24570 cm(-1)) was determined from the 12 K emission spectrum of the Gd(3+) compound. The (5)D(0) and (5)D(4) lifetime values (0.333 +/- 0.006 and 0.577 +/- 0.017 ms) and the absolute emission quantum yields (0.13 +/- 0.01 and 0.05 +/- 0.01) were determined for the Eu(3+) and Tb(3+) compounds, respectively. For the Eu(3+) compound the energy transfer efficiency arising from the ligands' excited states was estimated (0.93 +/- 0.01).

Selective chelation and extraction of lanthanides and actinides with supercritical fluids

International Nuclear Information System (INIS)

Brauer, R.D.; Carleson, T.E.; Harrington, J.D.; Jean, F.; Jiang, H.; Lin, Y.; Wai, C.M.

1994-01-01

This report is made up of three independent papers: (1) Supercritical Fluid Extraction of Thorium and Uranium with Fluorinated Beta-Diketones and Tributyl Phosphate, (2) Supercritical Fluid Extraction of Lanthanides with Beta-Diketones and Mixed Ligands, and (3) A Group Contribution Method for Predicting the Solubility of Solid Organic Compounds in Supercritical Carbon Dioxide. Experimental data are presented demonstrating the successful extraction of thorium and uranium using fluorinated beta-diketones to form stable complexes that are extracted with supercritical carbon dioxide. The conditions for extracting the lanthanide ions from liquid and solid materials using supercritical carbon dioxide are presented. In addition, the Peng-Robison equation of state and thermodynamic equilibrium are used to predict the solubilities of organic solids in supercritical carbon dioxide from the sublimation pressure, critical properties, and a centric factor of the solid of interest

Aerogels of 1D Coordination Polymers: From a Non-Porous Metal-Organic Crystal Structure to a Highly Porous Material

Directory of Open Access Journals (Sweden)

Adrián Angulo-Ibáñez

2016-01-01

Full Text Available The processing of an originally non-porous 1D coordination polymer as monolithic gel, xerogel and aerogel is reported as an alternative method to obtain novel metal-organic porous materials, conceptually different to conventional crystalline porous coordination polymer (PCPs or metal-organic frameworks (MOFs. Although the work herein reported is focused upon a particular kind of coordination polymer ([M(μ-ox(4-apy2]n, M: Co(II, Ni(II, the results are of interest in the field of porous materials and of MOFs, as the employed synthetic approach implies that any coordination polymer could be processable as a mesoporous material. The polymerization conditions were fixed to obtain stiff gels at the synthesis stage. Gels were dried at ambient pressure and at supercritical conditions to render well shaped monolithic xerogels and aerogels, respectively. The monolithic shape of the synthesis product is another remarkable result, as it does not require a post-processing or the use of additives or binders. The aerogels of the 1D coordination polymers are featured by exhibiting high pore volumes and diameters ranging in the mesoporous/macroporous regions which endow to these materials the ability to deal with large-sized molecules. The aerogel monoliths present markedly low densities (0.082–0.311 g·cm−3, an aspect of interest for applications that persecute light materials.

VANADIUM ALLOYS

Science.gov (United States)

Smith, K.F.; Van Thyne, R.J.

1959-05-12

This patent deals with vanadium based ternary alloys useful as fuel element jackets. According to the invention the ternary vanadium alloys, prepared in an arc furnace, contain from 2.5 to 15% by weight titanium and from 0.5 to 10% by weight niobium. Characteristics of these alloys are good thermal conductivity, low neutron capture cross section, good corrosion resistance, good welding and fabricating properties, low expansion coefficient, and high strength.

Patents on Membranes Based on Non-Fluorinated Polymers for Vanadium Redox Flow Batteries.

Science.gov (United States)

Choi, So-Won; Kim, Tae-Ho; Cha, Sang-Ho

2017-07-10

Vanadium redox flow batteries (VRFBs) have received considerable attention as large-scale electrochemical energy storage systems. In particular, VRFBs offer a higher power and energy density than other RFBs and mitigate undesirable performance fading, such as inevitable ion crossover, because of the unique advantage that only the vanadium ion is employed as the active species in the two electrolytes. The key constituent of VRFBs is a separator to conduct protons and prevent cross-mixing of the positive and negative electrolytes. For this purpose, ion exchange membranes like sulfonated polymer membranes can be used. Although this type of membrane does not have ion exchange groups, it can achieve an ion exchange capacity by the formation of pores. This review highlights the patents on the preparation of non-fluorinated membranes (sulfonated aromatic polymer membranes and porous membranes) as alternatives to high-cost perfluorinated polymers and their VRFB performance. Copyright© Bentham Science Publishers; For any queries, please email at epub@benthamscience.org.

Modular organization of functional network connectivity in healthy controls and patients with schizophrenia during the resting state

Directory of Open Access Journals (Sweden)

Qingbao eYu

2012-01-01

Full Text Available Neuroimaging studies have shown that functional brain networks composed from select regions of interest (ROIs have a modular community structure. However, the organization of functional network connectivity (FNC, comprising a purely data-driven network built from spatially independent brain components, is not yet clear. The aim of this study is to explore the modular organization of FNC in both healthy controls (HCs and patients with schizophrenia (SZs. Resting state functional magnetic resonance imaging (R-fMRI data of HCs and SZs were decomposed into independent components (ICs by group independent component analysis (ICA. Then weighted brain networks (in which nodes are brain components were built based on correlations among of ICA time courses. Clustering coefficients and connectivity strength of the networks were computed. A dynamic branch cutting algorithm was used to identify modules of the FNC in HCs and SZs. Results show stronger connectivity strength and higher clustering coefficient in HCs with more and smaller modules in SZs. In addition, HCs and SZs had some different hubs. Our findings demonstrate altered modular architecture of the FNC in schizophrenia and provide insights into abnormal topological organization of intrinsic brain networks in this mental illness.

Porous-Shell Vanadium Nitride Nanobubbles with Ultrahigh Areal Sulfur Loading for High-Capacity and Long-Life Lithium-Sulfur Batteries.

Science.gov (United States)

Ma, Lianbo; Yuan, Hao; Zhang, Wenjun; Zhu, Guoyin; Wang, Yanrong; Hu, Yi; Zhao, Peiyang; Chen, Renpeng; Chen, Tao; Liu, Jie; Hu, Zheng; Jin, Zhong

2017-12-13

Lithium-sulfur (Li-S) batteries hold great promise for the applications of high energy density storage. However, the performances of Li-S batteries are restricted by the low electrical conductivity of sulfur and shuttle effect of intermediate polysulfides. Moreover, the areal loading weights of sulfur in previous studies are usually low (around 1-3 mg cm -2 ) and thus cannot fulfill the requirement for practical deployment. Herein, we report that porous-shell vanadium nitride nanobubbles (VN-NBs) can serve as an efficient sulfur host in Li-S batteries, exhibiting remarkable electrochemical performances even with ultrahigh areal sulfur loading weights (5.4-6.8 mg cm -2 ). The large inner space of VN-NBs can afford a high sulfur content and accommodate the volume expansion, and the high electrical conductivity of VN-NBs ensures the effective utilization and fast redox kinetics of polysulfides. Moreover, VN-NBs present strong chemical affinity/adsorption with polysulfides and thus can efficiently suppress the shuttle effect via both capillary confinement and chemical binding, and promote the fast conversion of polysulfides. Benefiting from the above merits, the Li-S batteries based on sulfur-filled VN-NBs cathodes with 5.4 mg cm -2 sulfur exhibit impressively high areal/specific capacity (5.81 mAh cm -2 ), superior rate capability (632 mAh g -1 at 5.0 C), and long cycling stability.

Luminescent lanthanide coordination polymers

Energy Technology Data Exchange (ETDEWEB)

Ma, L.; Evans, O.R.; Foxman, B.M.; Lin, W.

1999-12-13

One-dimensional lanthanide coordination polymers with the formula Ln(isonicotinate){sub 3}(H{sub 2}O){sub 2} (Ln = Ce, Pr, Nd, Sm, Eu, Tb; 1a-f) were synthesized by treating nitrate or perchlorate salts of Ln(III) with 4-pyridinecarboxaldehyde under hydro(solvo)thermal conditions. Single-crystal and powder X-ray diffraction studies indicate that these lanthanide coordination polymers adopt two different structures. While Ce(III), Pr(III), and Nd(III) complexes adopt a chain structure with alternating Ln-(carboxylate){sub 2}-Ln and Ln-(carboxylate){sub 4}-Ln linkages, Sm(III), Eu(III), and Tb(III) complexes have a doubly carboxylate-bridged infinite-chain structure with one chelating carboxylate group on each metal center. In both structures, the lanthanide centers also bind to two water molecules to yield an eight-coordinate, square antiprismatic geometry. The pyridine nitrogen atoms of the isonicotinate groups do not coordinate to the metal centers in these lanthanide(III) complexes; instead, they direct the formation of Ln(III) coordination polymers via hydrogen bonding with coordinated water molecules. Photoluminescence measurements show that Tb(isonicotinate){sub 3}(H{sub 2}O){sub 2} is highly emissive at room temperature with a quantum yield of {approximately}90%. These results indicate that highly luminescent lanthanide coordination polymers can be assembled using a combination of coordination and hydrogen bonds. Crystal data for 1a: monoclinic space group P2{sub 1}/c, a = 9.712(2) {angstrom}, b = 19.833(4) {angstrom}, c = 11.616(2) {angstrom}, {beta} = 111.89(3){degree}, Z = 4. Crystal data for 1f: monoclinic space group C2/c, a = 20.253(4) {angstrom}, b = 11.584(2) {angstrom}, c = 9.839(2) {angstrom}, {beta} = 115.64(3){degree}, Z = 8.

Sol-gel growth of vanadium dioxide

International Nuclear Information System (INIS)

Speck, K.R.

1990-01-01

This thesis examines the chemical reactivity of vanadium (IV) tetrakis(t-butoxide) as a precursor for the sol-gel synthesis of vanadium dioxide. Hydrolysis and condensation of the alkoxide was studied by FTIR spectroscopy. Chemical modification of the vanadium tetraalkoxide by alcohol interchange was studied using 51 V NMR and FTIR. Vanadium dioxide thin films and powders were made from vanadium tetrakis(t-butoxide) by standard sol-gel techniques. Post-deposition heating under nitrogen was necessary to transform amorphous gels into vanadium dioxide. Crystallization of films and powders was studied by FTIR, DSC, TGA, and XRD. Gel-derived vanadium dioxide films undergo a reversible semiconductor-to-metal phase transition near 68C, exhibiting characteristic resistive and spectral changes. The electrical resistance decreased by two to three orders of magnitude and the infrared transmission sharply dropped as the material was cycled through this thermally induced phase transition. The sol-gel method was also used to make doped vanadium dioxide films. Films were doped with tungsten and molybdenum ions to effectively lower the temperature at which the transition occurs

Defining Modules, Modularity and Modularization

DEFF Research Database (Denmark)

Miller, Thomas Dedenroth; Pedersen, Per Erik Elgård

The paper describes the evolution of the concept of modularity in a historical perspective. The main reasons for modularity are: create variety, utilize similarities, and reduce complexity. The paper defines the terms: Module, modularity, and modularization.......The paper describes the evolution of the concept of modularity in a historical perspective. The main reasons for modularity are: create variety, utilize similarities, and reduce complexity. The paper defines the terms: Module, modularity, and modularization....

Modular networks with hierarchical organization

Indian Academy of Sciences (India)

Several networks occurring in real life have modular structures that are arranged in a hierarchical fashion. In this paper, we have proposed a model for such networks, using a stochastic generation method. Using this model we show that, the scaling relation between the clustering and degree of the nodes is not a necessary ...

Spectral studies of Lanthanide interactions with membrane surfaces

Energy Technology Data Exchange (ETDEWEB)

Karukstis, K.K.; Kao, M.Y.; Savin, D.A.; Bittker, R.A.; Kaphengst, K.J.; Emetarom, C.M.; Naito, N.R.; Takamoto, D.Y. [Harvey Mudd College, Claremont, CA (United States)

1995-03-23

We have monitored the interactions of the series of trivalent lanthanide cations with the thylakoid membrane surface of spinach chloroplasts using two complementary spectral techniques. Measurements of the fluorescence emission of the extrinsic probe 2-p-toluidinonaphthalene-6-sulfonate (TNS) and the absorbance of the intrinsic chromophore chlorophyll provide two sensitive means of characterizing the dependence of the cation-membrane interaction on the nature of the cation. In these systems, added lanthanide cations adsorb onto the membrane surface to neutralize exposed segments of membrane-embedded protein complexes. The lanthanide-induced charge neutralization increases the proximity of added TNS anion to the membrane surface as evidenced by variations in the TNS fluorescence level and wavelength of maximum emission. Our results reveal a strong dependence of TNS fluorescence parameters on both lanthanide size and total orbital angular momentum L value. Lanthanides with greater charge density (small size and/or low L value) enhance the TNS fluorescence level to a greater extent. A possible origin for the lanthanide-dependent TNS fluorescence levels is suggested in terms of a heterogeneity in the number and type of TNS binding sites. The data are consistent with the proposal that larger lanthanides with smaller enthalpies of hydration induce more significant membrane appression. 59 refs., 9 figs., 2 tabs.

Fabrication of multi-functional porous microspheres in a modular fashion for the detection, adsorption, and removal of pollutants in wastewater.

Science.gov (United States)

Ding, Baojun; Wang, Jie; Tao, Shengyang; Ding, Yunzhe; Zhang, Lijing; Gao, Ning; Li, Guangtao; Shi, Haonan; Li, Weijun; Ge, Shuo

2018-07-15

Water pollution control has become significant challenges in recent years because of their extensive species diversity. It is critical to developing general-purpose materials for environmental rehabilitation. In this paper, a novel module-assembly method is developed to prepare multi-functional materials for treating pollutants in water. Building blocks are porous nanoparticles with a different function. Microspheres (MS) with a diameter of 90 μm are prepared and have a coefficient of variation of 6.8%. The modular fashion of self-assembly process in a microfluidic chip is the crucial factor in fabricating the multifunction material. The assembled microspheres with different building modules still have a specific surface area larger than 400 m 2 g -1 , and exhibit excellent performance in adsorbing various pollutants in water, such as heavy metal ions and organic dyes. The adsorption capacities of them to Hg 2+ and orange II reach 150 mg g -1 and 333 mg g -1 , respectively. The integrated fluorescence probes in microspheres can detect low concentration (9.8 ppb) of Hg 2+ . Microspheres integrated with Fe 3 O 4 nanoparticles have a magnetic susceptibility of 6.01 emu g -1 and can be easily removed from wastewater by applying an external magnetic. Due to the stability of inorganic building blocks, each function in the assembled system is well performed, and multi-functional "All-in-One" materials can be easily fabricated. Copyright © 2018 Elsevier Inc. All rights reserved.

A method for recovery of iron, titanium, and vanadium from vanadium-bearing titanomagnetite

Science.gov (United States)

Zhang, Yi-min; Wang, Li-na; Chen, De-sheng; Wang, Wei-jing; Liu, Ya-hui; Zhao, Hong-xin; Qi, Tao

2018-02-01

An innovative method for recovering valuable elements from vanadium-bearing titanomagnetite is proposed. This method involves two procedures: low-temperature roasting of vanadium-bearing titanomagnetite and water leaching of roasting slag. During the roasting process, the reduction of iron oxides to metallic iron, the sodium oxidation of vanadium oxides to water-soluble sodium vanadate, and the smelting separation of metallic iron and slag were accomplished simultaneously. Optimal roasting conditions for iron/slag separation were achieved with a mixture thickness of 42.5 mm, a roasting temperature of 1200°C, a residence time of 2 h, a molar ratio of C/O of 1.7, and a sodium carbonate addition of 70wt%, as well as with the use of anthracite as a reductant. Under the optimal conditions, 93.67% iron from the raw ore was recovered in the form of iron nugget with 95.44% iron grade. After a water leaching process, 85.61% of the vanadium from the roasting slag was leached, confirming the sodium oxidation of most of the vanadium oxides to water-soluble sodium vanadate during the roasting process. The total recoveries of iron, vanadium, and titanium were 93.67%, 72.68%, and 99.72%, respectively.

A stimuli-responsive smart lanthanide nanocomposite for multidimensional optical recording and encryption

Energy Technology Data Exchange (ETDEWEB)

Li, Xiang; Xie, Yujie; Zhang, Hao-Li; Chen, Hao; Cai, Huijuan; Liu, Weisheng; Tang, Yu [State Key Lab. of Applied Organic Chemistry, Key Lab. of Nonferrous Metal Chemistry and Resources Utilization of Gansu Province, College of Chemistry and Chemical Engineering, Lanzhou Univ. (China); Song, Bo [State Key Lab. of Fine Chemicals, School of Chemistry, Dalian Univ. of Technology, Dalian (China)

2017-03-01

A stimuli-responsive lanthanide-based smart nanocomposite has been fabricated by supramolecular assembly and applied as an active material in multidimensional memory materials. Conjugation of the lanthanide complexes with carbon dots provides a stimuli response that is based on the modulation of the energy level of the ligand and affords microsecond-to-nanosecond fluorescence lifetimes, giving rise to intriguing memory performance in the spatial and temporal dimension. The present study points to a new direction for the future development of multidimensional memory materials based on inorganic-organic hybrid nanosystems. (copyright 2017 Wiley-VCH Verlag GmbH and Co. KGaA, Weinheim)

Low-voltage organic field-effect transistors based on novel high-κ organometallic lanthanide complex for gate insulating materials

Energy Technology Data Exchange (ETDEWEB)

Liu, Qi; Li, Yi; Zhang, Yang; Song, You, E-mail: wangxzh@nju.edu.cn, E-mail: yli@nju.edu.cn, E-mail: yousong@nju.edu.cn; Wang, Xizhang, E-mail: wangxzh@nju.edu.cn, E-mail: yli@nju.edu.cn, E-mail: yousong@nju.edu.cn; Hu, Zheng [Key Laboratory of Mesoscopic Chemistry of MOE, Jiangsu Provincial Lab for Nanotechnology, School of Chemistry and Chemical Engineering, Nanjing University, Nanjing 210093, China. High-Tech Research Institute of Nanjing University (Suzhou), Suzhou 215123 (China); Sun, Huabin; Li, Yun, E-mail: wangxzh@nju.edu.cn, E-mail: yli@nju.edu.cn, E-mail: yousong@nju.edu.cn; Shi, Yi [School of Electronic Science and Engineering and Jiangsu Provincial Key Laboratory of Photonic and Electronic Materials, Nanjing University, Nanjing 210093 (China)

2014-08-15

A novel high-κ organometallic lanthanide complex, Eu(tta){sub 3}L (tta=2-thenoyltrifluoroacetonate, L = 4,5-pinene bipyridine), is used as gate insulating material to fabricate low-voltage pentacene field-effect transistors (FETs). The optimized gate insulator exhibits the excellent properties such as low leakage current density, low surface roughness, and high dielectric constant. When operated under a low voltage of −5 V, the pentacene FET devices show the attractive electrical performance, e.g. carrier mobility (μ{sub FET}) of 0.17 cm{sup 2} V{sup −1} s{sup −1}, threshold voltage (V{sub th}) of −0.9 V, on/off current ratio of 5 × 10{sup 3}, and subthreshold slope (SS) of 1.0 V dec{sup −1}, which is much better than that of devices obtained on conventional 300 nm SiO{sub 2} substrate (0.13 cm{sup 2} V{sup −1} s{sup −1}, −7.3 V and 3.1 V dec{sup −1} for μ{sub FET}, V{sub th} and SS value when operated at −30 V). These results indicate that this kind of high-κ organometallic lanthanide complex becomes a promising candidate as gate insulator for low-voltage organic FETs.

Energetic lanthanide complexes: coordination chemistry and explosives applications

International Nuclear Information System (INIS)

Manner, V W; Barker, B J; Sanders, V E; Laintz, K E; Scott, B L; Preston, D N; Sandstrom, M; Reardon, B L

2014-01-01

Metals are generally added to organic molecular explosives in a heterogeneous composite to improve overall heat and energy release. In order to avoid creating a mixture that can vary in homogeneity, energetic organic molecules can be directly bonded to high molecular weight metals, forming a single metal complex with Angstrom-scale separation between the metal and the explosive. To probe the relationship between the structural properties of metal complexes and explosive performance, a new series of energetic lanthanide complexes has been prepared using energetic ligands such as NTO (5-nitro-2,4-dihydro-1,2,4-triazole-3-one). These are the first examples of lanthanide NTO complexes where no water is coordinated to the metal, demonstrating novel control of the coordination environment. The complexes have been characterized by X-ray crystallography, NMR and IR spectroscopies, photoluminescence, and sensitivity testing. The structural and energetic properties are discussed in the context of enhanced blast effects and detection. Cheetah calculations have been performed to fine-tune physical properties, creating a systematic method for producing explosives with 'tailor made' characteristics. These new complexes will be benchmarks for further study in the field of metalized high explosives.

Extraction-complexonometric determination of vanadium(4) in the presence of vanadium(3)

International Nuclear Information System (INIS)

Gordeeva, M.N.; Ryndina, A.M.; Stanevich, T.V.

1976-01-01

The extraction-complexonometric method has been investigated for determining vanadium(4) in the presence of vanadium (3) with high contents of these forms in the solution analyzed. The method of separation of V(4) and V(3) is based on extraction of the ion acetate of vanadium(4) with eriochrome red B(ERCB) and diphenyl quanidinium (DPG) by a mixture of chloroform and isoamyl alcohol (3:1). To control the content of V(4) and V(3) the method of reciprocal complexonometric titration is used (the titrating solution was a solution of thorium nitride, and xylenol orange was a solution of thorium nitride, and xylenol orange was used as metal indicator). Titration has been carried out in an acid solution at pH=2.8. The developed method has been applied to analysis of lithium-zinc spinels containing both forms of vanadium

Characterization of vanadium-doped mesoporous titania and its adsorption of gaseous benzene

Energy Technology Data Exchange (ETDEWEB)

Nguyen-Phan, Thuy-Duong; Song, Myoung Bock; Yun, Hyunran; Kim, Eui Jung; Oh, Eun-Suok [School of Chemical Engineering and Bioengineering, University of Ulsan, Mugeo-dong, Nam-gu, Ulsan 680-749 (Korea, Republic of); Shin, Eun Woo, E-mail: ewshin@mail.ulsan.ac.kr [School of Chemical Engineering and Bioengineering, University of Ulsan, Mugeo-dong, Nam-gu, Ulsan 680-749 (Korea, Republic of)

2011-01-01

A series of vanadium-doped mesoporous titania with different metal contents was synthesized in the study via a sol-gel process with the assistance of a dodecylamine surfactant. The existence of vanadium ions not only suppressed crystallization and sintering but also enhanced the porosity of the mesoporous TiO{sub 2}. Varying the vanadium concentration led to significant changes in the chemical oxidation state of each component. The presence of metal dopants significantly improved the removal efficiency of benzene and the doping the titania with 5 mol% vanadium removed the most benzene, regardless of the adsorption temperature. The adsorption behavior was elucidated by the specific surface area, the interactions between surface hydroxyl groups and the {pi}-electrons of benzene, and the formation of {sigma}-bonding and d-{pi}* back-donation between the adsorbent and organic compounds.

Synthesis, structural characterization, luminescent properties and theoretical study of three novel lanthanide metal-organic frameworks of Ho(III), Gd(III) and Eu(III) with 2,5-thiophenedicarboxylate anion

Energy Technology Data Exchange (ETDEWEB)

Marques, Lippy F. [Instituto de Química, Universidade do Estado do Rio de Janeiro, Rio de Janeiro 20550-013 (Brazil); Correa, Charlane C. [Departamento de Química-ICE, Universidade Federal de Juiz de Fora, Juiz de Fora-MG, 36036-330 (Brazil); Ribeiro, Sidney J.L.; Santos, Molíria V. dos [Institute of Chemistry, São Paulo State University − UNESP, CP 355 Araraquara-SP 14801-970 Brazil (Brazil); Dutra, José Diogo L.; Freire, Ricardo O. [Pople Computational Chemistry Laboratory, Departamento de Química, Universidade Federal de Sergipe, São Cristóvão-SE 49100-000 (Brazil); Machado, Flávia C., E-mail: flavia.machado@ufjf.edu.br [Departamento de Química-ICE, Universidade Federal de Juiz de Fora, Juiz de Fora-MG, 36036-330 (Brazil)

2015-07-15

In this paper, the synthesis of three new metal-organic frameworks of lanthanides (LnMOFs) ([Ln{sub 2}(2,5-tdc){sub 3}(dmso){sub 2}]·H{sub 2}O){sub n} (Ln=Ho (1); Gd (2); Eu (3); 2,5-tdc=2,5-thiophenedicarboxylate anion; dmso=dimethylsulfoxide), and their complete characterization, including single crystal X-ray diffraction, FTIR spectroscopy and thermogravimetric analysis are reported. In especial, photophysical properties of Eu(III) complex have been studied in detail via both theoretical and experimental approaches. Crystal structure of (1) reveals that each lanthanide ion is seven-coordinated by oxygen atoms in an overall distorted capped trigonal – prismatic geometry. The 2,5-tdc{sup 2−} ligands connect four Ln(III) centers, adopting (κ{sup 1}–κ{sup 1})–(κ{sup 1}–κ{sup 1})–μ{sub 4} coordination mode, generating an 8-connected uninodal 3D network. In addition, theoretical studies for Eu(III) complex were performed using the Sparkle model for lanthanide complexes. - Graphical abstract: Three new metal-organic frameworks of lanthanides (LnMOFs) ([Ln{sub 2}(2,5-tdc){sub 3}(dmso){sub 2}]·H{sub 2}O){sub n} (Ln=Ho (1); Gd (2); Eu (3); 2,5-tdc=2,5-thiophenedicarboxylate anion; dmso=dimethylsulfoxide), were synthesized and their complete characterization, including single crystal X-ray diffraction, FTIR spectroscopy and thermogravimetric analysis are reported. In especial, photophysical properties of Eu(III) complex have been studied in detail via both theoretical and experimental approaches. - Highlights: • Three new LnMOFs were synthesized and fully characterized. • Ho{sup 3+}, Gd{sup 3+} and Eu{sup 3+} complexes photoluminescence properties were investigated. • Theoretical approaches for Eu{sup 3+} complex luminescence has been performed. • An energy level diagram is used to establish the ligand-to-metal energy transfer. • These metal−organic frameworks can act as light conversion molecular devices.

Studies on electronic spectrum and electron spin resonance of vanadium (IV) complexes with organophosphorus compounds and high molecular weight amines

International Nuclear Information System (INIS)

Sato, Taichi; Nakamura, Takato

1981-01-01

In the extraction of vanadium (IV) from aqueous solutions containing hydrochloric acid and/or a mixture of hydrochloric acid and lithium chloride by bis(2-ethylhexyl) hydrogenphosphate (DEHPA; HX), trioctylmethylammonium chloride (Aliquat-336), trioctylamine (TOA), trioctylphosphine oxide (TOPO) and tributyl phosphate (TBP), the complexes formed in the organic phases have been examined by spectrophotometry and electron spin resonance spectroscopy. It is found that in the extraction by DEHPA, the vanadium in the organic phase exists as the monomeric species, VO(X 2 H) 2 , or the polymeric one, (VOX 2 )sub(n), and that in the extractions by Aliquat-336, TOA, TOPO, and TBP, tetravalent vanadium complexes are stable in the organic phases extracted from a mixed solution of hydrochloric acid and lithium chloride, while complexes containing pentavalent vanadium and VOV 4+ ions are formed in the organic phases extracted from hydrochloric acid solutions. (author)

Polymetallic lanthanide (III) complexes for the design of new luminescent materials

International Nuclear Information System (INIS)

Marchal, C.

2008-09-01

The incorporation of f elements in highly organized polymetallic complexes is of great interest in supramolecular chemistry and allows the combination of their nano-scopic size with the magnetic or optical properties of the metal ions. However due to the difficulty in controlling the coordination environment of these ions, the assembly of lanthanide-based polynuclear architectures has lagged behind that of other systems. These factors make the rational design for the construction of supramolecular lanthanide complexes quite challenging. In order to better understand the factors determining the assembly of lanthanide-based polymetallic arrays, we designed two different types of organic ligands, which favor, in one case, formation of infinite polymetallic complexes (coordination polymers), and in the case the assembly of discrete polymetallic architectures. Thus, we show that the use of flexible and multi-dentate picolinate-derivative ligands enables the formation of infinite and luminescent infinite frameworks which display very interesting luminescent properties. Geometry of the ligand has a great influence on the final network architecture. Particularly, implementation of four picolinate units within a tetrapodal ligand results in the controlled assembly of 1-D coordination polymers. Conversely to favor the controlled assembly of discrete polymetallic arrays we use dissymmetric ligands which displays low denticity. Complexation studies of a tridentate 8- hydroxyquinoline-derivative ligand as well as a tetradentate ligand possessing an oxazoline ring are presented. (author)

NMR study of structure of lanthanide complexes in solution

International Nuclear Information System (INIS)

Choppin, G.R.

1976-01-01

The diagnostic value PMR studies of diamagnetic lanthanide complexes to define the nature of the species in the lanthanide-pyruvate system is discussed. The use of NMR spectra of both diamagnetic and paramagnetic lanthanide complexes to obtain detailed structural information is reviewed

Domain organizations of modular extracellular matrix proteins and their evolution.

Science.gov (United States)

Engel, J

1996-11-01

Multidomain proteins which are composed of modular units are a rather recent invention of evolution. Domains are defined as autonomously folding regions of a protein, and many of them are similar in sequence and structure, indicating common ancestry. Their modular nature is emphasized by frequent repetitions in identical or in different proteins and by a large number of different combinations with other domains. The extracellular matrix is perhaps the largest biological system composed of modular mosaic proteins, and its astonishing complexity and diversity are based on them. A cluster of minireviews on modular proteins is being published in Matrix Biology. These deal with the evolution of modular proteins, the three-dimensional structure of domains and the ways in which these interact in a multidomain protein. They discuss structure-function relationships in calcium binding domains, collagen helices, alpha-helical coiled-coil domains and C-lectins. The present minireview is focused on some general aspects and serves as an introduction to the cluster.

Self-assembling Synthesis of Vanadium Oxide Nanotubes and Simple Determination of the Content of Ⅴ(Ⅳ)

Institute of Scientific and Technical Information of China (English)

MAI Li-qiang; CHEN Wen; XU Qing; ZHU Quan-yao; HAN Chun-hua; PENG Jun-feng

2003-01-01

High-yielding low-cost vanadium oxide nanotubes were prepared by the hydrothermal self-assembling process from vanadium pentoxide and organic molecules as structure-directing templates. Moreover, a new method was discovered for determining the content of V (Ⅳ) in vanadium oxide nanotubes by thermogravimetric analysis ( TGA ). This method is simple, precise and feasible and can be extended to determine the content of low oxidation state in the other transition metal oxide nanomaterials.

Extraction of Vanadium from Vanadium Slag Via Non-salt Roasting and Ammonium Oxalate Leaching

Science.gov (United States)

Li, Meng; Du, Hao; Zheng, Shili; Wang, Shaona; Zhang, Yang; Liu, Biao; Dreisinger, David Bruce; Zhang, Yi

2017-10-01

A clean method featuring non-salt roasting followed by (NH4)2C2O4 leaching to recover vanadium from vanadium slag was proposed. The carcinogenic Cr6+ compounds and exhaust gases were avoided, and the water generated from vanadate precipitation may be recycled and reused in this new leaching process. The leaching residues may be easily used by a blast furnace. Moreover, (NH4)2C2O4 solution was used as a leaching medium to avoid expensive and complicated ammonium controlling operations as a result of the stability of (NH4)2C2O4 at a high temperature. The transformation mechanisms of vanadium- and chromium-bearing phases were systematically investigated by x-ray diffraction analysis and scanning electron microscopy with energy-disperse x-ray spectrometry, respectively. In addition, the effects of oxygen concentration, roasting temperature, and holding time on vanadium recovery were investigated. Finally, the effects of leaching variables on the vanadium leaching rate were also examined.

Lanthanides, thorium, iodine in terrestrail invertebrates

International Nuclear Information System (INIS)

Zhulidov, A.V.; Pokarzhevskij, A.D.; Katargin, N.V.; AN SSSR, Moscow

1991-01-01

It is shown that among examined terrestrial invertebrates the highest levels on lanthanide and thorium concentration are typical for animals, feeding on plant tissues - earthworms, molluscs, diploid. It is shown that there are no reasons to hope, that regularities of migration of transuranium elements and lanthanides in tropic chains are identical

Ultrasmall lanthanide oxide nanoparticles for biomedical imaging and therapy

CERN Document Server

Lee, Gang Ho

2014-01-01

Most books discuss general and broad topics regarding molecular imagings. However, Ultrasmall Lanthanide Oxide Nanoparticles for Biomedical Imaging and Therapy, will mainly focus on lanthanide oxide nanoparticles for molecular imaging and therapeutics. Multi-modal imaging capabilities will discussed, along with up-converting FI by using lanthanide oxide nanoparticles. The synthesis will cover polyol synthesis of lanthanide oxide nanoparticles, Surface coatings with biocompatible and hydrophilic ligands will be discussed and TEM images and dynamic light scattering (DLS) patterns will be

How Does the Modular Organization of Entorhinal Grid Cells Develop?

Directory of Open Access Journals (Sweden)

Stephen eGrossberg

2014-06-01

Full Text Available The entorhinal-hippocampal system plays a crucial role in spatial cognition and navigation. Since the discovery of grid cells in layer II of medial entorhinal cortex (MEC, several types of models have been proposed to explain their development and operation; namely, continuous attractor network models, oscillatory interference models, and self-organizing map (SOM models. Recent experiments revealing the in vivo intracellular signatures of grid cells (Domnisoru et al., 2013; Schmidt-Heiber & Hausser, 2013, the primarily inhibitory recurrent connectivity of grid cells (Couey et al., 2013; Pastoll et al., 2013, and the topographic organization of grid cells within anatomically overlapping modules of multiple spatial scales along the dorsoventral axis of MEC (Stensola et al., 2012 provide strong constraints and challenges to existing grid cell models. This article provides a computational explanation for how MEC cells can emerge through learning with grid cell properties in modular structures. Within this SOM model, grid cells with different rates of temporal integration learn modular properties with different spatial scales. Model grid cells learn in response to inputs from multiple scales of directionally-selective stripe cells (Krupic et al., 2012; Mhatre et al., 2012 that perform path integration of the linear velocities that are experienced during navigation. Slower rates of grid cell temporal integration support learned associations with stripe cells of larger scales. The explanatory and predictive capabilities of the three types of grid cell models are comparatively analyzed in light of recent data to illustrate how the SOM model overcomes problems that other types of models have not yet handled.

Effect of a lanthanide ion on the micellation and self-organization of lyotropic liquid crystal systems

International Nuclear Information System (INIS)

Selivanova, N.M.; Osipova, V.V.; Galyametdinov, Yu.G.

2006-01-01

Lanthanide-containing lyotropic liquid-crystalline systems were synthesized and their phase behavior, as well as the micellar behavior of aqueous solutions of decaethylene glycol monodecyl ether in the absence and presence of a lanthanide ion, were studied. Tensimetry and conductometry were used to determine the critical micellation concentration, and the values obtained by these methods were found to be in close agreement with each other. Polarization microscopy observations showed that, in concentrated aqueous solutions, ordered lyotropic mesophases arise. The parameters of the phase transitions in the systems under study were determined. The mesophase obtained was demonstrated to have a 2D hexagonal supramolecular structure [ru

Exploring Trianglamine Derivatives and Trianglamine Coordination Complexes as Porous Organic Materials

KAUST Repository

Eziashi, Magdalene

2018-01-01

, they are still a poorly researched class of macrocycles today. Trianglamines have yet a role to play as porous organic molecules for separation processes, as macrocyclic precursors to build increasingly complex supramolecular assemblies and as building blocks

Diphenyl-phosphinyl-morpholide (DPPM) lanthanide trifluoroacetate adducts

International Nuclear Information System (INIS)

Carvalho, L.R.F. de; Kim, D.J.

1984-01-01

Preparation and properties of adducts of lanthanide salts and diphenyl-phosphinyl-morpholide (DPPM) have been described in the literature. Addition compounds containing lanthanide nitrates, isothiocyanates, perchlorates, chlorides, bromides with DPPM have been obtained. In this article, the preparation and characterization of the addition compounds of lanthanide trifluoroacetates (TFA) with DPPM are reported. The compounds of general formula Ln (TFA) 3 . 3DPPM, Ln= La-Lu, Y were characterized by elemental analysis, melting ranges, infrared spectra, absorption and emission visible spectra, X-ray powder patterns. (Author) [pt

Surface-Supported Robust 2D Lanthanide-Carboxylate Coordination Networks.

Science.gov (United States)

Urgel, José I; Cirera, Borja; Wang, Yang; Auwärter, Willi; Otero, Roberto; Gallego, José M; Alcamí, Manuel; Klyatskaya, Svetlana; Ruben, Mario; Martín, Fernando; Miranda, Rodolfo; Ecija, David; Barth, Johannes V

2015-12-16

Lanthanide-based metal-organic compounds and architectures are promising systems for sensing, heterogeneous catalysis, photoluminescence, and magnetism. Herein, the fabrication of interfacial 2D lanthanide-carboxylate networks is introduced. This study combines low- and variable-temperature scanning tunneling microscopy (STM) and X-ray photoemission spectroscopy (XPS) experiments, and density functional theory (DFT) calculations addressing their design and electronic properties. The bonding of ditopic linear linkers to Gd centers on a Cu(111) surface gives rise to extended nanoporous grids, comprising mononuclear nodes featuring eightfold lateral coordination. XPS and DFT elucidate the nature of the bond, indicating ionic characteristics, which is also manifest in appreciable thermal stability. This study introduces a new generation of robust low-dimensional metallosupramolecular systems incorporating the functionalities of the f-block elements. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Use of lanthanide catalysts in air electrodes

International Nuclear Information System (INIS)

Souza Parente, L.T. de

1982-01-01

A review on the lanthanide catalysts suitable for the reduction catalysis of oxygen in air electrodes is presented. The kinds of lanthanide indicated to be used as catalysts of oxygen reduction are shown. (A.R.H.) [pt

Effects of dietary vanadium in mallard ducks

Science.gov (United States)

White, D.H.; Dieter, M.P.

1978-01-01

Adult mallard ducks fed 0, 1, 10, or 100 ppm vanadyl sulfate in the diet were sacrificed after 12 wk on treatment; tissues were analyzed for vanadium. No birds died during the study and body weights did not change. Vanadium accumulated to higher concentrations in the bone and liver than in other tissues. Concentrations in bones of hens were five times those in bones of drakes, suggesting an interaction between vanadium and calcium mobilization in laying hens. Vanadium concentrations in most tissues were significantly correlated and increased with treatment level. Lipid metabolism was altered in laying hens fed 100 ppm vanadium. Very little vanadium accumulated in the eggs of laying hens.

Determination of stability constants of lanthanide nitrate complex formation using a solvent extraction technique

International Nuclear Information System (INIS)

Andersson, S.; Ekberg, C.; Liljenzin, J.O.; Nilsson, M.; Skarnemark, G.; Eberhardt, K.

2006-01-01

For lanthanides and actinides, nitrate complex formation is an important factor with respect to the reprocessing of nuclear fuels and in studies that treat partitioning and transmutation/conditioning. Different techniques, including microcalorimetry, various kinds of spectroscopy, ion-exchange and solvent extraction, can be used to determine stability constants of nitrate complex formation. However, it is uncommon that all lanthanides are studied at the same time, using the same experimental conditions and technique. The strengths of the complexes are different for lanthanides and actinides, a feature that may assist in the separation of the two groups. This paper deals with nitrate complex formation of lanthanides using a solvent extraction technique. Trace amounts of radioactive isotopes of lanthanides were produced at the TRIGA Mainz research reactor and at the Institutt for Energiteknikk in Kjeller, Norway (JEEP II reactor). The extraction of lanthanide ions into an organic phase consisting of 2, 6-bis-(benzoxazolyl)-4-dodecyloxylpyridine, 2-bromodecanoic acid and tert-butyl benzene as a function of nitrate ion concentration in the aqueous phase was studied in order to estimate the stability constants of nitrate complex formation. When the nitrate ion concentration is increased in the aqueous phase, the nitrate complex formation starts to compete with the extraction of metal ions. Thus the stability constants of nitrate complex formation can be estimated by measuring the decrease in extraction and successive fitting of an appropriate model. Extraction curves for La, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Dy, Ho and Er were obtained and stability constants for their nitrate complex formation were estimated. Tb, Tm, Yb and Lu were also investigated, but no stability constants could be determined. The distribution ratios for the metal ions at low nitrate ion concentration were obtained at the same time, showing the effect of lanthanide contraction resulting in decreasing

Calibration beads containing luminescent lanthanide ion complexes

Science.gov (United States)

The reliability of lanthanide luminescence measurements, by both flow cytometry and digital microscopy, will be enhanced by the availability of narrow-band emitting lanthanide calibration beads. These beads can also be used to characterize spectrographic instruments, including mi...

Spatial atomic layer deposition for coating flexible porous Li-ion battery electrodes

Energy Technology Data Exchange (ETDEWEB)

Yersak, Alexander S.; Sharma, Kashish; Wallas, Jasmine M.; Dameron, Arrelaine A.; Li, Xuemin; Yang, Yongan; Hurst, Katherine E.; Ban, Chunmei; Tenent, Robert C.; George, Steven M. [Department of Chemistry and Biochemistry, University of Colorado, Boulder, Colorado 80309 and Department of Mechanical Engineering, University of Colorado, Boulder, Colorado 80309

2018-01-01

Ultrathin atomic layer deposition (ALD) coatings on the electrodes of Li-ion batteries can enhance the capacity stability of the Li-ion batteries. To commercialize ALD for Li-ion battery production, spatial ALD is needed to decrease coating times and provide a coating process compatible with continuous roll-to-roll (R2R) processing. The porous electrodes of Li-ion batteries provide a special challenge because higher reactant exposures are needed for spatial ALD in porous substrates. This work utilized a modular rotating cylinder spatial ALD reactor operating at rotation speeds up to 200 revolutions/min (RPM) and substrate speeds up to 200 m/min. The conditions for spatial ALD were adjusted to coat flexible porous substrates. The reactor was initially used to characterize spatial Al2O3 and ZnO ALD on flat, flexible metalized polyethylene terephthalate foils. These studies showed that slower rotation speeds and spacers between the precursor module and the two adjacent pumping modules could significantly increase the reactant exposure. The modular rotating cylinder reactor was then used to coat flexible, model porous anodic aluminum oxide (AAO) membranes. The uniformity of the ZnO ALD coatings on the porous AAO membranes was dependent on the aspect ratio of the pores and the reactant exposures. Larger reactant exposures led to better uniformity in the pores with higher aspect ratios. The reactant exposures were increased by adding spacers between the precursor module and the two adjacent pumping modules. The modular rotating cylinder reactor was also employed for Al2O3 ALD on porous LiCoO2 (LCO) battery electrodes. Uniform Al coverages were obtained using spacers between the precursor module and the two adjacent pumping modules at rotation speeds of 25 and 50 RPM. The LCO electrodes had a thickness of ~49 um and pores with aspect ratios of ~12-25. Coin cells were then constructed using the ALD-coated LCO electrodes and were tested to determine their battery

Novel lanthanide doped micro- and mesoporous solids. Characterization of ion-host-interactions, species distribution and luminescence properties using time-resolved luminescence spectroscopy

International Nuclear Information System (INIS)

Gessner, Andre

2010-12-01

In this work lanthanide-doped microporous zeolites, microporous-mesoporous hybrid materials and mesoporous silicates were investigated regarding their luminescence properties and the ion-host-interactions using time-resolved luminescence spectroscopy. Thereby, time-resolved emission spectra (TRES) provide information in the wavelength and time domain. For the analysis of the TRES a broad set of analytic methods was applied and thus a corresponding ''toolbox'' developed. Fitting of the luminescence decays was performed with a discrete number of exponentials and supported by luminescence decay times distributions. Time-resolved area normalized emission spectra (TRANES), an advancement of TRES, could be used for the determination of the number of emissive lanthanide species in porous materials for the first time. Calculation of the decay-associated spectra (DAS) allowed the correlation of spectral information with luminescence decay times and thus delivered the luminescence spectra of the different europium species. For europium(III) we could use in addition the time-dependent asymmetry ratio and spectral evolution of the 5 D 0 - 7 F 0 -transition with time to obtain further information about the distribution of the lanthanide ions in the host material. Luminescence decay times and spectra allowed conclusions on the number of OH-oscillators in and the symmetry of the first coordination sphere. For the microporous and microporous-mesoporous materials were found different lanthanide species, which were characterized by the above mentioned methods. These lanthanide species can be found on different positions in the host material. One position is located deep in the pore system. Here, lanthanide ions are hardly accessible for water and mainly coordinated by framework oxygens. This results in long luminescence decay times and distorted coordination spheres. The second position can be found near or on the outer surface or in the mesopores. Lanthanide ions located here, are

Synthesis and luminescence properties of hybrid organic-inorganic transparent titania thin film activated by in- situ formed lanthanide complexes

Science.gov (United States)

Wang, Yige; Wang, Li; Li, Huanrong; Liu, Peng; Qin, Dashan; Liu, Binyuan; Zhang, Wenjun; Deng, Ruiping; Zhang, Hongjie

2008-03-01

Stable transparent titania thin films were fabricated at room temperature by combining thenoyltrifluoroacetone (TTFA)-modified titanium precursors with amphiphilic triblock poly(ethylene oxide)-poly(propylene oxide)-poly(ethylene oxide) (PEO-PPO-PEO, P123) copolymers. The obtained transparent titania thin films were systematically investigated by IR spectroscopy, PL emission and excitation spectroscopy and transmission electron microscopy. IR spectroscopy indicates that TTFA coordinates the titanium center during the process of hydrolysis and condensation. Luminescence spectroscopy confirms the in-situ formation of lanthanide complexes in the transparent titania thin film. TEM image shows that the in-situ formed lanthanide complexes were homogeneously distributed throughout the whole thin film. The quantum yield and the number of water coordinated to lanthanide metal center have been theoretically determined based on the luminescence data.

Gas storage in porous metal-organic frameworks for clean energy applications.

Science.gov (United States)

Ma, Shengqian; Zhou, Hong-Cai

2010-01-07

Depletion of fossil oil deposits and the escalating threat of global warming have put clean energy research, which includes the search for clean energy carriers such as hydrogen and methane as well as the reduction of carbon dioxide emissions, on the urgent agenda. A significant technical challenge has been recognized as the development of a viable method to efficiently trap hydrogen, methane and carbon dioxide gas molecules in a confined space for various applications. This issue can be addressed by employing highly porous materials as storage media, and porous metal-organic frameworks (MOFs) which have exceptionally high surface areas as well as chemically-tunable structures are playing an unusual role in this respect. In this feature article we provide an overview of the current status of clean energy applications of porous MOFs, including hydrogen storage, methane storage and carbon dioxide capture.

Experimental solubility measurements of lanthanides in liquid alkalis

Science.gov (United States)

Isler, Jeremy; Zhang, Jinsuo; Mariani, Robert; Unal, Cetin

2017-11-01

In metallic nuclear fuel, lanthanide fission products play a crucial role in the fuel burnup-limiting phenomena of fuel cladding-chemical interaction (FCCI). The lanthanides have been hypothesized to transport by a 'liquid-like' mechanism out of the metallic fuel to the fuel peripheral to cause FCCI. By liquid fission product cesium and liquid bond sodium, the lanthanides are transported to the peripheral of the fuel through the porosity of the fuel. This work investigates the interaction between the lanthanides and the alkali metals by experimentally measuring the solubility of lanthanides within liquid sodium, and neodymium in liquid cesium and mixtures of cesium and sodium. The temperature dependence of the solubility is experimentally determined within an inert environment. In addition, the dependence of the solubility on the alkali metal concentration in liquid mixtures of cesium and sodium was examined. In quantifying the solubility, the fundamental understanding of this transport mechanism can be better determined.

3D-printed conductive static mixers enable all-vanadium redox flow battery using slurry electrodes

Science.gov (United States)

Percin, Korcan; Rommerskirchen, Alexandra; Sengpiel, Robert; Gendel, Youri; Wessling, Matthias

2018-03-01

State-of-the-art all-vanadium redox flow batteries employ porous carbonaceous materials as electrodes. The battery cells possess non-scalable fixed electrodes inserted into a cell stack. In contrast, a conductive particle network dispersed in the electrolyte, known as slurry electrode, may be beneficial for a scalable redox flow battery. In this work, slurry electrodes are successfully introduced to an all-vanadium redox flow battery. Activated carbon and graphite powder particles are dispersed up to 20 wt% in the vanadium electrolyte and charge-discharge behavior is inspected via polarization studies. Graphite powder slurry is superior over activated carbon with a polarization behavior closer to the standard graphite felt electrodes. 3D-printed conductive static mixers introduced to the slurry channel improve the charge transfer via intensified slurry mixing and increased surface area. Consequently, a significant increase in the coulombic efficiency up to 95% and energy efficiency up to 65% is obtained. Our results show that slurry electrodes supported by conductive static mixers can be competitive to state-of-the-art electrodes yielding an additional degree of freedom in battery design. Research into carbon properties (particle size, internal surface area, pore size distribution) tailored to the electrolyte system and optimization of the mixer geometry may yield even better battery properties.

Efficient Separation and Extraction of Vanadium and Chromium in High Chromium Vanadium Slag by Selective Two-Stage Roasting-Leaching

Science.gov (United States)

Wen, Jing; Jiang, Tao; Xu, Yingzhe; Liu, Jiayi; Xue, Xiangxin

2018-04-01

Vanadium and chromium are important rare metals, leading to a focus on high chromium vanadium slag (HCVS) as a potential raw material to extract vanadium and chromium in China. In this work, a novel method based on selective two-stage roasting-leaching was proposed to separate and extract vanadium and chromium efficiently in HCVS. XRD, FT-IR, and SEM were utilized to analyze the phase evolutions and microstructure during the whole process. Calcification roasting, which can calcify vanadium selectively using thermodynamics, was carried out in the first roasting stage to transfer vanadium into acid-soluble vanadate and leave chromium in the leaching residue as (Fe0.6Cr0.4)2O3 after H2SO4 leaching. When HCVS and CaO were mixed in the molar ratio CaO/V2O3 (n(CaO)/n(V2O3)) of 0.5 to 1.25, around 90 pct vanadium and less than 1 pct chromium were extracted in the first leaching liquid, thus achieving the separation of vanadium and chromium. In the second roasting stage, sodium salt, which combines with chromium easily, was added to the first leaching residue to extract chromium and 95.16 pct chromium was extracted under the optimal conditions. The total vanadium and chromium leaching rates were above 95 pct, achieving the efficient separation and extraction of vanadium and chromium. The established method provides a new technique to separate vanadium and chromium during roasting rather than in the liquid form, which is useful for the comprehensive application of HCVS.

Efficient Separation and Extraction of Vanadium and Chromium in High Chromium Vanadium Slag by Selective Two-Stage Roasting-Leaching

Science.gov (United States)

Wen, Jing; Jiang, Tao; Xu, Yingzhe; Liu, Jiayi; Xue, Xiangxin

2018-06-01

Vanadium and chromium are important rare metals, leading to a focus on high chromium vanadium slag (HCVS) as a potential raw material to extract vanadium and chromium in China. In this work, a novel method based on selective two-stage roasting-leaching was proposed to separate and extract vanadium and chromium efficiently in HCVS. XRD, FT-IR, and SEM were utilized to analyze the phase evolutions and microstructure during the whole process. Calcification roasting, which can calcify vanadium selectively using thermodynamics, was carried out in the first roasting stage to transfer vanadium into acid-soluble vanadate and leave chromium in the leaching residue as (Fe0.6Cr0.4)2O3 after H2SO4 leaching. When HCVS and CaO were mixed in the molar ratio CaO/V2O3 (n(CaO)/n(V2O3)) of 0.5 to 1.25, around 90 pct vanadium and less than 1 pct chromium were extracted in the first leaching liquid, thus achieving the separation of vanadium and chromium. In the second roasting stage, sodium salt, which combines with chromium easily, was added to the first leaching residue to extract chromium and 95.16 pct chromium was extracted under the optimal conditions. The total vanadium and chromium leaching rates were above 95 pct, achieving the efficient separation and extraction of vanadium and chromium. The established method provides a new technique to separate vanadium and chromium during roasting rather than in the liquid form, which is useful for the comprehensive application of HCVS.

High performance separation of lanthanides and actinides

International Nuclear Information System (INIS)

Sivaraman, N.; Vasudeva Rao, P.R.

2011-01-01

The major advantage of High Performance Liquid Chromatography (HPLC) is its ability to provide rapid and high performance separations. It is evident from Van Deemter curve for particle size versus resolution that packing materials with particle sizes less than 2 μm provide better resolution for high speed separations and resolving complex mixtures compared to 5 μm based supports. In the recent past, chromatographic support material using monolith has been studied extensively at our laboratory. Monolith column consists of single piece of porous, rigid material containing mesopores and micropores, which provide fast analyte mass transfer. Monolith support provides significantly higher separation efficiency than particle-packed columns. A clear advantage of monolith is that it could be operated at higher flow rates but with lower back pressure. Higher operating flow rate results in higher column permeability, which drastically reduces analysis time and provides high separation efficiency. The above developed fast separation methods were applied to assay the lanthanides and actinides from the dissolver solutions of nuclear reactor fuels

Vanadium recycling in the United States in 2004

Science.gov (United States)

Goonan, Thomas G.

2011-01-01

As one of a series of reports that describe the recycling of metal commodities in the United States, this report discusses the flow of vanadium in the U.S. economy in 2004. This report includes a description of vanadium supply and demand in the United States and illustrates the extent of vanadium recycling and recycling trends. In 2004, apparent vanadium consumption, by end use, in the United States was 3,820 metric tons (t) in steelmaking and 232 t in manufacturing, of which 17 t was for the production of superalloys and 215 t was for the production of other alloys, cast iron, catalysts, and chemicals. Vanadium use in steel is almost entirely dissipative because recovery of vanadium from steel scrap is chemically impeded under the oxidizing conditions in steelmaking furnaces. The greatest amount of vanadium recycling is in the superalloy, other-alloy, and catalyst sectors of the vanadium market. Vanadium-bearing catalysts are associated with hydrocarbon recovery and refining in the oil industry. In 2004, 2,850 t of vanadium contained in alloy scrap and spent catalysts was recycled, which amounted to about 44 percent of U.S. domestic production. About 94 percent of vanadium use in the United States was dissipative (3,820 t in steel/4,050 t in steel+fabricated products).

Selective removal of lanthanides from natural waters, acidic streams and dialysate

Energy Technology Data Exchange (ETDEWEB)

Yantasee, Wassana, E-mail: wassana.yantasee@pnl.gov [Pacific Northwest National Laboratory (PNNL), P.O. Box 999, Richland, WA 99352 (United States); Fryxell, Glen E.; Addleman, R. Shane; Wiacek, Robert J.; Koonsiripaiboon, View; Pattamakomsan, Kanda; Sukwarotwat, Vichaya [Pacific Northwest National Laboratory (PNNL), P.O. Box 999, Richland, WA 99352 (United States); Xu Jide; Raymond, Kenneth N. [Chemistry Department, University of California, Berkeley, CA 94720 (United States); LBNL, Berkeley, CA 94720 (United States)

2009-09-15

The increased demand for the lanthanides in commercial products result in increased production of lanthanide containing ores, which increases public exposure to the lanthanides, both from various commercial products and from production wastes/effluents. This work investigates lanthanide (La, Ce, Pr, Nd, Eu, Gd and Lu) binding properties of self-assembled monolayers on mesoporous silica supports (SAMMS{sup TM}), that were functionalized with diphosphonic acid (DiPhos), acetamide phosphonic acid (AcPhos), propionamide phosphonic acid (Prop-Phos), and 1-hydroxy-2-pyridinone (1,2-HOPO), from natural waters (river, ground and sea waters), acid solutions (to mimic certain industrial process streams), and dialysate. The affinity, capacity, and kinetics of the lanthanide sorption, as well as regenerability of SAMMS materials were investigated. Going from the acid side over to the alkaline side, the AcPhos- and DiPhos-SAMMS maintain their outstanding affinity for lanthanides, which enable the use of the materials in the systems where the pH may fluctuate. In acid solutions, Prop-Phos- and 1,2-HOPO-SAMMS have differing affinity along the lanthanide series, suggesting their use in chromatographic lanthanide separation. Over 95% of 100 {mu}g/L of Gd in dialysate was removed by the Prop-Phos-SAMMS after 1 min and 99% over 10 min. SAMMS can be regenerated with an acid wash (0.5 M HCl) without losing the binding properties. Thus, they have a great potential to be used as in large-scale treatment of lanthanides, lanthanide separation prior to analytical instruments, and in sorbent dialyzers for treatment of acute lanthanide poisoning.

Selective removal of lanthanides from natural waters, acidic streams and dialysate

International Nuclear Information System (INIS)

Yantasee, Wassana; Fryxell, Glen E.; Addleman, R. Shane; Wiacek, Robert J.; Koonsiripaiboon, View; Pattamakomsan, Kanda; Sukwarotwat, Vichaya; Xu Jide; Raymond, Kenneth N.

2009-01-01

The increased demand for the lanthanides in commercial products result in increased production of lanthanide containing ores, which increases public exposure to the lanthanides, both from various commercial products and from production wastes/effluents. This work investigates lanthanide (La, Ce, Pr, Nd, Eu, Gd and Lu) binding properties of self-assembled monolayers on mesoporous silica supports (SAMMS TM ), that were functionalized with diphosphonic acid (DiPhos), acetamide phosphonic acid (AcPhos), propionamide phosphonic acid (Prop-Phos), and 1-hydroxy-2-pyridinone (1,2-HOPO), from natural waters (river, ground and sea waters), acid solutions (to mimic certain industrial process streams), and dialysate. The affinity, capacity, and kinetics of the lanthanide sorption, as well as regenerability of SAMMS materials were investigated. Going from the acid side over to the alkaline side, the AcPhos- and DiPhos-SAMMS maintain their outstanding affinity for lanthanides, which enable the use of the materials in the systems where the pH may fluctuate. In acid solutions, Prop-Phos- and 1,2-HOPO-SAMMS have differing affinity along the lanthanide series, suggesting their use in chromatographic lanthanide separation. Over 95% of 100 μg/L of Gd in dialysate was removed by the Prop-Phos-SAMMS after 1 min and 99% over 10 min. SAMMS can be regenerated with an acid wash (0.5 M HCl) without losing the binding properties. Thus, they have a great potential to be used as in large-scale treatment of lanthanides, lanthanide separation prior to analytical instruments, and in sorbent dialyzers for treatment of acute lanthanide poisoning.

Comparison of Ultrasound-Assisted and Regular Leaching of Vanadium and Chromium from Roasted High Chromium Vanadium Slag

Science.gov (United States)

Wen, Jing; Jiang, Tao; Gao, Huiyang; Liu, Yajing; Zheng, Xiaole; Xue, Xiangxin

2018-02-01

Ultrasound-assisted leaching (UAL) was used for vanadium and chromium leaching from roasted material obtained by the calcification roasting of high-chromium-vanadium slag. UAL was compared with regular leaching. The effect of the leaching time and temperature, acid concentration, and liquid-solid ratio on the vanadium and chromium leaching behaviors was investigated. The UAL mechanism was determined from particle-size-distribution and microstructure analyses. UAL decreased the reaction time and leaching temperature significantly. Furthermore, 96.67% vanadium and less than 1% chromium were leached at 60°C for 60 min with 20% H2SO4 at a liquid-solid ratio of 8, which was higher than the maximum vanadium leaching rate of 90.89% obtained using regular leaching at 80°C for 120 min. Ultrasonic waves broke and dispersed the solid sample because of ultrasonic cavitation, which increased the contact area of the roasted sample and the leaching medium, the solid-liquid mass transfer, and the vanadium leaching rate.

Fabrication of vanadium cans for neutron diffraction experiments

Energy Technology Data Exchange (ETDEWEB)

Chung, Chin man; Baik, Sung Hoon; Park, Sun Kyu

1999-12-01

The laser weld technique of vanadium developed to experiment for neutron diffraction of HANARO. The demands for this laser welding technique were applied to process control in vanadium film welding and to fabricate various sizing vanadium cans. The vanadium can had a advantage to have less coherent in neutron. KAERI developed the fabrication jig of 6-12 mm diameter cans using 0.125 mm vanadium thin film, and investigated the laser welding procedure for making the various diameter and length of vanadium cans using the fabricated jigs and Nd:YAG laser. (author)

Lanthanide phosphonates: Synthesis, thermal stability and magnetic characterization

Energy Technology Data Exchange (ETDEWEB)

Amghouz, Z., E-mail: amghouz.uo@uniovi.es [Departamentos de Quimica Fisica y Analitica y Quimica Organica e Inorganica, Universidad de Oviedo - CINN, 33006 Oviedo (Spain); Garcia, J.R.; Garcia-Granda, S. [Departamentos de Quimica Fisica y Analitica y Quimica Organica e Inorganica, Universidad de Oviedo - CINN, 33006 Oviedo (Spain); Clearfield, A. [Department of Chemistry, Texas A and M University, College Station, TX 77842-3012 (United States); Rodriguez Fernandez, J.; Pedro, I. de [CITIMAC, Facultad de Ciencias, Universidad de Cantabria, 39005 Santander (Spain); Blanco, J.A. [Departamento de Fisica, Universidad de Oviedo, 33007 Oviedo (Spain)

2012-09-25

Highlights: Black-Right-Pointing-Pointer Report of the complete series of lanthanide 1,4-phenylbis(phosphonate). Black-Right-Pointing-Pointer Synthesis under conventional hydrothermal synthesis or microwave-assisted hydrothermal synthesis. Black-Right-Pointing-Pointer Cation size is the key factor for the structural and particles size variations. Black-Right-Pointing-Pointer Thermal behaviour is characterized by unusual very high thermal stability. - Abstract: Series of novel organic-inorganic hybrids materials based on trivalent lanthanides (Ln = Y, La, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu) and 1,4-phenylbis(phosphonate) obtained under hydrothermal conditions either by oven heat or microwave irradiation. The anhydrous compounds containing La, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, and Ho, are isostructural. However, the compounds based on Y, Er, Tm, Yb, and Lu are hydrated and their structures have not yet been solved. The series of compounds are characterized by PXRD, TEM, SEM-EDX and thermal analyses (TG-MS and DSC). TEM study show a variable particles size with a minimum mean-particle size of ca. 30 nm. These compounds exhibit unusual very high thermal stability. The size of particles and the thermal stability are depending on lanthanide(III) cation features. All the investigated materials show paramagnetic behaviour. The magnetic susceptibility data follow a Curie-Weiss laws with paramagnetic effective moments in good agreement with those expected for Ln{sup 3+} free ions.

The modularity of pollination networks

DEFF Research Database (Denmark)

Olesen, Jens Mogens; Bascompte, J.; Dupont, Yoko

2007-01-01

In natural communities, species and their interactions are often organized as nonrandom networks, showing distinct and repeated complex patterns. A prevalent, but poorly explored pattern is ecological modularity, with weakly interlinked subsets of species (modules), which, however, internally...... consist of strongly connected species. The importance of modularity has been discussed for a long time, but no consensus on its prevalence in ecological networks has yet been reached. Progress is hampered by inadequate methods and a lack of large datasets. We analyzed 51 pollination networks including...... almost 10,000 species and 20,000 links and tested for modularity by using a recently developed simulated annealing algorithm. All networks with >150 plant and pollinator species were modular, whereas networks with

Physicochemical properties of vanadium impregnated Al-PILCs: Effect of vanadium source

Energy Technology Data Exchange (ETDEWEB)

Balci, Suna, E-mail: sunabalci@gazi.edu.tr; Tecimer, Aylin

2015-03-01

Graphical abstract: - Highlights: • Vanadium was incorporated into Al-PILC using NaVO{sub 3} or VOSO{sub 4}·3H{sub 2}O precursors by wet impregnation, washing after wet impregnation and impregnation from solution methods. • The layered structure of the supports was retained after the vanadium incorporation. • Incorporation took place both by settling and ion exchange mechanism with the treatment VOSO{sub 4}·3H{sub 2}O precursor while settling was dominant in the use of NaVO{sub 3} precursor. • Treatment with VOSO{sub 4}·3H{sub 2}O which was acidic in solution resulted in more structural deformation. • V{sub 2}O{sub 5} and VO{sub 2} were found as the major oxide forms on the impregnated samples. Loading of vanadyl sulfate hydrate (VOSO{sub 4}·H{sub 2}O) resulted in higher V/Si ratio. Most of the vanadium was bonded in +5 oxide form. • Changes in the FTIR signals after vanadium incorporation caused by Brønsted and Lewis sites, silanol, water and vanadium vibrations were occured. • Dehydroxylation of the structure took place around 300 °C. Samples obtained by impregnation and washing after wet impregnation methods resulted in similar mass losses and the wet impregnated sample showed the highest mass loss among the impregnated samples. - Summary: Clay from the Middle Anatolian previously pillared by Al{sub 13}-Keggin ions and then calcined at 300 °C (Al-PILC) was impregnated with aqueous solutions of vanadium precursors by impregnation from solution (I), wet impregnation (WI) and washing after wet impregnation (WWI) methods. The crystal and textural properties were evaluated by X-ray powder diffraction (XRD), nitrogen sorption and transmission electron microscopy (TEM) images. Vanadium incorporation into the Al-PILC resulted decreases in the basal spacing from 1.75 nm to 1.35 nm with the preserved typical layered structure. The use of sodium metavanadate (NaVO{sub 3}) as the source and the impregnation from solution as the incorporation method

Bioleaching of vanadium from barren stone coal and its effect on the transition of vanadium speciation and mineral phase

Science.gov (United States)

Wang, Xin; Lin, Hai; Dong, Ying-bo; Li, Gan-yu

2018-03-01

This study determined the optimal conditions required to obtain maximum vanadium extraction and examined the transition of mineral phases and vanadium speciation during the bioleaching process. Parameters including the initial pH value, initial Fe2+ concentration, solid load, and inoculum quantity were examined. The results revealed that 48.92wt% of the vanadium was extracted through bioleaching under optimal conditions. Comparatively, the chemical leaching yield (H2SO4, pH 2.0) showed a slower and milder increase in vanadium yield. The vanadium bioleaching yield was 35.11wt% greater than the chemical leaching yield. The Community Bureau of Reference (BCR) sequential extraction results revealed that 88.62wt% of vanadium existed in the residual fraction. The bacteria substantially changed the distribution of the vanadium speciation during the leaching process, and the residual fraction decreased to 48.44wt%. The X-ray diffraction (XRD) and Fourier transform infrared (FTIR) results provided evidence that the crystal lattice structure of muscovite was destroyed by the bacteria.

Modularity and its effects on innovation

DEFF Research Database (Denmark)

Boer, Henrike Engele Elisabeth; Hansen, Poul H. Kyvsgård

systematic work and management type of tasks, although it conflicts with the typical characteristics associated with the entrepreneur. If not managed properly, modularization can foster the modularity trap over time. At this stage intrapreneurial activities can help the organization stay ahead of the game...

Separation and estimation of lanthanides using high performance liquid chromatography

International Nuclear Information System (INIS)

Datta, Arpita; Sivaraman, N.; Vasudeva Rao, P.R.

2012-01-01

The separation efficiency of individual lanthanides depends on the stability constant of the metal-ligand complex. Therefore, stability constant data of lanthanide complexes is important in the development of high performance separation procedures. The dynamic ion exchange HPLC technique was employed at our laboratory to estimate the stability constant of lanthanides with various complexing agents. In these studies, the retention times as well as capacity factors of lanthanides and some actinides were measured as a function of CSA, complexing agent concentrations and mobile phase pH. From these studies, a correlation has been established between capacity factor of a metal ion, concentrations of ion-pairing reagent and complexing agent with the stability constant of lanthanide complex

Recovery of vanadium oxide

International Nuclear Information System (INIS)

Bates, C.P.; Clark, N.E.

1985-01-01

This invention relates to the recovery of vanadium oxide from molten metal. The invention provides a method for recovering vanadium oxide from molten metal, which includes passing oxygen and at least one coolant gas or shroud into the molten metal by way of at least one elongate lance. The invention also provides an arrangement for the recovery of vanadium oxide from molten metal, which includes at least one elongate lance extending into the molten metal. The lance is provided with at least one elongate bore extending therethrough. Means are provided to allow at least oxygen and at least one coolant gas to pass through the lance and into the molten metal

Uncovering intrinsic modular organization of spontaneous brain activity in humans.

Directory of Open Access Journals (Sweden)

Yong He

Full Text Available The characterization of topological architecture of complex brain networks is one of the most challenging issues in neuroscience. Slow (<0.1 Hz, spontaneous fluctuations of the blood oxygen level dependent (BOLD signal in functional magnetic resonance imaging are thought to be potentially important for the reflection of spontaneous neuronal activity. Many studies have shown that these fluctuations are highly coherent within anatomically or functionally linked areas of the brain. However, the underlying topological mechanisms responsible for these coherent intrinsic or spontaneous fluctuations are still poorly understood. Here, we apply modern network analysis techniques to investigate how spontaneous neuronal activities in the human brain derived from the resting-state BOLD signals are topologically organized at both the temporal and spatial scales. We first show that the spontaneous brain functional networks have an intrinsically cohesive modular structure in which the connections between regions are much denser within modules than between them. These identified modules are found to be closely associated with several well known functionally interconnected subsystems such as the somatosensory/motor, auditory, attention, visual, subcortical, and the "default" system. Specifically, we demonstrate that the module-specific topological features can not be captured by means of computing the corresponding global network parameters, suggesting a unique organization within each module. Finally, we identify several pivotal network connectors and paths (predominantly associated with the association and limbic/paralimbic cortex regions that are vital for the global coordination of information flow over the whole network, and we find that their lesions (deletions critically affect the stability and robustness of the brain functional system. Together, our results demonstrate the highly organized modular architecture and associated topological properties in

Physically-based impedance modeling of the negative electrode in All-Vanadium Redox Flow Batteries: insight into mass transport issues

International Nuclear Information System (INIS)

Zago, M.; Casalegno, A.

2017-01-01

Highlights: •Performance losses induced by migration though the porous electrode are negligible. •Convection at carbon fiber results in a linear branch at low frequency in Nyquist plot. •When the reaction is concentrated, diffusion losses though the electrode diminishes. •Diffusion process in the pores becomes more limiting at high current. •Charge transfer resistance decreases with increasing current. -- Abstract: Mass transport of the electrolyte over the porous electrode is one of the most critical issues hindering Vanadium Redox Flow Battery commercialization, leading to increased overpotential at high current and limiting system power density. In this work, a 1D physically based impedance model of Vanadium Redox Flow Battery negative electrode is developed, taking into account electrochemical reactions, convection at carbon fiber, diffusion in the pores and migration and diffusion through electrode thickness. The model is validated with respect to experimental data measured in a symmetric cell hardware, which allows to keep the State of Charge constant during the measurement. The physically based approach permits to elucidate the origin of different impedance features and quantify the corresponding losses. Charge transfer resistance decreases with increasing current and is generally lower compared to the ones related to mass transport phenomena. Migration losses through the porous electrode are negligible, while convection at carbon fiber is relevant and in Nyquist plot results in a linear branch at low frequency. In presence of significant convection losses the reaction tends to concentrate close to the channel: this leads to a reduction of diffusion losses through the electrode, while diffusion process in the pores becomes more limiting.

The extraction of vanadium (IV) from hydrochloric acid solutions by tricaprylmethylammonium chloride and trioctylamine

International Nuclear Information System (INIS)

Nakamura, Takato; Sato, Taichi

1980-01-01

The extraction of vanadium (IV) from hydrochloric acid solutions by tricaprylmethylammonium chloride (R 3 RNCl, Aliquat-336) and trioctylamine (R 3 N, TOA) in benzene has been investigated under various conditions. In addition, the extraction behaviour of vanadium into the organic phase has been examined by spectrophotometry and electron spin resonance (ESR) spectroscopy. From the distribution data, it is concluded that the extractions of vanadium (IV) from hydrochloric acid solutions by Aliquat-336 and TOA are expressed as VOCl 3 - (aq) + R 3 R'NCl(org) reversible R 3 R'NVOCl 3 (org) + Cl - (aq) and VOCl 2 (aq) + R 3 NHCl(org) reversible R 3 NHVOCl 3 (org) The electronic spectral and ESR results suggest that the complexes, R 3 R'NVOCl 3 and R 3 NH.VOCl 3 , formed in the organic phase are not always stable, but easily hydrolized or oxidized. (author)

Systemic analysis of thermodynamic properties of lanthanide halides

International Nuclear Information System (INIS)

Mirsaidov, U.; Badalov, A.; Marufi, V.K.

1992-01-01

System analysis of thermodynamic characteristics of lanthanide halides was carried out. A method making allowances for the influence of spin and orbital moments of momentum of the main states of lanthanide trivalent ions in their natural series was employed. Unknown in literature thermodynamic values were calculated and corrected for certain compounds. The character of lanthanide halide thermodynamic parameter change depending on ordinal number of the metals was ascertained. Pronouncement of tetrad-effect in series of compounds considered was pointed out

Syntheses, structures, photoluminescence and photocatalysis of 2D layered lanthanide-carboxylates with 2, 2′-dithiodibenzoic acid

Energy Technology Data Exchange (ETDEWEB)

Ding, Ling; Zhong, Jie-Cen; Qiu, Xing-Tai; Sun, Yan-Qiong, E-mail: sunyq@fzu.edu.cn; Chen, Yi-Ping

2017-02-15

Two series of lanthanide-carboxylates, [Ln(2,2′-dtba)(2,2′-Hdtba)(EtOH)]{sub n} (I:Ln=Eu(1a), Dy(1b)) and [Ln(2,2′-dtba)(2,2′-Hdtba)(4,4′-bpy){sub 0.5}]{sub n} (II:Ln=Eu(2a), Dy(2b), Tb(2c) 2,2′-H{sub 2}dtba=2,2′-dithiodibenzoic acid, 4,4′-bpy=4,4′-bipyridine) have been synthesized under hydrothermal conditions. Interestingly, the H{sub 2}dtba organic ligand was generated by in situ S–S reaction of 2-mercaptobenzoic acid. Compounds I and II possess different 2D layered structures based on similar 1D [Ln(2,2′-dtba)]{sup +} chains. Photoluminescence studies reveal that compounds I and II exhibit strong lanthanide characteristic emission bands. Remarkably, Compounds 1b and 2a both exhibit good photocatalytic activity for degradation of Rhodamine-B (Rh-B) under the simulated sunlight irradiation. - Graphical abstract: Two series of lanthanide-carboxylates have been in situ synthesized under hydrothermal conditions. The lanthanide-carboxylates exhibit strong lanthanide characteristic emission bands and good photocatalytic activity for degradation of Rhodamine-B. - Highlights: • 2D layered lanthanide-carboxylates with 2,2′-dithiodibenzoic acid. • In situ S–S reaction of 2-mercaptobenzoic acid under hydrothermal condition. • The Emission spectra of I and II exhibit the characteristic transition of lanthanide ions. • Compounds 1b and 2a exhibit good photocatalytic activity for degradation of Rhodamine-B.

Determination of vanadium

International Nuclear Information System (INIS)

Stepin, V.V.; Kurbatova, V.I.; Fedorova, N.D.

1980-01-01

Titrimetric and potentiometric methods of vanadium determination in ferrovanadium are developed. The essence of the titrimetric method using phenylanthranilic acid as indicator is in the following. Ferrovanadium weighed amount is dissolved in H 2 SO 4 , vanadium is oxidated by potassium permanganate to V(5) and is titrated by a solution of double salt of sulfuric Fe(2) and ammonium in the presence of indicator. Potentiometric titration is carried out using the same indicator [ru

Slag recycling of irradiated vanadium

International Nuclear Information System (INIS)

Gorman, P.K.

1995-01-01

An experimental inductoslag apparatus to recycle irradiated vanadium was fabricated and tested. An experimental electroslag apparatus was also used to test possible slags. The testing was carried out with slag materials that were fabricated along with impurity bearing vanadium samples. Results obtained include computer simulated thermochemical calculations and experimentally determined removal efficiencies of the transmutation impurities. Analyses of the samples before and after testing were carried out to determine if the slag did indeed remove the transmutation impurities from the irradiated vanadium

Lanthanide-doped luminescent nanomaterials from fundamentals to bioapplications

CERN Document Server

Chen, Xueyuan; Tu, Datao

2014-01-01

Lanthanide-Doped Luminescent Nanomaterials reviews the latest advances in the development of lanthanide-doped luminescent inorganic nanoparticles for potential bioapplications. This book covers the chemical and physical fundamentals of these nanoparticles, such as the controlled synthesis methodology, surface modification chemistry, optical physics, and their promising applications in diverse bioassays, with an emphasis on heterogeneous and homogeneous in-vitro biodetection of tumor biomarkers. This book is intended for those readers who are interested in systematically understanding the materials design strategy, optical behavior of lanthanide ions, and practical bioapplications of lanthanide nanoparticles. It primarily focuses on the interdisciplinary frontiers in chemistry, physics and biological aspects of luminescent nanomaterials. All chapters were written by scientists active in this field and for a broad audience, providing both beginners and advanced researchers with comprehensive information on the ...

Modularity and hierarchical organization of action programs in children's acquisition of graphic skills.

Science.gov (United States)

Manoel, Edison de J; Dantas, Luiz; Gimenez, Roberto; de Oliveira, Dalton Lustosa

2011-10-01

The organization of actions is based on modules in memory as a result of practice, easing the demand of performing more complex actions. If this modularization occurs, the elements of the module must remain invariant in new tasks. To test this hypothesis, 35 children, age 10 yr., practiced a graphic criterion task on a digital tablet and completed a complex graphic task enclosing the previous one. Total movement and pause times to draw the figure indicated skill acquisition. A module was identified by the variability of relative timing, pause time, and sequencing. Total movement to perform the criterion task did not increase significantly when it was embedded in the more complex task. Modularity was evidenced by the stability of relative timing and pause time and sequencing. The spatial position of new elements did not perturb the module, so the grammar of action may still have been forming.

Methods for making lithium vanadium oxide electrode materials

Science.gov (United States)

Schutts, Scott M.; Kinney, Robert J.

2000-01-01

A method of making vanadium oxide formulations is presented. In one method of preparing lithium vanadium oxide for use as an electrode material, the method involves: admixing a particulate form of a lithium compound and a particulate form of a vanadium compound; jet milling the particulate admixture of the lithium and vanadium compounds; and heating the jet milled particulate admixture at a temperature below the melting temperature of the admixture to form lithium vanadium oxide.

Optimization of the radio lanthanides separation device

International Nuclear Information System (INIS)

Vera T, A. L.

2009-01-01

At present, cancer is a major cause of mortality in our country, therefore, its prevention, diagnosis and treatment are vital to health systems. The cancer treatment and other diseases, from monoclonal antibodies, peptides, or amino macro aggregates marked with beta particle emitting radionuclides, is a highly promising field. The radioactive lanthanides: Pm, Tb, Ho, and Lu are beta emitters, which possess nuclear and chemical properties, which have shown their feasibility as radioisotopes of radiotherapeutic use. However, these radioisotopes are not available commercially in this connection, the Research Laboratory of Radioactive Materials of the National Institute of Nuclear Research, has developed the methodology of production of these radioisotopes and based on this work is designed, constructed and installed the radio lanthanides separation device for the radioisotopes production routinely. This device is part of the cell, , which has and auxiliary air service, an extraction system and is protected with a 10 cm of lead shielding. The radio lanthanides separation device is manual and easy to handle. The main function of this equipment is the radio lanthanides separation from extractive chromatography through packed columns with a commercial resin (Ln SPS) and coated on the top and bottom by fiberglass. The radio lanthanides separation device comprises a main carrousel where the separation columns and elution containers are mounted. It also has a system of open irradiation vials, carrier samples for columns and glassware. This paper presents a detailed description of the radio lanthanides separation device and its management, which allows the radioisotopes production Pm, Tb, Ho, and Lu from the separation of its parents Nd, Dy, Gd, and Yb respectively. (Author)

Nonaqueous method for dissolving lanthanide and actinide metals

International Nuclear Information System (INIS)

Crisler, L.R.

1975-01-01

Lanthanide and actinide beta-diketonate complex molecular compounds are produced by reacting a beta-diketone compound with a lanthanide or actinide element in the elemental metallic state in a mixture of carbon tetrachloride and methanol

A comparative assessment of the acute inhalation toxicity of vanadium compounds.

Science.gov (United States)

Rajendran, N; Seagrave, J C; Plunkett, L M; MacGregor, J A

2016-11-01

Vanadium compounds have become important in industrial processes, resulting in workplace exposure potential and are present in ambient air as a result of fossil fuel combustion. A series of acute nose-only inhalation toxicity studies was conducted in both rats and mice in order to obtain comparative data on the acute toxicity potential of compounds used commercially. V 2 O 3 , V 2 O 4 , and V 2 O 5 , which have different oxidation states (+3, +4, +5, respectively), were delivered as micronized powders; the highly water-soluble and hygroscopic VOSO 4 (+4) could not be micronized and was instead delivered as a liquid aerosol from an aqueous solution. V 2 O 5 was the most acutely toxic micronized powder in both species. Despite its lower overall percentage vanadium content, a liquid aerosol of VOSO 4 was more toxic than the V 2 O 5 particles in mice, but not in rats. These data suggest that an interaction of characteristics, i.e., bioavailability, solubility and oxidation state, as well as species sensitivity, likely affect the toxicity potential of vanadium compounds. Based on clinical observations and gross necropsy findings, the lung appeared to be the target organ for all compounds. The level of hazard posed will depend on the specific chemical form of the vanadium. Future work to define the inhalation toxicity potential of vanadium compounds of various oxidation states after repeated exposures will be important in understanding how the physico-chemical and biological characteristics of specific vanadium compounds interact to affect toxicity potential and the potential risks posed to human health.

Vanadium pentoxide nanoparticles mimic vanadium haloperoxidases and thwart biofilm formation

Science.gov (United States)

Natalio, Filipe; André, Rute; Hartog, Aloysius F.; Stoll, Brigitte; Jochum, Klaus Peter; Wever, Ron; Tremel, Wolfgang

2012-08-01

Marine biofouling--the colonization of small marine microorganisms on surfaces that are directly exposed to seawater, such as ships' hulls--is an expensive problem that is currently without an environmentally compatible solution. Biofouling leads to increased hydrodynamic drag, which, in turn, causes increased fuel consumption and greenhouse gas emissions. Tributyltin-free antifouling coatings and paints based on metal complexes or biocides have been shown to efficiently prevent marine biofouling. However, these materials can damage the environment through metal leaching (for example, of copper and zinc) and bacteria resistance. Here, we show that vanadium pentoxide nanowires act like naturally occurring vanadium haloperoxidases to prevent marine biofouling. In the presence of bromide ions and hydrogen peroxide, the nanowires catalyse the oxidation of bromide ions to hypobromous acid (HOBr). Singlet molecular oxygen (1O2) is formed and this exerts strong antibacterial activity, which prevents marine biofouling without being toxic to marine biota. Vanadium pentoxide nanowires have the potential to be an alternative approach to conventional anti-biofouling agents.

Vanadium recycling for fusion reactors

International Nuclear Information System (INIS)

Dolan, T.J.; Butterworth, G.J.

1994-04-01

Very stringent purity specifications must be applied to low activation vanadium alloys, in order to meet recycling goals requiring low residual dose rates after 50--100 years. Methods of vanadium production and purification which might meet these limits are described. Following a suitable cooling period after their use, the vanadium alloy components can be melted in a controlled atmosphere to remove volatile radioisotopes. The aim of the melting and decontamination process will be the achievement of dose rates low enough for ''hands-on'' refabrication of new reactor components from the reclaimed metal. The processes required to permit hands-on recycling appear to be technically feasible, and demonstration experiments are recommended. Background information relevant to the use of vanadium alloys in fusion reactors, including health hazards, resources, and economics, is provided

Modularity and the spread of perturbations in complex dynamical systems.

Science.gov (United States)

Kolchinsky, Artemy; Gates, Alexander J; Rocha, Luis M

2015-12-01

We propose a method to decompose dynamical systems based on the idea that modules constrain the spread of perturbations. We find partitions of system variables that maximize "perturbation modularity," defined as the autocovariance of coarse-grained perturbed trajectories. The measure effectively separates the fast intramodular from the slow intermodular dynamics of perturbation spreading (in this respect, it is a generalization of the "Markov stability" method of network community detection). Our approach captures variation of modular organization across different system states, time scales, and in response to different kinds of perturbations: aspects of modularity which are all relevant to real-world dynamical systems. It offers a principled alternative to detecting communities in networks of statistical dependencies between system variables (e.g., "relevance networks" or "functional networks"). Using coupled logistic maps, we demonstrate that the method uncovers hierarchical modular organization planted in a system's coupling matrix. Additionally, in homogeneously coupled map lattices, it identifies the presence of self-organized modularity that depends on the initial state, dynamical parameters, and type of perturbations. Our approach offers a powerful tool for exploring the modular organization of complex dynamical systems.

Vacancy distribution in nonstoichiometric vanadium monoxide

International Nuclear Information System (INIS)

Gusev, A.I.; Davydov, D.A.; Valeeva, A.A.

2011-01-01

Graphical abstract: Display Omitted Research highlights: → A certain fraction of vanadium atoms in disordered cubic vanadium monoxide VO y and ordered tetragonal phase V 52 O 64 is located in tetrahedral positions of a basic cubic lattice. → These positions are never occupied by any atoms in other strongly nonstoichiometric carbides, nitrides and oxides. → Both disordered and ordered structures of vanadium monoxide are characterized by the presence of short-range order of displacements in the oxygen sublattice and short-range order of substitution in the metal sublattice. → The short-range order of displacement is caused by the local displacements of O atoms from V (t) atoms occupying tetrahedral positions. The short-range order of substitution appears because V (t) atoms in the tetrahedral positions are always in the environment of four vacancies □ of the vanadium sublattice. - Abstract: Structural vacancy distribution in the crystal lattice of the tetragonal V 52 O 64 superstructure which is formed on the basis of disordered superstoichiometric cubic vanadium monoxide VO y ≡V x O z is experimentally determined and the presence of significant local atomic displacements and large local microstrains in a crystal lattice of real ordered phase is established. It is shown that the relaxation of local microstrains takes place owing to the basic disordered cubic phase grain refinement and a formation of ordered phase domains. The ordered phase domains grow in the direction from the boundaries to the centre of grains of the disordered basic cubic phase. Isothermal evolution at 970 K of the average domain size in ordered VO 1.29 vanadium monoxide is established. It is shown that the short-range order presents in a metal sublattice of disordered cubic VO y vanadium monoxide. The character of the short-range order is such that vanadium atoms occupying tetrahedral positions are in the environment of four vacant sites of the vanadium sublattice. This means that the

A sensitive fluorescent sensor of lanthanide ions

CERN Document Server

Bekiari, V; Lianos, P

2003-01-01

A fluorescent probe bearing a diazostilbene chromophore and a benzo-15-crown-5 ether moiety is a very efficient sensor of lanthanide ions. The ligand emits strong fluorescence only in the presence of specific ions, namely lanthanide ions, while the emission wavelength is associated with a particular ion providing high sensitivity and resolution.

Chiral Silver-Lanthanide Metal-Organic Frameworks Comprised of One-Dimensional Triple Right-Handed Helical Chains Based on [Ln7(μ3-OH)8]13+ Clusters.

Science.gov (United States)

Guo, Yan; Zhang, Lijuan; Muhammad, Nadeem; Xu, Yan; Zhou, Yunshan; Tang, Fang; Yang, Shaowei

2018-02-05

Three new isostructural chiral silver-lanthanide heterometal-organic frameworks [Ag 3 Ln 7 (μ 3 -OH) 8 (bpdc) 6 (NO 3 ) 3 (H 2 O) 6 ](NO 3 )·2H 2 O [Ln = Eu (1), Tb (2, Sm (3); H 2 bpdc = 2,2'-bipyridine-3,3'-dicarboxylic acid] based on heptanuclear lanthanide clusters [Ln 7 (μ 3 -OH) 8 ] 13+ comprised of one-dimensional triple right-handed helical chains were hydrothermally synthesized. Various means such as UV-vis spectroscopy, IR spectroscopy, elemental analysis, powder X-ray diffraction, and thermogravimetric/differential thermal analysis were used to characterize the compounds, wherein compound 3 was crystallographically characterized. In the structure of compound 3, eight μ 3 -OH - groups link seven Sm 3+ ions, forming a heptanuclear cluster, [Sm 7 (μ 3 -OH) 8 ] 13+ , and the adjacent [Sm 7 (μ 3 -OH) 8 ] 13+ clusters are linked by the carboxylic groups of bpdc 2- ligands, leading to the formation of a one-dimensional triple right-handed helical chain. The adjacent triple right-handed helical chains are further joined together by coordinating the pyridyl N atoms of the bpdc 2- ligands with Ag + , resulting in a chiral three-dimensional silver(I)-lanthanide(III) heterometal-organic framework with one-dimensional channels wherein NO 3 - anions and crystal lattice H 2 O molecules are trapped. The compounds were studied systematically with respect to their photoluminescence properties and energy-transfer mechanism, and it was found that H 2 bpdc (the energy level for the triplet states of the ligand H 2 bpdc is 21505 cm -1 ) can sensitize Eu 3+ luminescence more effectively than Tb 3+ and Sm 3+ luminescence because of effective energy transfer from bpdc 2- to Eu 3+ under excitation in compound 1.

Hierarchical modular structure enhances the robustness of self-organized criticality in neural networks

International Nuclear Information System (INIS)

Wang Shengjun; Zhou Changsong

2012-01-01

One of the most prominent architecture properties of neural networks in the brain is the hierarchical modular structure. How does the structure property constrain or improve brain function? It is thought that operating near criticality can be beneficial for brain function. Here, we find that networks with modular structure can extend the parameter region of coupling strength over which critical states are reached compared to non-modular networks. Moreover, we find that one aspect of network function—dynamical range—is highest for the same parameter region. Thus, hierarchical modularity enhances robustness of criticality as well as function. However, too much modularity constrains function by preventing the neural networks from reaching critical states, because the modular structure limits the spreading of avalanches. Our results suggest that the brain may take advantage of the hierarchical modular structure to attain criticality and enhanced function. (paper)

Possible Cardiotoxic Effects of Vanadium

Directory of Open Access Journals (Sweden)

Parveen Parkash

1990-12-01

Full Text Available Vanadium, a ubiquitous element, is physiologically and pharmacologically an active substance and is present in most of mammalian tissues Jandhala and Horn, 1983. Large corpus of information exists on the mode of action of vanadium on cardiac muscles (Jandhala and Horn, 1983., Solaro et al, 1980, but the basis of pharma­cological lesion underlying its cardiac toxi­city is still poorly understood. Except for the solitary report of Lewis (1958 to best of our knowledge no information exists on the effect of vanadium on the functioning of heart as shown by electrocardiography.Large amounts of vanadium are relea­sed into atmosphere by combustion of fossil fuel (Vouk, 1979 and due to rapid indus­trialisation its environmental concentra­tion is reported to be increasing (Goldberg et al, 1974., Jaffe and Walters, 1977., Vouk, 1979. This necessitates the monitoring of its environmental and occupational hazards. In the present study cardiac side effects of vanadium, as revealed through ECG has been investigated in rabbits, since the electrocardiogram of rabbit resembles with of man in essential details (Weisborth et al, 1974.

Thermophysical data of liquid vanadium

International Nuclear Information System (INIS)

Pottlacher, G.; Huepf, T.; Wilthan, B.; Cagran, C.

2007-01-01

Although vanadium is commonly used as an additive in the steel production, literature data for thermophysical properties of vanadium around the melting point are sparse and show, where available a variation over a wide range. This manifests especially in the melting temperature (variation of ±30 K), heat of fusion, or specific enthalpy. This recent work presents the results of thermophysical measurements on vanadium including normal spectral emissivity at 684.5 nm. The aim was to obtain another full dataset of properties (enthalpy, heat of fusion, electrical resistivity, thermal conductivity, emissivity) of liquid vanadium to either confirm existing recommendations for certain properties or presenting newer measurements for comparison leading towards such recommendations. Summarizing, the following results for thermophysical properties at the melting point have been obtained: radiance temperature at melting (650 nm) T r,m = 1993 K, melting temperature T m = 2199 K, normal spectral emissivity at melting (684.5 nm) ε = 0.353. An observed feature of all measured data and results is, that a much better agreement with literature references exists for the liquid phase than in the solid state, thus we have restricted the presentation to liquid vanadium

Hierarchical modularity in human brain functional networks

Directory of Open Access Journals (Sweden)

David Meunier

2009-10-01

Full Text Available The idea that complex systems have a hierarchical modular organization originates in the early 1960s and has recently attracted fresh support from quantitative studies of large scale, real-life networks. Here we investigate the hierarchical modular (or “modules-within-modules” decomposition of human brain functional networks, measured using functional magnetic resonance imaging (fMRI in 18 healthy volunteers under no-task or resting conditions. We used a customized template to extract networks with more than 1800 regional nodes, and we applied a fast algorithm to identify nested modular structure at several hierarchical levels. We used mutual information, 0 < I < 1, to estimate the similarity of community structure of networks in different subjects, and to identify the individual network that is most representative of the group. Results show that human brain functional networks have a hierarchical modular organization with a fair degree of similarity between subjects, I=0.63. The largest 5 modules at the highest level of the hierarchy were medial occipital, lateral occipital, central, parieto-frontal and fronto-temporal systems; occipital modules demonstrated less sub-modular organization than modules comprising regions of multimodal association cortex. Connector nodes and hubs, with a key role in inter-modular connectivity, were also concentrated in association cortical areas. We conclude that methods are available for hierarchical modular decomposition of large numbers of high resolution brain functional networks using computationally expedient algorithms. This could enable future investigations of Simon's original hypothesis that hierarchy or near-decomposability of physical symbol systems is a critical design feature for their fast adaptivity to changing environmental conditions.

Organização do trabalho na cadeia de suprimentos: os casos de uma planta modular e de uma tradicional na indústria automobilística Work organization in the supply chain: the cases of a modular and a traditional plant in the automotive industry

Directory of Open Access Journals (Sweden)

Alessandra Rachid

2006-08-01

Full Text Available Este artigo analisa a influência das empresas clientes na organização do trabalho de seus fornecedores em duas cadeias de suprimentos da indústria automobilística, uma comandada por uma planta modular e outra organizada num arranjo tradicional. Na cadeia tradicional, são examinadas as formas de organização do trabalho de uma fábrica de motores e de dez de seus fornecedores diretos. No caso da planta modular, produtora de caminhões e ônibus, examina-se a organização do trabalho no sistema modular como um todo, explorando-se as peculiaridades deste tipo de arranjo. Os resultados da pesquisa apontam que, na planta modular, a influência da montadora sobre a organização do trabalho configura-se de forma mais direta com relação a salários e jornada de trabalho. Na cadeia tradicional, a influência ocorre de forma indireta, por meio de exigências voltadas para outras áreas de gestão.This paper analyzes the influence that buyer firms have on their suppliers' work organization in two supply chains in the automotive industry. One of the supply chains is controlled by a modular plant and the other is organized in the traditional way. In the traditional supply chain, the work organization of an engine manufacturer plant as well as of ten of its suppliers is examined. In the modular plant, a truck and bus manufacturer, the work organization of the whole modular system is examined, exploring the peculiarities of this kind of arrangement. The results of the research shows that in the modular plant the assembler's influence over the work organization, relating to aspects like wages and work time, is more direct. In the traditional supply chain, the influence happens in a indirect way, through requirements done to other areas of management.

From metal-organic squares to porous zeolite-like supramolecular assemblies

KAUST Repository

Wang, Shuang

2010-12-29

We report the synthesis, structure, and characterization of two novel porous zeolite-like supramolecular assemblies, ZSA-1 and ZSA-2, having zeolite gis and rho topologies, respectively. The two compounds were assembled from functional metal-organic squares (MOSs) via directional hydrogen-bonding interactions and exhibited permanent microporosity and thermal stability up to 300 °C. © 2010 American Chemical Society.

Vanadium alloys for structural applications in fusion systems: A review of vanadium alloy mechanical and physical properties

Energy Technology Data Exchange (ETDEWEB)

Loomis, B.A.; Smith, D.L.

1991-12-16

The current knowledge is reviewed on (1) the effects of neutron irradiation on tensile strength and ductility, ductile-brittle transition temperature, creep, fatigue, and swelling of vanadium-base alloys, (2) the compatibility of vanadium-base alloys with liquid lithium, water, and helium environments, and (3) the effects of hydrogen and helium on the physical and mechanical properties of vanadium alloys that are potential candidates for structural materials applications in fusion systems. Also, physical and mechanical properties issues are identified that have not been adequately investigated in order to qualify a vanadium-base alloy for the structural material in experimental fusion devices and/or in fusion reactors.

Vanadium alloys for structural applications in fusion systems: A review of vanadium alloy mechanical and physical properties

International Nuclear Information System (INIS)

Loomis, B.A.; Smith, D.L.

1991-01-01

The current knowledge is reviewed on (1) the effects of neutron irradiation on tensile strength and ductility, ductile-brittle transition temperature, creep, fatigue, and swelling of vanadium-base alloys, (2) the compatibility of vanadium-base alloys with liquid lithium, water, and helium environments, and (3) the effects of hydrogen and helium on the physical and mechanical properties of vanadium alloys that are potential candidates for structural materials applications in fusion systems. Also, physical and mechanical properties issues are identified that have not been adequately investigated in order to qualify a vanadium-base alloy for the structural material in experimental fusion devices and/or in fusion reactors

Vanadium bioavailability in soils amended with blast furnace slag

Energy Technology Data Exchange (ETDEWEB)

Larsson, Maja A., E-mail: maja.larsson@slu.se [Department of Soil and Environment, Swedish University of Agricultural Sciences, P.O. Box 7014, 750 07 Uppsala (Sweden); Baken, Stijn, E-mail: stijn.baken@ees.kuleuven.be [Department of Earth and Environmental Sciences, Leuven University, Kasteelpark Arenberg 20 bus 2459, 3001 Leuven (Belgium); Smolders, Erik, E-mail: erik.smolders@ees.kuleuven.be [Department of Earth and Environmental Sciences, Leuven University, Kasteelpark Arenberg 20 bus 2459, 3001 Leuven (Belgium); Cubadda, Francesco, E-mail: francesco.cubadda@iss.it [Department of Food Safety and Veterinary Public Health, Istituto Superiore di Sanità, Viale Regina Elena 299, Rome 00161 (Italy); Gustafsson, Jon Petter, E-mail: jon-petter.gustafsson@slu.se [Department of Soil and Environment, Swedish University of Agricultural Sciences, P.O. Box 7014, 750 07 Uppsala (Sweden); Division of Land and Water Resources Engineering, KTH Royal Institute of Technology, Brinellvägen 28, 100 44 Stockholm (Sweden)

2015-10-15

Blast furnace (BF) slags are commonly applied as soil amendments and in road fill material. In Sweden they are also naturally high in vanadium. The aim of this study was to assess the vanadium bioavailability in BF slags when applied to soil. Two soils were amended with up to 29% BF slag (containing 800 mg V kg{sup −1}) and equilibrated outdoors for 10 months before conducting a barley shoot growth assay. Additional soil samples were spiked with dissolved vanadate(V) for which assays were conducted two weeks (freshly spiked) and 10 months (aged) after spiking. The BF slag vanadium was dominated by vanadium(III) as shown by V K-edge XANES spectroscopy. In contrast, results obtained by HPLC-ICP-MS showed that vanadium(V), the most toxic vanadium species, was predominant in the soil solution. Barley shoot growth was not affected by the BF slag additions. This was likely due to limited dissolution of vanadium from the BF slag, preventing an increase of dissolved vanadium above toxic thresholds. The difference in vanadium bioavailability among treatments was explained by the vanadium concentration in the soil solution. It was concluded that the vanadium in BF slag is sparingly available. These findings should be of importance in environmental risk assessment.

Lanthanides in the frame of Molecular Magnetism

Directory of Open Access Journals (Sweden)

Gatteschi D.

2014-07-01

Full Text Available Molecular magnetism is producing new types of materials which cover up to date aspects of basic science together with possible applications. This article highlights recent results from the point of view of lanthanides which are now intensively used to produce single molecule magnets, single chain and single ion magnets. After a short introduction reminding the main steps of development of molecular magnetism, the basic properties of lanthanides will be covered highlighting important features which are enhanced by the electronic structure of lanthanides, like spin frustration and chirality, anisotropy and non collinear axes in zero and one dimensional materials. A paragraph of conclusions will discuss what has been done and theperspectives to be expected.

Highly Water-Stable Lanthanide-Oxalate MOFs with Remarkable Proton Conductivity and Tunable Luminescence.

Science.gov (United States)

Zhang, Kun; Xie, Xiaoji; Li, Hongyu; Gao, Jiaxin; Nie, Li; Pan, Yue; Xie, Juan; Tian, Dan; Liu, Wenlong; Fan, Quli; Su, Haiquan; Huang, Ling; Huang, Wei

2017-09-01

Although proton conductors derived from metal-organic frameworks (MOFs) are highly anticipated for various applications including solid-state electrolytes, H 2 sensors, and ammonia synthesis, they are facing serious challenges such as poor water stability, fastidious working conditions, and low proton conductivity. Herein, we report two lanthanide-oxalate MOFs that are highly water stable, with so far the highest room-temperature proton conductivity (3.42 × 10 -3 S cm -1 ) under 100% relative humidity (RH) among lanthanide-based MOFs and, most importantly, luminescent. Moreover, the simultaneous response of both the proton conductivity and luminescence intensity to RH allows the linkage of proton conductivity with luminescence intensity. This way, the electric signal of proton conductivity variation versus RH will be readily translated to optical signal of luminescence intensity, which can be directly visualized by the naked eye. If proper lanthanide ions or even transition-metal ions are used, the working wavelengths of luminescence emissions can be further extended from visible to near infrared light for even wider-range applications. © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Direct nano ESI time-of-flight mass spectrometric investigations on lanthanide BTP complexes in the extraction-relevant diluent 1-octanol

International Nuclear Information System (INIS)

Steppert, M.; Walther, C.; Geist, A.; Fanghanel, Th.

2009-01-01

The present work focuses on investigations of a highly selective ligand for Am(III)/Ln(III) separation: bis-triazinyl-pyridine (BTP). By means of nano-electro-spray mass spectrometry, complex formation of BTP with selected elements of the lanthanide series is investigated. We show that the diluent drastically influences complex speciation. Measurements obtained in the extraction-relevant diluent 1-octanol show the occurrence of Ln(BTP) i (i 1-3) species in different relative abundances, depending on the lanthanide used. Here, the relative abundances of the Ln(BTP) 3 complexes correlate with the distribution ratios for extraction to the organic phase of the respective lanthanide. (authors)

Determination of Leachable Vanadium (V) in Sediment

African Journals Online (AJOL)

NICO

A method for speciation of vanadium in solid samples was developed for quantification of vanadium(+5) in solid samples of sediment Certified Reference Materials ... element in such environmental samples as soil, sediments and plants.3,4–5 Validation of the ... Sample Preparation for the Determination of. Vanadium(+5).

Effect of lanthanide contraction on the mixed polyamine systems Ln/Sb/Se/(en+dien) and Ln/Sb/Se/(en+trien): Syntheses and characterizations of lanthanide complexes with a tetraelenidoantimonate ligand

International Nuclear Information System (INIS)

Zhao Jing; Liang Jingjing; Pan Yingli; Zhang Yong; Jia Dingxian

2011-01-01

Mixed polyamine systems Ln/Sb/Se/(en+dien) and Ln/Sb/Se/(en+trien) (Ln=lanthanide, en=ethylenediamine, dien=diethylenetriamine, trien=triethylenetetramine) were investigated under solvothermal conditions, and novel mixed-coordinated lanthanide(III) complexes [Ln(en) 2 (dien)(η 2 -SbSe 4 )] (Ln=Ce(1a), Nd(1b)), [Ln(en) 2 (dien)(SbSe 4 )] (Ln=Sm(2a), Gd(2b), Dy(2c)), [Ln(en)(trien)(μ-η 1 ,η 2 -SbSe 4 )] ∞ (Ln=Ce(3a), Nd(3b)) and [Sm(en)(trien)(η 2 -SbSe 4 )] (4a) were prepared. Two structural types of lanthanide selenidoantimonates were obtained across the lanthanide series in both en+dien and en+trien systems. The tetrahedral anion [SbSe 4 ] 3- acts as a monodentate ligand mono-SbSe 4 , a bidentate chelating ligand η 2 -SbSe 4 or a tridentate bridging ligand μ-η 1 ,η 2 -SbSe 4 to the lanthanide(III) center depending on the Ln 3+ ions and the mixed ethylene polyamines, indicating the effect of lanthanide contraction on the structures of the lanthanide(III) selenidoantimonates. The lanthanide selenidoantimonates exhibit semiconducting properties with E g between 2.08 and 2.51 eV. - Graphical Abstract: Two structural types of lanthanide(III) selenidoantimonates are formed in both en-dien and en-trien mixed polyamines across lanthanide series, indicating the lanthanide contraction effect on the structures of the lanthanide(III) selenidoantimonates. Highlights: → Two structural types of lanthanide selenidoantimonates are prepared across the lanthanide series in both Ln/Sb/Se/(en+dien) and Ln/Sb/Se/(en+trien) systems. → The [SbSe 4 ] 3- anion acts as a mono-SbSe 4 , a η 2 -SbSe 4 or a μ-η 1 ,η 2 -SbSe 4 ligand to the Ln 3+ ions. → The soft base ligand [SbSe 4 ] 3- can be controlled to coordinate to the Ln 3+ ions with en+dien and en+trien as co-ligands.

Study of interactions between lanthanides/actinides and humic substances by a steric exclusion chromatographic method

International Nuclear Information System (INIS)

Moulin, V.

1986-01-01

The knowledge of cation-humic matter interactions has a great importance in order to have a better understanding of the contribution of these substances to the possible transport of radioactive elements in the geosphere via groundwaters. The method chosen to study the formation of soluble species between lanthanides/actinides ions and humic acids from different origins is a chromatographic technique of gel filtration. This dynamic equilibrium method is based on the separation of the formed complex and the free cation by the porous packing gel. Different elements have been studied by this method: UO 2 2+ , Eu 3+ , Th 4+ and global interaction constants have been calculated. The application to transuranic elements is undertaken. (orig.)

Electronic structure of lanthanide scandates

Science.gov (United States)

Mizzi, Christopher A.; Koirala, Pratik; Marks, Laurence D.

2018-02-01

X-ray photoelectron spectroscopy, ultraviolet photoelectron spectroscopy, and density functional theory calculations were used to study the electronic structure of three lanthanide scandates: GdSc O3,TbSc O3 , and DySc O3 . X-ray photoelectron spectra simulated from first-principles calculations using a combination of on-site hybrid and GGA +U methods were found to be in good agreement with experimental x-ray photoelectron spectra. The hybrid method was used to model the ground state electronic structure and the GGA +U method accounted for the shift of valence state energies due to photoelectron emission via a Slater-Janak transition state approach. From these results, the lanthanide scandate valence bands were determined to be composed of Ln 4 f ,O 2 p , and Sc 3 d states, in agreement with previous work. However, contrary to previous work the minority Ln 4 f states were found to be located closer to, and in some cases at, the valence band maximum. This suggests that minority Ln 4 f electrons may play a larger role in lanthanide scandate properties than previously thought.

Structural investigation of the complexation of uranyl and lanthanide ions by CMPO-functionalized calixarenes

International Nuclear Information System (INIS)

Cherfa, S.

1998-12-01

A way to reduce the volume of nuclear wastes is to make a simultaneous extraction of actinides and lanthanides for their ulterior separation. Historically, the two first series of extractants used for the reprocessing of these wastes are the phosphine oxides and the CMPO (carbamoyl methyl phosphine oxide). In order to better know the type of complexes formed during the extraction, have been carried out structural studies concerning these two series (uranyl complexes and lanthanide nitrates). These studies have been carried out by X-ray diffraction on monocrystals. More recently, a new series of extracting molecules of lanthanides (III) and actinides (III) have been developed. It has been shown that in functionalizing an organic macrocycle of calixarene type (cyclic oligomer resulting of the poly-condensation of phenolic units) by a ligand of CMPO type, the extracting power of these molecules in terms of yield and selectivity towards the lighter lanthanides was superior to those of the CMPO alone. This study, carried out by X-ray diffraction on monocrystals of complexes formed between these ligands calix[4]arenes-CMPO (with 4 phenolic units) with uranyl and lanthanides nitrates, has allowed to define the type of the formed complexes, that is to say to establish the stoichiometry and the coordination mode (monodentate or bidentate) of the CMPO functions. These different steps of characterization have allowed too to determine the correlations existing between the complexes structures in the one hand and the selectivity and the exacerbation of the extracting power measured in liquid phase on the other hand. (O.M.)

New family of lanthanide-based inorganic-organic hybrid frameworks: Ln2(OH)4[O3S(CH2)nSO3]·2H2O (Ln = La, Ce, Pr, Nd, Sm; n = 3, 4) and their derivatives.

Science.gov (United States)

Liang, Jianbo; Ma, Renzhi; Ebina, Yasuo; Geng, Fengxia; Sasaki, Takayoshi

2013-02-18

We report the synthesis and structure characterization of a new family of lanthanide-based inorganic-organic hybrid frameworks, Ln(2)(OH)(4)[O(3)S(CH(2))(n)SO(3)]·2H(2)O (Ln = La, Ce, Pr, Nd, Sm; n = 3, 4), and their oxide derivatives. Highly crystallized samples were synthesized by homogeneous precipitation of Ln(3+) ions from a solution containing α,ω-organodisulfonate salts promoted by slow hydrolysis of hexamethylenetetramine. The crystal structure solved from powder X-ray diffraction data revealed that this material comprises two-dimensional cationic lanthanide hydroxide {[Ln(OH)(2)(H(2)O)](+)}(∞) layers, which are cross-linked by α,ω-organodisulfonate ligands into a three-dimensional pillared framework. This hybrid framework can be regarded as a derivative of UCl(3)-type Ln(OH)(3) involving penetration of organic chains into two {LnO(9)} polyhedra. Substitutional modification of the lanthanide coordination promotes a 2D arrangement of the {LnO(9)} polyhedra. A new hybrid oxide, Ln(2)O(2)[O(3)S(CH(2))(n)SO(3)], which is supposed to consist of alternating {[Ln(2)O(2)](2+)}(∞) layers and α,ω-organodisulfonate ligands, can be derived from the hydroxide form upon dehydration/dehydroxylation. These hybrid frameworks provide new opportunities to engineer the interlayer chemistry of layered structures and achieve advanced functionalities coupled with the advantages of lanthanide elements.

Effects of vanadium on population growth and Na-K-ATPase activity of the brackish water hydroid Cordylophora caspia

Energy Technology Data Exchange (ETDEWEB)

Ringelband, U.; Karbe, L. [Institut fuer Hydrobiologie und Fischereiwissenschaft, Hamburg (Germany)

1996-07-01

Vanadium, a relatively abundant heavy metal, enters the environment naturally through rock weathering. A large fraction of vanadium input is of human origin. The combustion of petroleum- and coal-products, which contain relatively high concentrations of vanadium, is one of the most important sources of the enrichment of vanadium in the environment. As it is used as an alloy, and vanadium rich iron-ores of various origin are used in steel production, the residual slag-stones of the steel industry can contain considerable vanadium concentrations. Wherever slag-stones serve as a cheap and convenient material in riverbank reinforcement, vanadium can leach into the aquatic environment. Vanadium is regarded as an essential trace element for higher animals. Cantley et al. indicated a regulatory function of vanadate in vivo. Although considerable information is available on the toxic effects of vanadium on humans, very little is known about the toxicity of vanadium towards aquatic organisms, especially invertebrates. Bell and Sargent have shown an inhibition of Na-K-ATPase activity in gills of the eel Anguilla anguilla. Holleland and Towle have demonstrated the inhibition of Na-K-ATPase activity in the gills of the shore crab Carcinus maenas. The aim of this study was to determine the toxicity of vanadium towards the brackish water hydroid Cordylophora caspia. Hydroids are known to be particularly sensitive to heavy metals and their asexual reproduction can be used in a well-established population growth test. Furthermore, the effects of vanadium on Na-K-ATPase activity in hydroids were studied in in vivo experiments, wherein the animals were exposed to sublethal concentrations of vanadium. In addition, the inhibition of Na-K-ATPase was measured in vitro, by adding vanadium to a microsomal preparation. 16 refs., 4 figs.

The role of phosphate additive in stabilization of sulphuric-acid-based vanadium(V) electrolyte for all-vanadium redox-flow batteries

Science.gov (United States)

Roznyatovskaya, Nataliya V.; Roznyatovsky, Vitaly A.; Höhne, Carl-Christoph; Fühl, Matthias; Gerber, Tobias; Küttinger, Michael; Noack, Jens; Fischer, Peter; Pinkwart, Karsten; Tübke, Jens

2017-09-01

Catholyte in all-vanadium redox-flow battery (VRFB) which consists of vanadium salts dissolved in sulphuric acid is known to be stabilized by phosphoric acid to slow down the thermal aging at temperatures higher than 40 °C. To reveal the role of phosphoric acid, the thermally-induced aggregation is investigated using variable-temperature 51V, 31P, 17O, 1H nuclear magnetic resonance (NMR) spectroscopy and dynamic light scattering (DLS). The results indicate that the thermal stabilization of vanadium(V) electrolyte is attained by the involvement of monomeric and dimeric vanadium(V) species in the reaction with phosphoric acid which is concurrent to the formation of neutral hydroxo-aqua vanadium(V) precipitation precursor. The dimers are stabilized by counter ions due to association reaction or if such stabilization is not possible, precipitation of vanadium pentoxide is favored. The evolution of particles size distributions at 50 °C in electrolyte samples containing 1.6 M vanadium and 4.0 M total sulphate and the pathways of precipitate formation are discussed. The optimal total phosphate concentration is found to be of 0.15 M. However, the induction time is assumed to be dependent not only on the total phosphate concentrations, but also on the ratio of total vanadium(V) to sulphate concentrations.

Investigations for the influence of geochemical parameters on the sorption and desorption of lanthanides and uranium onto opalinus clay as potential host rock for a repository

International Nuclear Information System (INIS)

Moeser, Christina

2010-01-01

The development of a disposal in deep geological formations for radioactive waste is a very important task for the future. The safety assessment for more than a hundred thousand years needs a full understanding of all processes of interaction between the radioactive waste and the surrounded formations. This work contributes to this understanding. The interaction between lanthanides (homologues of the actinides americium, curium and berkelium) / uranium and the host rock opalinus clay under influence of organic substances (NOM) have been analyzed and discussed. The complex system was split into 3 binary basic systems with the following interactions - Interactions between lanthanides / uranium and NOM - Interactions between lanthanides / uranium and the opalinus clay - Interactions between NOM and opalinus clay All binary systems can be influenced by geological parameters like pH, ion strength and competing cations. The sorption / desorption of the lanthanides onto the opalinus clay is analyzed via inductively coupled plasma mass spectrometry. For the investigation of the complexation behavior of metals with NOM we used capillary electrophoresis coupled with inductively coupled plasma mass spectrometry. Under these conditions the chosen model organic humic acid affected the sorption of the lanthanides onto opalinus clay favorably. The smaller organic compounds, which dominate in the composition of the clay organics, remobilized the metals after sorption onto clay and the sorption can be inhibited by NOM. Due to the reduced metal sorption onto Opalinus clay by NOM, a migration through the clay may be possible.

Influence of structure of carrier (silica gel) on texture and catalytic properties of vanadium catalysts for sulfur dioxide oxidation

International Nuclear Information System (INIS)

Simonova, L.G.; Fenelonov, V.B.; Dzis'ko, V.A.; Noskova, S.P.; Kryukova, G.N.; Litvak, G.S.

1982-01-01

The influence of initial porous structure of a carrier-silica gel on texture and catalytic properties of vanadium catalysts is considered. It is shown that low thermal stability of the carrier results not only in considerable decrease of the catalyst surface during heat treatment but also in blocking part of active component in locked pores which accounts for the activity decrease in kinetic region and formation of active component forms that can not be extracted by acid

Evaluation of the nanomechanical properties of vanadium and native oxide vanadium thin films prepared by RF magnetron sputtering

International Nuclear Information System (INIS)

Mamun, M.A.; Zhang, K.; Baumgart, H.; Elmustafa, A.A.

2015-01-01

Graphical abstract: - Highlights: • V films of 50, 75, 100 nm thickness were deposited on Si by RF magnetron sputtering. • We studied structural/mechanical properties by XRD, FE-SEM, AFM, and nanoindentation. • The hardness increased from 9.0 to 14.0 GPa for 100 to 50 nm. • The modulus showed no correlation with thickness or native oxide formation. • Native oxide formation resulted in grain enlargement and roughness reduction. - Abstract: Polycrystalline vanadium thin films of 50, 75, and 100 nm thickness were deposited by magnetron sputtering of a vanadium metal target of 2 inch diameter with 99.9% purity on native oxide covered Si substrates. One set of the fabricated samples were kept in moisture free environment and the other set was exposed to ambient air at room temperature for a long period of time that resulted in formation of native oxide prior to testing. The crystal structure and phase purity of the vanadium and the oxidized vanadium thin films were characterized by X-ray diffraction (XRD). The XRD results yield a preferential (1 1 0), and (2 0 0) orientation of the polycrystalline V films and (0 0 4) vanadium oxide (V 3 O 7 ). The vanadium films thickness were verified using field emission scanning electron microscopy and the films surface morphologies were inspected using atomic force microscopy (AFM). AFM images reveal surface roughness was observed to increase with increasing film thickness and also subsequent to oxidation at room temperature. The nanomechanical properties were measured by nanoindentation to evaluate the modulus and hardness of the vanadium and the oxidized vanadium thin films. The elastic modulus of the vanadium and the oxidized vanadium films was estimated as 150 GPa at 30% film thickness and the elastic modulus of the bulk vanadium target is estimated as 135 GPa. The measured hardness of the vanadium films at 30% film thickness varies between 9 and 14 GPa for the 100 and 50 nm films, respectively, exhibiting size effects

Color and vanadium valency in V-doped ZrO2

International Nuclear Information System (INIS)

Ren, Feng; Ishida, Shingo; Takeuchi, Nobuyuki

1993-01-01

The distribution and chemical states of vanadium in V-doped ZrO 2 were studied to clarify the origin of the color of vanadium-zirconium yellow pigment in comparison with vanadium-tin yellow pigment. ESCA data and measurements of lattice constants of V-doped ZrO 2 revealed that vanadium was dissolved mainly as V 4+ substituting for Zr in ZrO 2 lattice, and its solubility limit was 0.5 wt% as V 2 O 5 . It was found that the yellow color of vanadium-zirconium yellow was produced predominantly by the dissolved vanadium and that the contribution of vanadium oxide on ZrO 2 grains to the yellow color was about 1.30 of that of the dissolved vanadium when compared on the basis of equimolar quantity of vanadium. Most of the undissolved vanadium oxide was in an amorphous or a poorly crystallized state

A new oxidimetric reagent: potassium dichromate in a strong phosphoric acid medium-VI Potentiometric titration of vanadium(III) alone and in mixture with vanadium(IV).

Science.gov (United States)

Rao, G G; Rao, P K

1966-09-01

Vanadium(III) can be titrated at room temperature with potassium dichromate in an 8-12M phosphoric acid medium. Two potential breaks are observed in 12M phosphoric add with 0.2N potassium dichromate, the first corresponding to the oxidation of vanadium(III) to vanadium(IV) and the second to the oxidation of vanadium(IV) to vanadium(V). In titrations with 0.05N dichromate only the first break in potential is clearly observed. The method has been extended to the titration of mixtures of vanadium(III) and vanadium(IV). Conditions have also been found for the visual titration of vanadium(III) using ferroln or barium diphenylamine sulphonate as indicator.

Lanthanide ions as spectral converters for solar cells

NARCIS (Netherlands)

van der Ende, B.M.; Aarts, L.; Meijerink, A.

2009-01-01

The use of lanthanide ions to convert photons to different, more useful, wavelengths is well-known from a wide range of applications (e.g. fluorescent tubes, lasers, white light LEDs). Recently, a new potential application has emerged: the use of lanthanide ions for spectral conversion in solar

High temperature vaporization/decomposition studies of lanthanide and actinide fluorides

International Nuclear Information System (INIS)

Gibson, J.K.; Haire, R.G.

1987-01-01

Binary fluorides of the lanthanide and actinide elements comprise a fundamental class of compounds. The authors' investigations of their basic high temperature vaporization and/or decomposition behavior are aimed at elucidating more fully the thermal properties of selected tri- and tetrafluorides and extending such investigations to fluorides which have not been studied previously. Depending on the particular system and the specific experimental conditions, the authors' measurements can provide such information as the enthalpy associated with a congruent vaporization process and/or the relative stabilities of fluorides containing a lanthanide/actinide element in different oxidation states. The authors are also studying the congruent vaporization of selected lanthanide trifluorides with particular emphasis on two areas. The first concerns the variation in the enthalpies of sublimation of the trifluorides across the lanthanide series. Although this variation is rather small (δ5 kcal where ΔH/sub subl/ is approximately 100 kcal), it is larger than observed for other lanthanide trihalides and is unusually irregular. To examine this reported variation more closely, they are attempting to measure relative vapor pressures/enthalpies of vaporization by studying mixtures of two or more lanthanide trifluorides by the technique discussed above

Thermal-Economic Modularization of Small, Organic Rankine Cycle Power Plants for Mid-Enthalpy Geothermal Fields

Directory of Open Access Journals (Sweden)

Yodha Y. Nusiaputra

2014-07-01

Full Text Available The costs of the surface infrastructure in mid-enthalpy geothermal power systems, especially in remote areas, could be reduced by using small, modular Organic Rankine Cycle (ORC power plants. Thermal-economic criteria have been devised to standardize ORC plant dimensions for such applications. We designed a modular ORC to utilize various wellhead temperatures (120–170 °C, mass flow rates and ambient temperatures (−10–40 °C. A control strategy was developed using steady-state optimization, in order to maximize net power production at off-design conditions. Optimum component sizes were determined using specific investment cost (SIC minimization and mean cashflow (MCF maximization for three different climate scenarios. Minimizing SIC did not yield significant benefits, but MCF proved to be a much better optimization function.

Lanthanide Selective Sorbents: Self-Assembled Monolayers on Mesoporous Supports (SAMMS)

Energy Technology Data Exchange (ETDEWEB)

Fryxell, Glen E.; Wu, Hong; Lin, Yuehe; Shaw, Wendy J.; Birnbaum, Jerome C.; Linehan, John C.; Nie, Zimin; Kemner, K. M.; Kelly, Shelley

2004-11-01

Through the marriage of mesoporous ceramics with self-assembled monolayer chemistry, the genesis of a powerful new class of environmental sorbent materials has been realized. By coating the mesoporous ceramic backbone with a monolayer terminated with a lanthanide-specific ligand, it is possible to couple high lanthanide binding affinity with the high loading capacity (resulting from the extremely high surface area of the support). This lanthanide-specific ligand field is created by pairing a ''hard'' anionic Lewis base with a suitable synergistic ligand, in a favorable chelating geometry. Details of the synthesis, characterization, lanthanide binding studies, binding kinetics, competition experiments and sorbent regeneration studies are summarized

Lanthanide Selective Sorbents: Self-Assembled Monolayers on Mesoporous Supports (SAMMS)

Energy Technology Data Exchange (ETDEWEB)

Fryxell, Glen E.; Wu, Hong; Lin, Yuehe; Shaw, Wendy J.; Birnbaum, Jerome C.; Linehan, John C.; Nie, Zimin; Kemner, Kenneth M.; Kelly, Shelley

2004-11-01

Through the marriage of mesoporous ceramics with self-assembled monolayer chemistry, the genesis of a powerful new class of environmental sorbent materials has been realized. By coating the mesoporous ceramic backbone with a monolayer terminated with a lanthanide-specific ligand, it is possible to couple high lanthanide binding affinity with the high loading capacity (resulting from the extremely high surface area of the support). This lanthanide-specific ligand field is created by pairing a “hard” anionic Lewis base with a suitable synergistic ligand, in a favorable chelating geometry. Details of the synthesis, characterization, lanthanide binding studies, binding kinetics, competition experiments and sorbent regeneration studies are summarized.

A combined theoretical-experimental study of interactions between vanadium ions and Nafion membrane in all-vanadium redox flow batteries

Science.gov (United States)

Intan, Nadia N.; Klyukin, Konstantin; Zimudzi, Tawanda J.; Hickner, Michael A.; Alexandrov, Vitaly

2018-01-01

Vanadium redox flow batteries (VRFBs) are a promising solution for large-scale energy storage, but a number of problems still impede the deployment of long-lifetime VRFBs. One important aspect of efficient operation of VRFBs is understanding interactions between vanadium species and the membrane. Herein, we investigate the interactions between all four vanadium cations and Nafion membrane by a combination of infrared (IR) spectroscopy and density-functional-theory (DFT)-based static and molecular dynamics simulations. It is observed that vanadium species primarily lead to changes in the IR spectrum of Nafion in the SO3- spectral region which is attributed to the interaction between vanadium species and the SO3- exchange sites. DFT calculations of vanadium -Nafion complexes in the gas phase show that it is thermodynamically favorable for all vanadium cations to bind to SO3- via a contact pair mechanism. Car-Parrinello molecular dynamics-based metadynamics simulations of cation-Nafion systems in aqueous solution suggest that V2+ and V3+ species coordinate spontaneously to SO3-, which is not the case for VO2+ and VO2+ . The interaction behavior of the uncycled membrane determined in this study is used to explain the experimentally observed changes in the vibrational spectra, and is discussed in light of previous results on device-cycled membranes.

Vaporization study on vanadium monoxide and two-phase mixture of vanadium and vanadium monoxide by mass-spectrometric method

International Nuclear Information System (INIS)

Banchorndhevakul, W.; Matsui, Tsuneo; Naito, Keiji

1986-01-01

The vapor pressures over single phase vanadium monoxide VO 1.022 (s) and the two-phase mixture of vanadium metal (β phase) and vanadium monoxide were measured by mass-spectrometric method in the temperature range of 1,803 ∼ 1,990 and 1,703 ∼ 1,884 K, respectively. The main gas species over both systems were found to be VO(g) and V(g). The vapor pressure of VO(g) over the two-phase mixture of V(s) and VO(s) was a little lower than that over single phase VO(s). The vapor pressure of V(g) over the two-phase mixture was nearly equal to that over single phase. From the vapor pressure data, the enthalpies of vaporization, the enthalpies of formation for VO(g) and V(g) and the dissociation energy of VO(g) were determined. The oxygen partial pressure was calculated as a function of temperature from the vapor pressures of VO(g) and V(g), from which the partial molar enthalpies and entropies of oxygen in both systems were obtained. (author)

A modular optical sensor

Science.gov (United States)

Conklin, John Albert

This dissertation presents the design of a modular, fiber-optic sensor and the results obtained from testing the modular sensor. The modular fiber-optic sensor is constructed in such manner that the sensor diaphragm can be replaced with different configurations to detect numerous physical phenomena. Additionally, different fiber-optic detection systems can be attached to the sensor. Initially, the modular sensor was developed to be used by university of students to investigate realistic optical sensors and detection systems to prepare for advance studies of micro-optical mechanical systems (MOMS). The design accomplishes this by doing two things. First, the design significantly lowers the costs associated with studying optical sensors by modularizing the sensor design. Second, the sensor broadens the number of physical phenomena that students can apply optical sensing techniques to in a fiber optics sensor course. The dissertation is divided into seven chapters covering the historical development of fiber-optic sensors, a theoretical overview of fiber-optic sensors, the design, fabrication, and the testing of the modular sensor developed in the course of this work. Chapter 1 discusses, in detail, how this dissertation is organized and states the purpose of the dissertation. Chapter 2 presents an historical overview of the development of optical fibers, optical pressure sensors, and fibers, optical pressure sensors, and optical microphones. Chapter 3 reviews the theory of multi-fiber optic detection systems, optical microphones, and pressure sensors. Chapter 4 presents the design details of the modular, optical sensor. Chapter 5 delves into how the modular sensor is fabricated and how the detection systems are constructed. Chapter 6 presents the data collected from the microphone and pressure sensor configurations of the modular sensor. Finally, Chapter 7 discusses the data collected and draws conclusions about the design based on the data collected. Chapter 7 also

Effect of substrate temperature on thermochromic vanadium dioxide thin films sputtered from vanadium target

Science.gov (United States)

Madiba, I. G.; Kotsedi, L.; Ngom, B. D.; Khanyile, B. S.; Maaza, M.

2018-05-01

Vanadium dioxide films have been known as the most promising thermochromic thin films for smart windows which self-control the solar radiation and heat transfer for energy saving, comfort in houses and automotives. Such an attractive technological application is due to the fact that vanadium dioxide crystals exhibit a fast semiconductor-to-metal phase transition at a transition temperature Tc of about 68 °C, together with sharp optical changes from high transmitive to high reflective coatings in the IR spectral region. The phase transition has been associated with the nature of the microstructure, stoichiometry and stresses related to the oxide. This study reports on the effect of the crystallographic quality controlled by the substrate temperature on the thermochromic properties of vanadium dioxide thin films synthesized by reactive radio frequency inverted cylindrical magnetron sputtering from vanadium target. The reports results are based on X-ray diffraction, Atomic force microscopy, and UV-Visible spectrophotometer. The average crystalline grain size of VO2 increases with the substrate temperature, inducing stress related phenomena within the films.

Peculiarities of powder metallurgy of vanadium and its alloys

International Nuclear Information System (INIS)

Radomysel'skij, I.D.; Solntsev, V.P.; Evtushenko, O.V.

1987-01-01

Literature data on preparation of vanadium powder and powder materials on the vanadium base are generalized. Application of powder metallurgy engineering, allowing simulaneously to introduce practically any strengthening and solid-lubricating components as well as to alloy vanadium, permits undoubtedly to develop composite materials on the vanadium base

Factors in the complexation of lanthanides

International Nuclear Information System (INIS)

Choppin, G.R.

1976-01-01

The lanthanide cations are classified as hard acids and thus will coordinate strongly with oxygen and fluorine donor atoms. The electrostatic model is applied to lanthanide complexes with the dielectric constant as a parameter; the plot of ΔG vs sum of ionic radii confirm the ionic nature of the bonding. The enthalpy and entropy changes are shown to compensate each other to produce an almost linear variation in the free energy of complexation. Outer-sphere and inner-sphere complexation is discussed

Reaction between vanadium trichloride oxide and hydrogen sulfide

International Nuclear Information System (INIS)

Yajima, Akimasa; Matsuzaki, Ryoko; Saeki, Yuzo

1978-01-01

The details of the reaction between vanadium trichloride oxide and hydrogen sulfide were examined at 20 and 60 0 C. The main products by the reaction were vanadium dichloride oxide, sulfur, and hydrogen chloride. In addition to these products, small amounts of vanadium trichloride, vanadium tetrachloride, disulfur dichloride, and sulfur dioxide were formed. The formations of the above-mentioned reaction products can be explained as follows: The first stage is the reaction between vanadium trichloride oxide and hydrogen sulfide, 2VOCl 3 (l) + H 2 S(g)→2VOCl 2 (s) + S(s) + 2HCl(g). Then the resulting sulfur reacts with the unreacted vanadium trichloride oxide, 2VOCl 3 (l) + 2S(s)→2VOCl 2 (s) + S 2 Cl 2 (l). The resulting disulfur dichloride subsequently reacts with the unreacted vanadium trichloride oxide, 2VOCl 3 (l) + S 2 Cl 2 (l)→2VCl 4 (l) + S(s) + SO 2 (g). The resulting vanadium tetrachloride reacts with the sulfur formed during the reaction, 2VCl 4 (l) + 2S(s)→2VCl 3 (s) + S 2 Cl 2 (l), and also reacts with hydrogen sulfide, 2VCl 4 (l) + H 2 S(g)→2VCl 3 (s) + S(s) + 2HCl(g). (auth.)

Lanthanide-doped upconverting phosphors for bioassay and therapy

Science.gov (United States)

Guo, Huichen; Sun, Shiqi

2012-10-01

Lanthanide-doped fluorescent materials have gained increasing attention in recent years due to their unique luminescence properties which have led to their use in wide-ranging fields including those of biological applications. Aside from being used as agents for in vivo imaging, lanthanide-doped fluorescent materials also present many advantages for use in bioassays and therapy. In this review, we summarize the applications of lanthanide-doped up-converting phosphors (UCPs) in protein and gene detection, as well as in photodynamic and gene therapy in recent years, and outline their future potential in biological applications. The current report could serve as a reference for researchers in relevant fields.

Efficient Separation of Lanthanides Using Poly (Styrene-Divinyl Benzene) Aminated Anion Exchanger

International Nuclear Information System (INIS)

Borai, E.H.; Hassan, R.S.; El- Dessouky, M.I.; Ghonem, A.

2008-01-01

New chromatographic method was developed for the determination and separation of lanthanides using AS4A anionic column. The behavior of the column towards lanthanides was studied through many parameters, From the data obtained it is found that, affinity of the column toward investigated ions increase by increasing eluent concentration and it decrease retention factors. With the two investigated eluent (oxalic and citric acids), elution order for lanthanide elements was obtained in their atomic number from La to Lu. Retention times and retention orders obtained at these conditions clearly show that, lanthanides in AS4A are displaced according to anion exchange mechanism. More over separation of lanthanides using AS4A was studied using isocratic and gradient elution programs. Light and the first intermediate lanthanide elements were separated successfully by applying a gradient program containing 70% oxalic acid (100 mM) and 30% water. The problem of separation for heavy and the last intermediate lanthanide elements was solved using 100 mM alpha hydroxy isobutyric acid (α-HIBA)

Curvature of the Lanthanide Contraction: An Explanation

Energy Technology Data Exchange (ETDEWEB)

Raymond, Kenneth; Wellman, Daniel; Sgarlata, Carmelo; Hill, Aru

2009-12-21

A number of studies have shown that for isostructural series of the lanthanides (elements La through Lu), a plot of equivalent metal-ligand bond lengths versus atomic number differs significantly from linearity and can be better fit as a quadratic equation. However, for hydrogen type wave functions, it is the inverse of the average distance of the electron from the nucleus (an estimate of size) that varies linearly with effective nuclear charge. This generates an apparent quadratic dependence of radius with atomic number. Plotting the inverse of lanthanide ion radii (the observed distance minus the ligand size) as a function of effective nuclear charge gives very good linear fits for a variety of lanthanide complexes and materials. Parameters obtained from this fit are in excellent agreement with the calculated Slater shielding constant, k.

Understanding Complex Construction Systems Through Modularity

DEFF Research Database (Denmark)

Jensen, Tor Clarke; Bekdik, Baris; Thuesen, Christian

2014-01-01

This paper develops a framework for understanding complexity in construction projects by combining theories of complexity management and modularization. The framework incorporates three dimensions of product, process, and organizational modularity with the case of gypsum wall elements. The analysis...... system, rather than a modular, although the industry forces modular organizational structures. This creates a high complexity degree caused by the non-alignment of building parts and organizations and the frequent swapping of modules....... finds that the main driver of complexity is the fragmentation of the design and production, which causes the production modules to construct and install new product types and variants for each project as the designers are swapped for every project. The many interfaces are characteristics of an integral...

Electronic, magnetic, and magnetocrystalline anisotropy properties of light lanthanides

Science.gov (United States)

Hackett, Timothy A.; Baldwin, D. J.; Paudyal, D.

2017-11-01

Theoretical understanding of interactions between localized and mobile electrons and the crystal environment in light lanthanides is important because of their key role in much needed magnetic anisotropy in permanent magnet materials that have a great impact in automobile and wind turbine applications. We report electronic, magnetic, and magnetocrystalline properties of these basic light lanthanide elements studied from advanced density functional theory (DFT) calculations. We find that the inclusion of onsite 4f electron correlation and spin orbit coupling within the full-potential band structure is needed to understand the unique magnetocrystalline properties of these light lanthanides. The onsite electron correlation, spin orbit coupling, and full potential for the asphericity of charge densities must be taken into account for the proper treatment of 4f states. We find the variation of total energy as a function of lattice constants that indicate multiple structural phases in Ce contrasting to a single stable structure obtained in other light lanthanides. The 4f orbital magnetic moments are partially quenched as a result of crystalline electric field splitting that leads to magnetocrystalline anisotropy. The charge density plots have similar asphericity and environment in Pr and Nd indicating similar magnetic anisotropy. However, Ce and Sm show completely different asphericity and environment as both orbital moments are significantly quenched. In addition, the Fermi surface structures exemplified in Nd indicate structural stability and unravel a cause of anisotropy. The calculated magnetocrystalline anisotropy energy (MAE) reveals competing c-axis and in-plane anisotropies, and also predicts possibilities of unusual structural deformations in light lanthanides. The uniaxial magnetic anisotropy is obtained in the double hexagonal closed pack structures of the most of the light lanthanides, however, the anisotropy is reduced or turned to planar in the low symmetry

Roasting and leaching behaviors of vanadium and chromium in calcification roasting-acid leaching of high-chromium vanadium slag

Science.gov (United States)

Wen, Jing; Jiang, Tao; Zhou, Mi; Gao, Hui-yang; Liu, Jia-yi; Xue, Xiang-xin

2018-05-01

Calcification roasting-acid leaching of high-chromium vanadium slag (HCVS) was conducted to elucidate the roasting and leaching behaviors of vanadium and chromium. The effects of the purity of CaO, molar ratio between CaO and V2O5 ( n(CaO)/ n(V2O5)), roasting temperature, holding time, and the heating rate used in the oxidation-calcification processes were investigated. The roasting process and mechanism were analyzed by X-ray diffraction (XRD), scanning electron microscopy (SEM), and thermogravimetry-differential scanning calorimetry (TG-DSC). The results show that most of vanadium reacted with CaO to generate calcium vanadates and transferred into the leaching liquid, whereas almost all of the chromium remained in the leaching residue in the form of (Fe0.6Cr0.4)2O3. Variation trends of the vanadium and chromium leaching ratios were always opposite because of the competitive reactions of oxidation and calcification between vanadium and chromium with CaO. Moreover, CaO was more likely to combine with vanadium, as further confirmed by thermodynamic analysis. When the HCVS with CaO added in an n(CaO)/ n(V2O5) ratio of 0.5 was roasted in an air atmosphere at a heating rate of 10°C/min from room temperature to 950°C and maintained at this temperature for 60 min, the leaching ratios of vanadium and chromium reached 91.14% and 0.49%, respectively; thus, efficient extraction of vanadium from HCVS was achieved and the leaching residue could be used as a new raw material for the extraction of chromium. Furthermore, the oxidation and calcification reactions of the spinel phases occurred at 592 and 630°C for n(CaO)/ n(V2O5) ratios of 0.5 and 5, respectively.

Local structure of vanadium in doped LiFePO4

International Nuclear Information System (INIS)

Zhao, Ting; Xu, Wei; Ye, Qing; Cheng, Jie; Zhao, Haifeng; Chu, Wangsheng; Wu, Ziyu; Univ. of Science and Technology of China, Hefei; Xia, Dingguo

2010-01-01

LiFePO 4 composites with 5 at.% vanadium doping are prepared by solid state reactions. X-ray absorption fine-structure spectroscopy is used as a novel technique to identify vanadium sites. Both experimental analyses and theoretical simulations show that vanadium does not enter into the LiFePO 4 crystal lattice. When the vanadium concentration is lower then 1 at.%, the dopant remains insoluble. Thus, a single-phase vanadium-doped LiFePO4 cannot be formed and the improved electrochemical properties of vanadium doped LiFePO 4 previously reported cannot be associated with crystal structure changes of the LiFePO 4 via vanadium doping. (orig.)

Stress induced reorientation of vanadium hydride

International Nuclear Information System (INIS)

Beardsley, M.B.

1977-10-01

The critical stress for the reorientation of vanadium hydride was determined for the temperature range 180 0 to 280 0 K using flat tensile samples containing 50 to 500 ppM hydrogen by weight. The critical stress was observed to vary from a half to a third of the macroscopic yield stress of pure vanadium over the temperature range. The vanadium hydride could not be stress induced to precipitate above its stress-free precipitation temperature by uniaxial tensile stresses or triaxial tensile stresses induced by a notch

Chemistry related to the procurement of vanadium alloys

International Nuclear Information System (INIS)

Smith, H.M.; Chung H.M.; Tsai, H.C.

1997-01-01

Evaluation of trace element concentrations in vanadium alloys is important to characterize the low-activation characteristics and possible effects of trace elements on the properties. Detailed chemical analysis of several vanadium and vanadium alloy heats procured for the Argonne vanadium alloy development program were analyzed by Johnson-Matthey (UK) as part of a joint activity to evaluate trace element effects on the performance characteristics. These heats were produced by normal production practices for high grade vanadium. The analyses include approximately 60 elements analyzed in most cases by glow-discharge mass spectrometry. Values for molybdenum and niobium, which are critical for low-activation alloys, ranged from 0.4 to 60 wppm for the nine heats

Chemistry related to the procurement of vanadium alloys

Energy Technology Data Exchange (ETDEWEB)

Smith, H.M.; Chung H.M.; Tsai, H.C. [Argonne National Lab., IL (United States)

1997-08-01

Evaluation of trace element concentrations in vanadium alloys is important to characterize the low-activation characteristics and possible effects of trace elements on the properties. Detailed chemical analysis of several vanadium and vanadium alloy heats procured for the Argonne vanadium alloy development program were analyzed by Johnson-Matthey (UK) as part of a joint activity to evaluate trace element effects on the performance characteristics. These heats were produced by normal production practices for high grade vanadium. The analyses include approximately 60 elements analyzed in most cases by glow-discharge mass spectrometry. Values for molybdenum and niobium, which are critical for low-activation alloys, ranged from 0.4 to 60 wppm for the nine heats.

Complexation of vanadium with amidoxime and carboxyl groups. Uncovering the competitive role of vanadium in uranium extraction from seawater

Energy Technology Data Exchange (ETDEWEB)

Wang, Cong-Zhi; Wu, Qun-Yan; Lan, Jian-Hui; Shi, Wei-Qun [Chinese Academy of Sciences, Beijing (China). Inst. of High Energy Physics; Chai, Zhi-Fang [Chinese Academy of Sciences, Beijing (China). Inst. of High Energy Physics; Soochow Univ., Suzhou (China). School of Radiological and Interdisciplinary Sciences (RAD-X); Wu, Guo-Zhong [Chinese Academy of Sciences, Shanghai (China). Shanghai Inst. of Applied Physics

2017-09-01

At present, amidoxime-based adsorbents are considered to be the most promising materials for extraction of uranium from seawater. However, the high concentrations of transition metals especially vanadium strongly compete with uranium in the sequestration process, which is extremely limited the commercial use of amidoxime-based adsorbents. In this work, the coordination modes, bonding nature, and stabilities of possible vanadium(IV) (VO{sup 2+}) and (V) (VO{sub 2}{sup +}, VO{sup 3+}, V{sup 5+}) complexes with amidoximate (AO{sup -}), carboxyl (Ac{sup -}), glutarimidedioximate (HA{sup -}) and deprotonated glutarimidedioximate (A{sup 2-}) on single and double alkyl chains (R=C{sub 13}H{sub 26}) are systematically explored by quantum chemical calculations. Different from the uranyl (UO{sub 2}{sup 2+}) complexes, the AO{sup -} groups of the vanadium(IV) and (V) complexes prefer to coordinate as monodentate and chelate ligands, while few species with AO{sup -} groups in η{sup 2}-binding mode have been observed in the vanadium complexes. Besides, the vanadium complexes are predicted to have obvious covalent metal-ligand bonds. According to thermodynamic stability analysis, all the vanadium complexes with AO{sup -}, Ac{sup -}, HA{sup -} and A{sup 2-} ligands on double alkyl chains are found to be more stable than corresponding complexes with ligands on a single chain. The synergistic effect of the amidoxime and carboxyl groups can be observed in most of VO{sub 2}{sup +} and VO{sup 3+} complexes with mixed ligands (AO{sup -}/Ac{sup -}). The vanadium(IV) and (V) complexes are more stable than the corresponding uranyl complexes, and the adsorption capability of the amidoxime-based adsorbents toward vanadium(V) ions decrease in the order of VO{sub 2}{sup +}>VO{sup 3+}> V{sup 5+}. The dioxovanadium cation VO{sub 2}{sup +} is predicted to form multinuclear vanadium complex in the sequestration process, possibly resulting in higher stable VO{sub 2}{sup +} complexes. Therefore

3D hybrid-porous carbon derived from carbonization of metal organic frameworks for high performance supercapacitors

Science.gov (United States)

Bao, Weizhai; Mondal, Anjon Kumar; Xu, Jing; Wang, Chengyin; Su, Dawei; Wang, Guoxiu

2016-09-01

We report a rational design and synthesis of 3D hybrid-porous carbon with a hierarchical pore architecture for high performance supercapacitors. It contains micropores (<2 nm diameter) and mesopores (2-4 nm), derived from carbonization of unique porous metal organic frameworks (MOFs). Owning to the synergistic effect of micropores and mesopores, the hybrid-porous carbon has exceptionally high ion-accessible surface area and low ion diffusion resistance, which is desired for supercapacitor applications. When applied as electrode materials in supercapacitors, 3D hybrid-porous carbon demonstrates a specific capacitance of 332 F g-1 at a constant charge/discharge current of 500 mA g-1. The supercapacitors can endure more than 10,000 cycles without degradation of capacitance.

The spectroscopy and structure of some lanthanide chlorides in amide solutions

International Nuclear Information System (INIS)

Legendziewicz, J.; Bukietynska, K; Jezowsky-Trzebiatowska, B.

1974-01-01

The absorption spectra of Pr, Nd, Ho, and Er anhydrous and hydrated chlorides in formamide, methyl-, dimethyl-, and diethylformamide solutions have been investigated in the range of 8000 - 4200 cm -1 . By the Judd-Oefelt method of intensity analysis and by calculating the nepheloauxetic effect, the first coordination sphere of lanthanide ions and the approximate symmetry of amide solvates of anhydrous and hydrated lanthanide chlorides were determined. A difference between symmetry and coordination numbers for light and heavy lanthanide solvates has been found. Some considerations regarding the structure of lanthanide solvates and structure of amide molecules have been made. (B.T.)

On the suitability of lanthanides as actinide analogs

International Nuclear Information System (INIS)

Raymond, Kenneth; Szigethy, Geza

2008-01-01

With the current level of actinide materials used in civilian power generation and the need for safe and efficient methods for the chemical separation of these species from their daughter products and for long-term storage requirements, a detailed understanding of actinide chemistry is of great importance. Due to the unique bonding properties of the f-elements, the lanthanides are commonly used as structural and chemical models for the actinides, but differences in the bonding between these 4f and 5f elements has become a question of immediate applicability to separations technology. This brief overview of actinide coordination chemistry in the Raymond group at UC Berkeley/LBNL examines the validity of using lanthanide analogs as structural models for the actinides, with particular attention paid to single crystal X-ray diffraction structures. Although lanthanides are commonly accepted as reasonable analogs for the actinides, these comparisons suggest the careful study of actinide materials independent of their lanthanide analogs to be of utmost importance to present and future efforts in nuclear industries. (authors)

Vanadium diffusion coating on HT-9 cladding for mitigating the fuel cladding chemical interactions

Science.gov (United States)

Lo, Wei-Yang; Yang, Yong

2014-08-01

Fuel cladding chemical interaction (FCCI) has been identified as one of the crucial issues for developing Ferritic/Martensitic (F/M) stainless steel claddings for metallic fuels in a fast reactor. The anticipated elevated temperature and high neutron flux can significantly aggravate the FCCI, in terms of formation of inter-diffusion and lower melting point eutectic phases. To mitigate the FCCI, vanadium carbide coating as a diffusion barrier was deposited on the HT-9 substrate using a pack cementation diffusion coating (PCDC) method, and the processing temperature was optimized down to 730 °C. A solid metallurgical bonding between the coating layer and substrate was achieved, and the coating is free from through depth cracks. The microstructural characterizations using SEM and TEM show a nanostructured grain structure. EDS/WDS and XRD analysis confirm the phase of coating layer as V2C. Diffusion couple tests at 660 °C for 100 h demonstrate that V2C layer with a thickness of less than 5 μm can effectively eliminate the inter-diffusion between the lanthanide cerium and HT-9 steel.

Vanadium diffusion coating on HT-9 cladding for mitigating the fuel cladding chemical interactions

Energy Technology Data Exchange (ETDEWEB)

Lo, Wei-Yang; Yang, Yong, E-mail: yongyang@ufl.edu

2014-08-01

Fuel cladding chemical interaction (FCCI) has been identified as one of the crucial issues for developing Ferritic/Martensitic (F/M) stainless steel claddings for metallic fuels in a fast reactor. The anticipated elevated temperature and high neutron flux can significantly aggravate the FCCI, in terms of formation of inter-diffusion and lower melting point eutectic phases. To mitigate the FCCI, vanadium carbide coating as a diffusion barrier was deposited on the HT-9 substrate using a pack cementation diffusion coating (PCDC) method, and the processing temperature was optimized down to 730 °C. A solid metallurgical bonding between the coating layer and substrate was achieved, and the coating is free from through depth cracks. The microstructural characterizations using SEM and TEM show a nanostructured grain structure. EDS/WDS and XRD analysis confirm the phase of coating layer as V{sub 2}C. Diffusion couple tests at 660 °C for 100 h demonstrate that V{sub 2}C layer with a thickness of less than 5 μm can effectively eliminate the inter-diffusion between the lanthanide cerium and HT-9 steel.

Porous carbon derived via KOH activation of a hypercrosslinked porous organic polymer for efficient CO_2, CH_4, H_2 adsorptions and high CO_2/N_2 selectivity

International Nuclear Information System (INIS)

Modak, Arindam; Bhaumik, Asim

2015-01-01

Microporous carbon having Brunauer-Emmett-Teller (BET) surface area of 2186 m"2 g"−"1 and micropore volume of 0.85 cm"3 g"−"1 has been synthesized via KOH induced high temperature carbonization of a non-conjugated hypercrosslinked organic polymer. Owing to the templating and activation by KOH, we have succeeded in making a microporous carbon from this porous polymer and the resultant carbon material showed high uptake for CO_2 (7.6 mmol g"−"1) and CH_4 (2.4 mmol g"−"1) at 1 atm, 273 K together with very good selectivity for the CO_2/N_2 (30.2) separation. Furthermore, low pressure (1 atm) H_2 (2.6 wt%, 77 K) and water uptake (57.4 wt%, 298 K) ability of this polymer derived porous activated carbon is noteworthy. - Graphical abstract: Microporous carbon with BET surface area of 2186 m"2 g"−"1 has been synthesized via KOH activation of a porous organic polymer and it showed high uptake for CO_2 (7.6 mmol g"−"1), CH_4 (2.4 mmol g"−"1) and H_2 (2.6 wt%) at 1 atm together with very good selectivity for CO_2. - Highlights: • Porous carbon from hypercrosslinked organic polymer. • KOH activated carbon with BET surface area 2186 m"2 g"−"1. • High CO2 uptake (7.6 mmol g"−"1) and CO_2/N_2 selectivity (30.2). • Porous carbon also showed high H_2 (2.6 wt%) and H_2O (57.4 wt%) uptakes.

Ultrafast triggered transient energy storage by atomic layer deposition into porous silicon for integrated transient electronics

Science.gov (United States)

Douglas, Anna; Muralidharan, Nitin; Carter, Rachel; Share, Keith; Pint, Cary L.

2016-03-01

Here we demonstrate the first on-chip silicon-integrated rechargeable transient power source based on atomic layer deposition (ALD) coating of vanadium oxide (VOx) into porous silicon. A stable specific capacitance above 20 F g-1 is achieved until the device is triggered with alkaline solutions. Due to the rational design of the active VOx coating enabled by ALD, transience occurs through a rapid disabling step that occurs within seconds, followed by full dissolution of all active materials within 30 minutes of the initial trigger. This work demonstrates how engineered materials for energy storage can provide a basis for next-generation transient systems and highlights porous silicon as a versatile scaffold to integrate transient energy storage into transient electronics.Here we demonstrate the first on-chip silicon-integrated rechargeable transient power source based on atomic layer deposition (ALD) coating of vanadium oxide (VOx) into porous silicon. A stable specific capacitance above 20 F g-1 is achieved until the device is triggered with alkaline solutions. Due to the rational design of the active VOx coating enabled by ALD, transience occurs through a rapid disabling step that occurs within seconds, followed by full dissolution of all active materials within 30 minutes of the initial trigger. This work demonstrates how engineered materials for energy storage can provide a basis for next-generation transient systems and highlights porous silicon as a versatile scaffold to integrate transient energy storage into transient electronics. Electronic supplementary information (ESI) available: (i) Experimental details for ALD and material fabrication, ellipsometry film thickness, preparation of gel electrolyte and separator, details for electrochemical measurements, HRTEM image of VOx coated porous silicon, Raman spectroscopy for VOx as-deposited as well as annealed in air for 1 hour at 450 °C, SEM and transient behavior dissolution tests of uniformly coated VOx on

Separation process for lanthanides based on solvation properties of non ionic surfactants

International Nuclear Information System (INIS)

Draye, M.; Favre-Reguillon, A.; Foos, J.; Cote, G.

2004-01-01

In the present study, cloud-point extraction is used with a lipophilic chelating agent (8-hydroxyquinoline) to extract and separate lanthanum (III) and gadolinium (III) from an aqueous solution. The methodology used is based on the formation of lanthanide (III) organic complexes that are soluble in a micellar phase of non-ionic surfactant. The lanthanide (III) complexes are then extracted into the surfactant-rich phase at a temperature above the cloud-point temperature. The cloud-point temperature, the structure of the lipophilic part of the nonionic surfactant and the chelating agent - metal molar ratio are identified as factors determining the extraction efficiency and selectivity. With Triton X-114, high selectivity and decontamination factor for Gd(III) is observed indicating that micelle mediated extraction involving cloud-point extraction is promising for the specific separation of actinide ions from nuclear waste solution. (authors)

Lanthanide Organophosphate Spiro Polymers: Synthesis, Structure, and Magnetocaloric Effect in the Gadolinium Polymer.

Science.gov (United States)

Gupta, Sandeep K; Bhat, Gulzar A; Murugavel, Ramaswamy

2017-08-07

Spirocyclic lanthanide organophosphate polymers, {[Ln(dipp)(dippH)(CH 3 OH)(H 2 O) 2 ](CH 3 OH) 2 } n [Ln = La (1), Ce (2), Pr (3), Nd (4), Sm (5), Eu (6), Gd (7), Tb (8), Dy (9), Ho (10), Er (11)], have been prepared from the reaction of Ln(NO 3 ) 3 ·xH 2 O with sterically hindered 2,6-diisopropylphenyl phosphate (dippH 2 ) using aqueous NaOH as the base. The one-dimensional chainlike lanthanide (III) organophosphate coordination polymers have been characterized with the aid of analytical and spectroscopic methods. The single crystal structure determination of polymers (2-5 and 7-11) reveals that in these compounds the hydrophobic organic groups of the phosphate provide a protective coating for the inorganic lanthanide phosphate polymeric chain. The encapsulation of inorganic lanthanide phosphate core, which has very low solubility product, within the organic groups assists in the facile crystallization of the polymers. The di- and monoanionic organophosphate ligands dipp 2- and dippH - display [2.111] and [2.110] binding modes, respectively, in 2-5 and 7. However, they exhibit only [2.110] binding mode in the case of 8-11. This results in the formation of two different types of polymers. While the lighter rare-earth metal ions in 2-5 and 7 display eight coordinate biaugmented trigonal prismatic geometry, the heavier rare-earth metal ions in 9-11 exhibit a seven coordinate capped trigonal prismatic environment. The Tb(III) ion in 8 displays distorted pentagonal bipyramidal geometry. Magnetic studies reveal the presence of weak antiferromagnetic interactions between the Ln(III) ions through the organophosphate ligand. The isotropic Gd(III) polymer 7 exhibits a maximum entropy change of 17.83 J kg -1 K -1 for a field change of 7.0 T at 2.5 K, which is significant considering the high molecular weight of the organophosphate ligand. These polymers represent the first family of any structurally characterized rare-earth organophosphate polymers derived from monoesters

Vanadium and affective disorders

International Nuclear Information System (INIS)

Naylor, G.J.

1985-01-01

The oxidation reduction state of vanadium will influence its inhibitory effect, and it has been suggested that the control of this oxidation reduction could be a physiological means of controlling Na-K ATPase and hence membrane transport. However, there is no general agreement on this. For such a hypothesis to be true, tissue concentrations of vanadium would need to be sufficient to cause inhibition of Na-K ATPase. There has been considerable variation in the concentration of vanadium reported to be present in human blood and plasma - e.g., 8.4 μmoleliter, 0.11 μmoleliter, 0.04 μmoleliter and 0.0006-0.018 μmliter. Methods of assay have varied, even including enzymic methods, but the two major methods now used are neutron activation analysis and atomic absorption spectrophotometry using an electrical flameless atomizer. Using neutron activation analysis, difficulties arise from the short half-ife of V 52 (3.76 min) and for the need to separate Na 24 and Cl 36 from the sample since their radiation interfere with those from V 52 . Results from preirradiation separation agree well with those from atomic absorption spectrophotometry, but those from postirradiation separation are usually much lower. Though there is no agreement on the physiological role of vanadium there is evidence that it plays a part in the etiology of manic-depressive psychosis

Lanthanide-Dependent Regulation of Methanol Oxidation Systems in Methylobacterium extorquens AM1 and Their Contribution to Methanol Growth.

Science.gov (United States)

Vu, Huong N; Subuyuj, Gabriel A; Vijayakumar, Srividhya; Good, Nathan M; Martinez-Gomez, N Cecilia; Skovran, Elizabeth

2016-04-01

Methylobacterium extorquens AM1 has two distinct types of methanol dehydrogenase (MeDH) enzymes that catalyze the oxidation of methanol to formaldehyde. MxaFI-MeDH requires pyrroloquinoline quinone (PQQ) and Ca in its active site, while XoxF-MeDH requires PQQ and lanthanides, such as Ce and La. Using MeDH mutant strains to conduct growth analysis and MeDH activity assays, we demonstrate that M. extorquens AM1 has at least one additional lanthanide-dependent methanol oxidation system contributing to methanol growth. Additionally, the abilities of different lanthanides to support growth were tested and strongly suggest that both XoxF and the unknown methanol oxidation system are able to use La, Ce, Pr, Nd, and, to some extent, Sm. Further, growth analysis using increasing La concentrations showed that maximum growth rate and yield were achieved at and above 1 μM La, while concentrations as low as 2.5 nM allowed growth at a reduced rate. Contrary to published data, we show that addition of exogenous lanthanides results in differential expression from the xox1 and mxa promoters, upregulating genes in the xox1 operon and repressing genes in the mxa operon. Using transcriptional reporter fusions, intermediate expression from both the mxa and xox1 promoters was detected when 50 to 100 nM La was added to the growth medium, suggesting that a condition may exist under which M. extorquens AM1 is able to utilize both enzymes simultaneously. Together, these results suggest that M. extorquens AM1 actively senses and responds to lanthanide availability, preferentially utilizing the lanthanide-dependent MeDHs when possible. The biological role of lanthanides is a nascent field of study with tremendous potential to impact many areas in biology. Our studies demonstrate that there is at least one additional lanthanide-dependent methanol oxidation system, distinct from the MxaFI and XoxF MeDHs, that may aid in classifying additional environmental organisms as methylotrophs. Further

Implementationof a modular software system for multiphysical processes in porous media

Science.gov (United States)

Naumov, Dmitri; Watanabe, Norihiro; Bilke, Lars; Fischer, Thomas; Lehmann, Christoph; Rink, Karsten; Walther, Marc; Wang, Wenqing; Kolditz, Olaf

2016-04-01

Subsurface georeservoirs are a candidate technology for large scale energy storage required as part of the transition to renewable energy sources. The increased use of the subsurface results in competing interests and possible impacts on protected entities. To optimize and plan the use of the subsurface in large scale scenario analyses,powerful numerical frameworks are required that aid process understanding and can capture the coupled thermal (T), hydraulic (H), mechanical (M), and chemical (C) processes with high computational efficiency. Due to having a multitude of different couplings between basic T, H, M, or C processes and the necessity to implement new numerical schemes the development focus has moved to software's modularity. The decreased coupling between the components results in two major advantages: easier addition of specialized processes and improvement of the code's testability and therefore its quality. The idea of modularization is implemented on several levels, in addition to library based separation of the previous code version, by using generalized algorithms available in the Standard Template Library and the Boost library, relying on efficient implementations of liner algebra solvers, using concepts when designing new types, and localization of frequently accessed data structures. This procedure shows certain benefits for a flexible high-performance framework applied to the analysis of multipurpose georeservoirs.

Determination of vanadium (4) and (5) in the presence of both

International Nuclear Information System (INIS)

Malyuta, V.F.; Solomatin, V.T.; Berezhnoj, A.I.

1983-01-01

A study was made on the possibility of vanadium (4) and (5) determination in the presence of both by titration with ferrocene in aqueous solutions. 5-6 M H 2 SO 4 is the optimal medium for vanadium (5) titration. Vanadium (4) is titrated in the mixture of 2-2.5 M H 2 SO 4 and 8-10 M H 3 PO 4 . The method for vanadium (4) and (5) determination in vanadium catalysts was developed. Vanadium (5) is titrated amperometrically or potentiometrically by propanol solution of ferrocence in H 2 SO 4 . Concentrated H 3 PO 4 is added and the summary vanadium (4) is titrated. The relative standard deviations for 0.04-2% vanadium (4) content and 0.3-4% vanadium (5) content equal 0.06-0.03 and 0.05-0.02, respectively

Transformation and precipitation in vanadium treated steels

Science.gov (United States)

Vassiliou, Andreas D.

A series of carbon manganese steels containing varying amounts of carbon, vanadium and nitrogen was investigated in relation to the solubility of VC and VN in austenite, the grain coarsening characteristics of austenite, the tempering of martensite and other structures, the transformation during continuous cooling, the effect of vanadium addition and increasing nitrogen content on the thermo-mechanical processing of austenite, and the transformation of various morphologies of austenite to ferrite.The sites for preferential nucleation and growth of ferrite were identified and the effect of ferrite grain size inhomogeneity was investigated with a view to minimising it.The C/N ratio in the V(CN) precipitates was largely controlled by C/N ratio in the steel and it was also influenced by the austenitising treatment. As expected, the solubility of VN was less than that of VC.A systematic investigation of austenitising time and temperature on the grain coarsening characteristics was carried out showing the effects of vanadium, carbon and nitrogen. It was tentatively suggested that C-C and N-N clustering in the vanadium free steels controlled the grain growth whereas in the presence of vanadium, it was shown that VN and VC pinned the austenite grain boundaries and restricted grain growth. However coarsening or solution of VC and VN allowed the grain bondaries to migrate and grain coarsening occurred. The grain coarsening temperature was controlled predominantly by VN, whilst the VC dissolved frequently below the grain coarsening temperature.In the as quenched martensite, increasing nitrogen progressively increased the as quenched hardness, and the hardness also greatly increased with increasing carbon and vanadium added together. Examining the precipitation strengthening in tempered martensite showed that in the absence of vanadium, martensite softened progressively with increasing temperature and time. Vanadium additions increased the hardness level during low temperature

Rare-earth organic frameworks involving three types of architecture tuned by the lanthanide contraction effect: hydrothermal syntheses, structures and luminescence.

Science.gov (United States)

Deng, Zhao-Peng; Kang, Wei; Huo, Li-Hua; Zhao, Hui; Gao, Shan

2010-07-21

The first example of rare-earth organic frameworks with 3-aminopyrazine-2-carboxylic acid (Hapca) was synthesized under hydrothermal conditions and characterized by elemental analysis, IR, PL, TG, powder and single-crystal X-ray diffraction. These ten complexes exhibit three different structure types with decreasing lanthanide radii: [La(apca)(3)](n) () for type I, {[Ln(apca)(ox)(H(2)O)(2)].H(2)O}(n) (Ln = Pr (2), Nd (3), ox = oxalate) for type II, and [Ln(2)(apca)(4)(OH)(2)(H(2)O)(2)](n) (Ln = Sm (4), Eu (5), Gd (6), Tb (7), Dy (8), Er (9), Y (10)) for type III. The structure of type I consists of 1D "snowflake" chains along a-axis, which are further interconnected by hydrogen bonds to produce a 3D sra net topology containing infinite (-C-O-La-)(n) rod-shaped SBU. Type II has 2D Ln-apca-ox 4(4)-net, in which a planar udud water tetramers (H(2)O)(4) are formed by coordinated and free water molecules. Type III also comprises of 2D 4(4)-layer network constructed from Ln-apca-OH. The structure diversity is mainly caused by the variation of coordinated ligand and lanthanide contraction effect. Remarkably, the oxalate in type II was in situ synthesized from 3-aminopyrazine-2-carboxylic acid through an oxidation-hydrolysis reaction. The luminescent investigations reveal that complex exhibits strong blue emission and complex exhibits characteristic luminescence of Eu(3+).

Phonon dispersion in vanadium

International Nuclear Information System (INIS)

Ivanov, A.S.; Rumiantsev, A.Yu.

1999-01-01

Complete text of publication follows. Phonon dispersion curves in Vanadium metal are investigated by neutron inelastic scattering using three-axis spectrometers. Due to extremely low coherent scattering amplitude of neutrons in natural isotope mixture of vanadium the phonon frequencies could be determined in the energy range below about 15 meV. Several phonon groups were measured with the polarised neutron scattering set-up. It is demonstrated that the intensity of coherent inelastic scattering observed in the non-spin-flip channel vanishes in the spin-flip channel. The phonon density of states is measured on a single crystal keeping the momentum transfer equal to a vector of reciprocal lattice where the coherent inelastic scattering is suppressed. Phonon dispersion curves in vanadium, as measured by neutron and earlier by X-ray scattering, are described in frames of a charge-fluctuation model involving monopolar and dipolar degrees of freedom. The model parameters are compared for different transition metals with body-centred cubic-structure. (author)

Low activation vanadium alloys

International Nuclear Information System (INIS)

Witzenburg, W. van.

1991-01-01

The properties and general characteristics of vanadium-base alloys are reviewed in terms of the materials requirements for fusion reactor first wall and blanket structures. In this review attention is focussed on radiation response including induced radioactivity, mechanical properties, compatibility with potential coolants, physical and thermal properties, fabricability and resources. Where possible, properties are compared to those of other leading candidate structural materials, e.g. austenitic and ferritic/martensitic steels. Vanadium alloys appear to offer advantages in the areas of long-term activation, mechanical properties at temperatures above 600 deg C, radiation resistance and thermo-hydraulic design, due to superior physical and thermal properties. They also have a potential for higher temperature operation in liquid lithium systems. Disadvantages are associated with their ability to retain high concentrations of hydrogen isotopes, higher cost, more difficult fabrication and welding. A particular concern regarding use of vanadium alloys relates their reactivity with non-metallic elements, such as oxygen and nitrogen. (author). 33 refs.; 2 figs.; 2 tabs

Advances in lanthanide-based luminescent peptide probes for monitoring the activity of kinase and phosphatase.

Science.gov (United States)

Pazos, Elena; Vázquez, M Eugenio

2014-02-01

Signaling pathways based on protein phosphorylation and dephosphorylation play critical roles in the orchestration of complex biochemical events and form the core of most signaling pathways in cells (i.e. cell cycle regulation, cell motility, apoptosis, etc.). The understanding of these complex signaling networks is based largely on the biochemical study of their components, i.e. kinases and phosphatases. The development of luminescent sensors for monitoring kinase and phosphatase activity is therefore an active field of research. Examples in the literature usually rely on the modulation of the fluorescence emission of organic fluorophores. However, given the exceptional photophysical properties of lanthanide ions, there is an increased interest in their application as emissive species for monitoring kinase and phosphatase activity. This review summarizes the advances in the development of lanthanide-based luminescent peptide sensors as tools for the study of kinases and phosphatases and provides a critical description of current examples and synthetic approaches to understand these lanthanide-based luminescent peptide sensors. Copyright © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Lanthanide coordination polymers based on multi-donor ligand containing pyridine and phthalate moieties: Structures, luminescence and magnetic properties

Energy Technology Data Exchange (ETDEWEB)

Feng, Xun [College of Chemistry and Chemical Engineering, Luoyang Normal University, Luoyang 471022 (China); Liu, Lang [College of Chemistry and Molecular Engineering, Zhengzhou University, Zhengzhou 450002 (China); College of Chemistry and Chemical Engineering, Luoyang Normal University, Luoyang 471022 (China); Wang, Li-Ya, E-mail: wlya@lynu.edu.cn [College of Chemistry and Chemical Engineering, Luoyang Normal University, Luoyang 471022 (China); College of Chemistry and Pharmacy Engineering, Nanyang Normal University, Nanyang 473601 (China); Song, Hong-Liang; Qiang Shi, Zhi; Wu, Xu-Hong [College of Chemistry and Chemical Engineering, Luoyang Normal University, Luoyang 471022 (China); Ng, Seik-Weng [Department of Chemistry, University of Malaya, Kuala Lumpur 50603 (Malaysia); Chemistry Department, Faculty of Science, King Abdulaziz University, Jeddah 80203 (Saudi Arabia)

2013-10-15

A new family of five lanthanide-organic coordination polymers incorporating multi-functional N-hetrocyclic dicarboxylate ligand, namely, [Ln{sub 2}(Hdpp){sub 2}(dpp){sub 2}]{sub n}Ln=Pr(1), Eu(2), Gd(3), Dy(4), Er(5) (H{sub 2}dpp=1-(3, 4-dicarboxyphenyl) pyridin-4-ol) have been fabricated successfully through solvothermal reaction of 1-(3,4-dicarboxyphenyl)-4-hydroxypyridin-1-ium chloride with trivalent lanthanide salts, and have been characterized systematically. The complexes 1–5 are isomorphous and isostructural. They all feature three dimensional (3D) frameworks based on the interconnection of 1D double chains composed of the binuclear moiety [Ln{sub 2}(Hdpp){sub 2}]{sup 4+} basic carboxylate as secondary building unit (SBU). The results of magnetic analysis shows the same bridging fashion of carboxylic group in this case results in the different magnetic properties occurring within lanthanide polymers. Moreover, the Eu(III) and Dy(III) complexes display characteristic luminescence emission in the visible regions. - Graphical abstract: A new family of lanthanide-organic frameworks incorporating multi-donor twisted ligand has been fabricated successfully, and has been characterized systematically. The complexes 1–5 are isostructural, and all feather three dimensional (3D) frameworks based on the interconnection of 1D double stride chains composed of the binuclear moiety [Ln{sub 2}(Hdpp){sub 2}]{sup 2+} basic carboxylate as secondary building unit (SBU). Display Omitted - Highlights: • New family of lanthanide–organic coordination polymers incorporating multifunctional N-hetrocyclic dicarboxylate ligand has been fabricated. • They have been characterized systematically. • They all feather three dimensional frameworks based on the binuclear moiety of [Ln{sub 2}(Hdpp){sub 2}]{sup 2+}. • The Eu(III) and Dy(III) analogues exhibit intense photoluminescence.

Behaviour of trivalent actinides and lanthanide elements in chloride solution; Comportement des lanthanides et transuraniens trivalents en milieu chlorhydrique

Energy Technology Data Exchange (ETDEWEB)

Marin, B [Commissariat a l' Energie Atomique, Fontenay-aux-Roses (France). Centre d' Etudes Nucleaires

1969-07-01

The aim of this work is to compare the complexation in chloride solutions of trivalent lanthanides and actinides. We have first studied the solvatation of these cations without complexation. We found a difference between Am, Cm and Rare Earths (we can separate lanthanides into Light and Heavy Rare Earths). For studying the complexation we choose the technic of electrophoresis on paper after establishing a simple theory of mobilities in complex solutions. The hydrolysis of these cations was studied and compared in chloride solutions. We have then studied the complexation with the Cl{sup -} ligand in some solutions: HCl, NH{sub 4}Cl, CaCl{sub 2}, CeCl{sub 3}, LiCl. We have established that the complexation is the same in dilute HCl solutions but in concentrated solutions the trivalent actinides are more complexed. This difference is sharper in LiCl solutions. We also proposed the different models of complex in these solutions. (author) [French] Le but de ce travail est de comparer les transuraniens et lanthanides trivalents au point de vue de leur complexation en solution chlorhydrique. Nous avons ete amenes tout d'abord a etudier la solvatation de ces cations non complexes. C'est ainsi que nous pouvons constater une difference entre Am, Cm et les lanthanides. Ces derniers pouvant se separer en lanthanides legers et lanthanides lourds. Pour etudier la complexation nous avons utilise l'electrophorese sur papier apres avoir donne une theorie simple des mobilites en milieu complexant. Apres avoir etudie et compare l'hydrolyse de ces divers cations en solution chlorhydrique, nous avons etudie leur complexation avec l'ion Cl{sup -} dans dans divers milieux: HCl, NH{sub 4}Cl, CaCl{sub 2}, CeCl{sub 3}, LiCl. ous avons note qu'en solution HCl les deux series se comportent de la meme facon pour des concentrations faibles en Cl{sup -} mais que les transuraniens se complexent plus fortement dans les solutions concentrees. Cette difference s'accroit encore dans les milieux

Vanadium extraction by combined process of lixiviation and toasting

International Nuclear Information System (INIS)

Coral, Aldo

1992-01-01

Combinated toasting and leaching processes were applied at laboratory level to vanadiferous ore from Puyango deposit in order to evaluate different rates. Before leaching, a pretreatment consisting in toasting at open atmosphere was given to the ore. Both raw and toasted ore were later washed in organic solvents. In reason of mineralogical and petrographic characteristics of the ore, only alcaline leaching was tested under different pressure temperature and pH conditions of leaching solution (pH=9.8) in order to optimize time and efficiency of each individual process. Four different unitary alcaline leaching processes were studied: MECHANICAL STIRRING, PNEUMATIC STIRRING, LEACHING IN AUTOCLAVE AND LEACHING IN COLUMNS. For these four processes were obtained recovery rates (in percentage) of 18.63 and 87.82; 17.03 and 82.57; 60.42 and 99.55; 2.5 and 30.10; respectively from raw and pre-toasted ore. After filtration, vanadium was extracted from enriched solutions by using liquid resin ALAMINE 336, selective for vanadium at pH=2.8. Vanadium was later discharged with a Sodium Carbonate solution (10 per cent) and finally precipitated as the commercial compound Ammonium Vanadate, NH4VO3. Nuclear techniques as X-ray fluorescence and Atomic Absorption spectroscopy were used for analysis all over the investigation

Nonaqueous phase liquid dissolution and soil organic matter sorption in porous media: review of system similarities

NARCIS (Netherlands)

Heyse, Edward; Augustijn, Dionysius C.M.; Suresh, P.; Rao, C.; Delfino, Joseph J.

2002-01-01

We examine similarities in constraints to mass transfer of hydrophobic organic compounds (HOCs) between the aqueous and various organic phases in porous media at the grain scale. Published research and data are reviewed regarding equilibrium coefficients and first-order rate constants for mass

Aqueous vanadium ion dynamics relevant to bioinorganic chemistry: A review.

Science.gov (United States)

Kustin, Kenneth

2015-06-01

Aqueous solutions of the four highest vanadium oxidation states exhibit four diverse colors, which only hint at the diverse reactions that these ions can undergo. Cationic vanadium ions form complexes with ligands; anionic vanadium ions form complexes with ligands and self-react to form isopolyanions. All vanadium species undergo oxidation-reduction reactions. With a few exceptions, elucidation of the dynamics of these reactions awaited the development of fast reaction techniques before the kinetics of elementary ligation, condensation, reduction, and oxidation of the aqueous vanadium ions could be investigated. As the biological roles played by endogenous and therapeutic vanadium expand, it is appropriate to bring the results of the diverse kinetics studies under one umbrella. To achieve this goal this review presents a systematic examination of elementary aqueous vanadium ion dynamics. Copyright © 2014 Elsevier Inc. All rights reserved.

Lanthanide (III) complexes of 2-(N-salicylideneamino)-4-phenylthiazole

International Nuclear Information System (INIS)

Sasidharan, G.N.; Mohanan, K.; Lakshmi Prabha, A.N.

2002-01-01

Lanthanide(III) complexes of 2-(N-salicylideneamino)-4- phenylthiazole (HSAT) have been synthesised and characterised by elemental, analytical, thermogravimetric, molar conductance, UV- visible, IR and NMR spectral data. The ligand coordinates to the lanthanide(III) ion in a tridentate fashion without deprotonation, giving complexes of the type [Ln(HSAT) 2 (NO 3 ) 3 ] and [Ln(HSAT) 2 (H 2 0) 3 Cl 3 ]. The spectral data reveal that the ligand is bonded to the lanthanide ion through azomethine nitrogen, ring nitrogen and phenolic oxygen without deprotonation. The nitrate group acts in a bidentate fashion. The ligand and the metal complexes exhibit antibacterial and antifungal activities. (author)

Equilibrium constants in aqueous lanthanide and actinide chemistry from time-resolved fluorescence spectroscopy: The role of ground and excited state reactions

International Nuclear Information System (INIS)

Billard, I.; Luetzenkirchen, K.

2003-01-01

Equilibrium constants for aqueous reactions between lanthanide or actinide ions and (in-) organic ligands contain important information for various radiochemical problems, such as nuclear reprocessing or the migration of radioelements in the geosphere. We study the conditions required to determine equilibrium constants by time-resolved fluorescence spectroscopy measurements. Based on a simulation study it is shown that the possibility to determine equilibrium constants depends upon the reaction rates in the photoexcited states of the lanthanide or actinide ions. (orig.)

Structural and silver/vanadium ratio effects on silver vanadium phosphorous oxide solution formation kinetics: impact on battery electrochemistry.

Science.gov (United States)

Bock, David C; Takeuchi, Kenneth J; Marschilok, Amy C; Takeuchi, Esther S

2015-01-21

The detailed understanding of non-faradaic parasitic reactions which diminish battery calendar life is essential to the development of effective batteries for use in long life applications. The dissolution of cathode materials including manganese, cobalt and vanadium oxides in battery systems has been identified as a battery failure mechanism, yet detailed dissolution studies including kinetic analysis are absent from the literature. The results presented here provide a framework for the quantitative and kinetic analyses of the dissolution of cathode materials which will aid the broader community in more fully understanding this battery failure mechanism. In this study, the dissolution of silver vanadium oxide, representing the primary battery powering implantable cardioverter defibrillators (ICD), is compared with the dissolution of silver vanadium phosphorous oxide (Ag(w)VxPyOz) materials which were targeted as alternatives to minimize solubility. This study contains the first kinetic analyses of silver and vanadium solution formation from Ag0.48VOPO4·1.9H2O and Ag2VP2O8, in a non-aqueous battery electrolyte. The kinetic results are compared with those of Ag2VO2PO4 and Ag2V4O11 to probe the relationships among crystal structure, stoichiometry, and solubility. For vanadium, significant dissolution was observed for Ag2V4O11 as well as for the phosphate oxide Ag0.49VOPO4·1.9H2O, which may involve structural water or the existence of multiple vanadium oxidation states. Notably, the materials from the SVPO family with the lowest vanadium solubility are Ag2VO2PO4 and Ag2VP2O8. The low concentrations and solution rates coupled with their electrochemical performance make these materials interesting alternatives to Ag2V4O11 for the ICD application.

Creep and creep rupture properties of unalloyed vanadium and solid-solution-strengthened vanadium-base alloys

International Nuclear Information System (INIS)

Kainuma, T.; Iwao, N.; Suzuki, T.; Watanabe, R.

1982-01-01

The creep and creep rupture properties of vanadium and vanadium-base alloys were studied at 700 and 1000 0 C. The alloys were vanadium-base binary alloys containing about 5 - 21 at.% Al, Ti, Nb, Ta, Cr, Mo or Fe, three V-20wt.%Nb-base ternary alloys containing 5 or 10 wt.% Al, Cr or Mo, V-10wt.%Ta-10wt.%Al and V-25wt.%Cr-0.8wt.%Zr. The creep rupture stress of the binary alloys, except the V-Al and V-Ti alloys, increased linearly with increasing concentration of the alloying elements. The V-Nb alloy had the best properties with respect to the rupture stress and creep rate at 700 0 C and the rupture stress at 1000 0 C, but the V-Mo alloy appeared likely to have better creep properties at longer times and higher temperatures. Of the five ternary alloys, V-20wt.%Nb-5wt.%Cr and V-20wt.%Nb-10wt.%Mo showed the best creep properties. The creep properties of these two alloys were compared with those of other vanadium alloys and of type 316 stainless steel. (Auth.)

Specialization can drive the evolution of modularity.

Directory of Open Access Journals (Sweden)

Carlos Espinosa-Soto

2010-03-01

Full Text Available Organismal development and many cell biological processes are organized in a modular fashion, where regulatory molecules form groups with many interactions within a group and few interactions between groups. Thus, the activity of elements within a module depends little on elements outside of it. Modularity facilitates the production of heritable variation and of evolutionary innovations. There is no consensus on how modularity might evolve, especially for modules in development. We show that modularity can increase in gene regulatory networks as a byproduct of specialization in gene activity. Such specialization occurs after gene regulatory networks are selected to produce new gene activity patterns that appear in a specific body structure or under a specific environmental condition. Modules that arise after specialization in gene activity comprise genes that show concerted changes in gene activities. This and other observations suggest that modularity evolves because it decreases interference between different groups of genes. Our work can explain the appearance and maintenance of modularity through a mechanism that is not contingent on environmental change. We also show how modularity can facilitate co-option, the utilization of existing gene activity to build new gene activity patterns, a frequent feature of evolutionary innovations.

Spectrophotometric, potentiometric, and gravimetric determination of lanthanides with peri-dihydroxynaphthindenone

International Nuclear Information System (INIS)

Hassan, S.S.M.; Mahmoud, W.H.

1982-01-01

Sensitive and reasonably selective methods are described for the spectrophotometric, potentiometric, and gravimetric determination of lanthanides using peri-dihydroxynaphthindenone as a novel chromogenic and precipitating reagent. The reagent forms a stable 1:2 (metal:reagent) type of complex with light lanthanides at pH 2-7 in 1:1 ethanol-water mixture. Low metal concentrations ( 4 L mol -1 cm -1 ) which obey Beer's law. Quantitative precipitation of the complexes from metal solutions of concentrations > 100 μg/mL permits both gravimetric quantitation by igniting the precipitates to the metal oxides and potentiometric titration of the excess reagent. Results with an average recovery of 98% (standard deviation 0.7%) are obtainable for 0.1 μg to 200 mg of all light lanthanides. Many foreign ions naturally occurring or frequently associated with lanthanides do not interfere or can be tolerated

Manufacturing development of low activation vanadium alloys

International Nuclear Information System (INIS)

Smith, J.P.; Johnson, W.R.; Baxi, C.B.

1996-10-01

General Atomics is developing manufacturing methods for vanadium alloys as part of a program to encourage the development of low activation alloys for fusion use. The culmination of the program is the fabrication and installation of a vanadium alloy structure in the DIII-D tokamak as part of the Radiative Divertor modification. Water-cooled vanadium alloy components will comprise a portion of the new upper divertor structure. The first step, procuring the material for this program has been completed. The largest heat of vanadium alloy made to date, 1200 kg of V-4Cr-4Ti, has been produced and is being converted into various product forms. Results of many tests on the material during the manufacturing process are reported. Research into potential fabrication methods has been and continues to be performed along with the assessment of manufacturing processes particularly in the area of joining. Joining of vanadium alloys has been identified as the most critical fabrication issue for their use in the Radiative Divertor Program. Joining processes under evaluation include resistance seam, electrodischarge (stud), friction and electron beam welding. Results of welding tests are reported. Metallography and mechanical tests are used to evaluate the weld samples. The need for a protective atmosphere during different welding processes is also being determined. General Atomics has also designed, manufactured, and will be testing a helium-cooled, high heat flux component to assess the use of helium cooled vanadium alloy components for advanced tokamak systems. The component is made from vanadium alloy tubing, machined to enhance the heat transfer characteristics, and joined to end flanges to allow connection to the helium supply. Results are reported

Mineralogy and geochemistry of vanadium in the Colorado Plateau

Science.gov (United States)

Weeks, A.D.

1961-01-01

The chief domestic source of vanadium is uraniferous sandstone in the Colorado Plateau. Vanadium is 3-, 4-, or 5-valent in nature and, as oxides or combined with other elements, it forms more than 40 minerals in the Plateau ores. These ores have been studied with regard to the relative amounts of vanadium silicates and oxide-vanadates, uranium-vanadium ratios, the progressive oxidation of black low-valent ores to high-valent carnotite-type ores, and theories of origin. ?? 1961.

Extraction and separation of molybdenum and vanadium from acidic and alkaline media using tertiary and quaternary amines

International Nuclear Information System (INIS)

Stas, J.; Dahdouh, A.; Rizkallah, I.

2010-01-01

The extraction of vanadium and molybdenum from alkaline leaching solutions coming from the leaching of fly ash of fired electrical power stations by tri-n dodecylamine (TDA) and metyl trioctyl ammonium chloride (QA) in the presence of octanol-2 as modifier in kerosene has been investigated. Some parameters influencing the extraction process have been studied (agitation time, octanol-2 percentage in the organic phase, pH of the aqueous phase, concentration of TDA and QA, concentration of vanadium in the aqueous phase and temperature). It has been shown that the extraction capacity of both V and Mo by TDA increases by decreasing the pH of the aqueous phase and reaches a maximum extraction at pH=2. The concentration of TDA plays an important role on the separation selectivity between these two elements, where the selectivity of Mo vs V (S M o, v=[Mo] o rg/[V] o rg) increases with the decrease of TDA concentration to reach a maximum selectivity value of S M o, v = 0.37 for [TDA]=1.5 M. It has been also shown that, whatever vanadium concentration in the aqueous phase, molybdenum will be first extracted, then the remaining free TDA will be occupied by vanadium. Concerning the quaternary amine QA, the pH value of the aqueous phase plays an important role in the separation process between vanadium and molybdenum, where the value of the selectivity of V vs Mo (S v , Mo=[V] o rg/[Mo] o rg) is maximal for pH>8 and the pH=8.5 is the best value which permit a good separation between these two elements at QA concentration equal to 6%, especially at high vanadium concentration. It is very important to note that for low vanadium concentration and at pH=1.5 the value of the selectivity of Mo vs V (S M o,v) increases with increasing Mo concentration in the aqueous phase which enable us the separation between these two elements under these experimental conditions, where Mo will be much more extracted than vanadium. The stripping of vanadium and molybdenum from the loaded organic

Optical spectra of vanadium (5, 4) compounds during extraction by di-2-ethylhexylphosphoric acid

International Nuclear Information System (INIS)

Kurbatova, L.D.; Medvedeva, N.I.

2000-01-01

Optical spectra of vanadium (5, 4) complexes with HDEHP are studied using literature data on quantum-chemical calculations of vanadium (5) and vanadium (4) oxides. Extraction of vanadium is conducted by undiluted HDEHP from sulfuric acid solutions. Absorption electron spectra (AES) of vanadium (5), vanadium (4) and vanadium (5, 4) compounds are presented. In AES of vanadium (5, 4) four absorption bands at 24000, 17000, 14500 and 13500 cm -1 appear. Comparison with spectra of vanadium (5) and vanadium (4) shows that band 17000 cm -1 which appears only during mutual extraction of vanadium (5) and vanadium (4) is caused by transitions appearing between filled and empty levels of d-zone broadened by vanadium (5) and vanadium (4) interaction [ru

Spectrally resolved confocal microscopy using lanthanide centred near-IR emission

DEFF Research Database (Denmark)

Liao, Zhiyu; Tropiano, Manuel; Mantulnikovs, Konstantins

2015-01-01

The narrow, near infrared (NIR) emission from lanthanide ions has attracted great interest, particularly with regard to developing tools for bioimaging, where the long lifetimes of lanthanide excited states can be exploited to address problems arising from autofluorescence and sample transparency...

Metric modular spaces

CERN Document Server

Chistyakov, Vyacheslav

2015-01-01

Aimed toward researchers and graduate students familiar with elements of functional analysis, linear algebra, and general topology; this book contains a general study of modulars, modular spaces, and metric modular spaces. Modulars may be thought of as generalized velocity fields and serve two important purposes: generate metric spaces in a unified manner and provide a weaker convergence, the modular convergence, whose topology is non-metrizable in general. Metric modular spaces are extensions of metric spaces, metric linear spaces, and classical modular linear spaces. The topics covered include the classification of modulars, metrizability of modular spaces, modular transforms and duality between modular spaces, metric  and modular topologies. Applications illustrated in this book include: the description of superposition operators acting in modular spaces, the existence of regular selections of set-valued mappings, new interpretations of spaces of Lipschitzian and absolutely continuous mappings, the existe...

Determination of Leachable Vanadium (V) in Sediment

African Journals Online (AJOL)

NICO

A method for speciation of vanadium in solid samples was developed for quantification of ... Experimental ... Sediments for Trace Metals), obtained from the National Research ... Determination of vanadium is not a simple task using ET-AAS.

Environmental versatility promotes modularity in genome-scale metabolic networks.

Science.gov (United States)

Samal, Areejit; Wagner, Andreas; Martin, Olivier C

2011-08-24

The ubiquity of modules in biological networks may result from an evolutionary benefit of a modular organization. For instance, modularity may increase the rate of adaptive evolution, because modules can be easily combined into new arrangements that may benefit their carrier. Conversely, modularity may emerge as a by-product of some trait. We here ask whether this last scenario may play a role in genome-scale metabolic networks that need to sustain life in one or more chemical environments. For such networks, we define a network module as a maximal set of reactions that are fully coupled, i.e., whose fluxes can only vary in fixed proportions. This definition overcomes limitations of purely graph based analyses of metabolism by exploiting the functional links between reactions. We call a metabolic network viable in a given chemical environment if it can synthesize all of an organism's biomass compounds from nutrients in this environment. An organism's metabolism is highly versatile if it can sustain life in many different chemical environments. We here ask whether versatility affects the modularity of metabolic networks. Using recently developed techniques to randomly sample large numbers of viable metabolic networks from a vast space of metabolic networks, we use flux balance analysis to study in silico metabolic networks that differ in their versatility. We find that highly versatile networks are also highly modular. They contain more modules and more reactions that are organized into modules. Most or all reactions in a module are associated with the same biochemical pathways. Modules that arise in highly versatile networks generally involve reactions that process nutrients or closely related chemicals. We also observe that the metabolism of E. coli is significantly more modular than even our most versatile networks. Our work shows that modularity in metabolic networks can be a by-product of functional constraints, e.g., the need to sustain life in multiple

Environmental versatility promotes modularity in genome-scale metabolic networks

Directory of Open Access Journals (Sweden)

Wagner Andreas

2011-08-01

Full Text Available Abstract Background The ubiquity of modules in biological networks may result from an evolutionary benefit of a modular organization. For instance, modularity may increase the rate of adaptive evolution, because modules can be easily combined into new arrangements that may benefit their carrier. Conversely, modularity may emerge as a by-product of some trait. We here ask whether this last scenario may play a role in genome-scale metabolic networks that need to sustain life in one or more chemical environments. For such networks, we define a network module as a maximal set of reactions that are fully coupled, i.e., whose fluxes can only vary in fixed proportions. This definition overcomes limitations of purely graph based analyses of metabolism by exploiting the functional links between reactions. We call a metabolic network viable in a given chemical environment if it can synthesize all of an organism's biomass compounds from nutrients in this environment. An organism's metabolism is highly versatile if it can sustain life in many different chemical environments. We here ask whether versatility affects the modularity of metabolic networks. Results Using recently developed techniques to randomly sample large numbers of viable metabolic networks from a vast space of metabolic networks, we use flux balance analysis to study in silico metabolic networks that differ in their versatility. We find that highly versatile networks are also highly modular. They contain more modules and more reactions that are organized into modules. Most or all reactions in a module are associated with the same biochemical pathways. Modules that arise in highly versatile networks generally involve reactions that process nutrients or closely related chemicals. We also observe that the metabolism of E. coli is significantly more modular than even our most versatile networks. Conclusions Our work shows that modularity in metabolic networks can be a by-product of functional

Effect of vanadium compounds on acid phosphatase activity.

Science.gov (United States)

Vescina, C M; Sálice, V C; Cortizo, A M; Etcheverry, S B

1996-01-01

The direct effect of different vanadium compounds on acid phosphatase (ACP) activity was investigated. Vanadate and vanadyl but not pervanadate inhibited the wheat germ ACP activity. These vanadium derivatives did not alter the fibroblast Swiss 3T3 soluble fraction ACP activity. Using inhibitors of tyrosine phosphatases (PTPases), the wheat germ ACP was partially characterized as a PTPase. This study suggests that the inhibitory ability of different vanadium derivatives to modulate ACP activity seems to depend on the geometry around the vanadium atom more than on the oxidation state. Our results indicate a correlation between the PTPase activity and the sensitivity to vanadate and vanadyl cation.

Topotactic synthesis of vanadium nitride solid foams

International Nuclear Information System (INIS)

Oyama, S.T.; Kapoor, R.; Oyama, H.T.; Hofmann, D.J.; Matijevic, E.

1993-01-01

Vanadium nitride has been synthesized with a surface area of 120 m 2 g -1 by temperature programmed nitridation of a foam-like vanadium oxide (35 m 2 g -1 ), precipitated from vanadate solutions. The nitridation reaction was established to be topotactic and pseudomorphous by x-ray powder diffraction and scanning electron microscopy. The crystallographic relationship between the nitride and oxide was {200}//{001}. The effect of precursor geometry on the product size and shape was investigated by employing vanadium oxide solids of different morphologies

Separation of lanthanides through hydroxyapatite; Separacion de lantanidos mediante hidroxiapatita

Energy Technology Data Exchange (ETDEWEB)

Garcia M, F.G

2006-07-01

With the objective of obtaining from an independent way to each one of the lanthanides {sup 151} Pm, {sup 161} Tb, {sup 166} Ho and {sup 177} Lu free of carrier and with high specific activities starting from the indirect irradiation via, it intends in this work to determine the viability of separation of the couples Nd/Pm, Dy/Ho, Gd/Tb and Yb/Lu, by means of ion exchange column chromatography, using hydroxyapatite (HAp) and fluorite like absorbent material in complexing media. It is important to mention that have registered separation studies among lanthanides of the heavy group with those of the slight group, using the same mass and, in comparison with this work, quantities different from the father were used and of the son, also, that the separation studies were carried out among neighboring lanthanides. In this investigation, it was determined the effect that its have the complexing media: KSCN, sodium tartrate, sodium citrate, EDTA and aluminon, their pH and concentration, in the adsorption of the lanthanides in both minerals, in order to determine the chromatographic conditions for separation of the couples Nd/Pm, Dy/Ho, Gd/Tb and Yb/Lu. The work consists of five chapters, in the first one they are presented a theoretical introduction of the characteristics more important of the lanthanides, the hydroxyapatite and the fluorite; in the second, it is deepened in the ion exchange, as well as the two techniques (XRD and High Vacuum Electron Microscopy) to make the characterization of LnCI{sub 3} (Ln = Nd, Gd, Dy or Yb) synthesized. The third chapter, it describes the methodology continued in our experimental work; in the room, its are presented the obtained results of the static and dynamic method to determine the viability of separation of neighboring lanthanides; and finally, the five chapter shows the conclusions. In this study, it is concludes that the separation among neighboring lanthanides cannot be carried out in the minerals and used media; because

Recycling of Ammonia Wastewater During Vanadium Extraction from Shale

Science.gov (United States)

Shi, Qihua; Zhang, Yimin; Liu, Tao; Huang, Jing

2018-03-01

In the vanadium metallurgical industry, massive amounts of ammonia hydroxide or ammonia salt are added during the precipitation process to obtain V2O5; therefore, wastewater containing a high level of NH4 + is generated, which poses a serious threat to environmental and hydrologic safety. In this article, a novel process was developed to recycle ammonia wastewater based on a combination of ammonia wastewater leaching and crystallization during vanadium extraction from shale. The effects of the NH4 + concentration, temperature, time and liquid-to-solid ratio on the leaching efficiencies of vanadium, aluminum and potassium were investigated, and the results showed that 93.2% of vanadium, 86.3% of aluminum and 96.8% of potassium can be leached from sulfation-roasted shale. Subsequently, 80.6% of NH4 + was separated from the leaching solution via cooling crystallization. Vanadium was recovered via a combined method of solvent extraction, precipitation and calcination. Therefore, ammonia wastewater was successfully recycled during vanadium extraction from shale.

Nickel and vanadium extraction from the Syrian petroleum coke

International Nuclear Information System (INIS)

Shlewit, H.; Alibrahim, M.

2007-01-01

Syrian petroleum coke samples were characterized and submitted for salt-roasting treatment in electric furnace to evaluate the convenience of this procedure for the extraction of the vanadium, nickel and sulfur from coke. Both solution and solid residue remaining after salt roasting were separated by filtration and were analyzed for vanadium, nickel and sulfur. The solution was analyzed by UV-Visible spectroscopy for vanadium and nickel and gravimetrically for sulfur. The solid residue and the untreated samples of petroleum coke were analyzed by XRF spectrometry. Results showed that more than 90% of sulfur and 60% of vanadium could be extracted by salt roasting treatment. An alternative procedure has been suggested, in which, more than 80% of sulfur and small percentage of vanadium can be leached by 0.75 M of Na 2 CO 3 solution at 70-80 Co. Vanadium was selectively extracted by DEHPA/TBP from the loaded leached solution. The extraction procedure flowsheet was also suggested. (authors)

Chloride supporting electrolytes for all-vanadium redox flow batteries.

Science.gov (United States)

Kim, Soowhan; Vijayakumar, M; Wang, Wei; Zhang, Jianlu; Chen, Baowei; Nie, Zimin; Chen, Feng; Hu, Jianzhi; Li, Liyu; Yang, Zhenguo

2011-10-28

This paper examines vanadium chloride solutions as electrolytes for an all-vanadium redox flow battery. The chloride solutions were capable of dissolving more than 2.3 M vanadium at varied valence states and remained stable at 0-50 °C. The improved stability appeared due to the formation of a vanadium dinuclear [V(2)O(3)·4H(2)O](4+) or a dinuclear-chloro complex [V(2)O(3)Cl·3H(2)O](3+) in the solutions over a wide temperature range. The all-vanadium redox flow batteries with the chloride electrolytes demonstrated excellent reversibility and fairly high efficiencies. Only negligible, if any, gas evolution was observed. The improved energy capacity and good performance, along with the ease in heat management, would lead to substantial reduction in capital cost and life-cycle cost, making the vanadium chloride redox flow battery a promising candidate for stationary applications. This journal is © the Owner Societies 2011

Robustness and modular structure in networks

DEFF Research Database (Denmark)

Bagrow, James P.; Lehmann, Sune; Ahn, Yong-Yeol

2015-01-01

-12]. Many complex systems, from power grids and the Internet to the brain and society [13-15], can be modeled using modular networks comprised of small, densely connected groups of nodes [16, 17]. These modules often overlap, with network elements belonging to multiple modules [18, 19]. Yet existing work...... on robustness has not considered the role of overlapping, modular structure. Here we study the robustness of these systems to the failure of elements. We show analytically and empirically that it is possible for the modules themselves to become uncoupled or non-overlapping well before the network disintegrates....... If overlapping modular organization plays a role in overall functionality, networks may be far more vulnerable than predicted by conventional percolation theory....

Synthesis and luminescent properties of PEO/lanthanide oxide nanoparticle hybrid films

International Nuclear Information System (INIS)

Goubard, F.; Vidal, F.; Bazzi, R.; Tillement, O.; Chevrot, C.; Teyssie, D.

2007-01-01

In this study, we investigate the optical properties of lanthanide oxide nanoparticles dispersed in poly(ethylene oxide) (PEO) network as thermally stable polymeric films. The aim of this work is both to keep a good optical transparency in the visible domain and to obtain luminescent materials after incorporation of nanoparticles. For this purpose, we develop luminescent nanocrystals of oxides containing terbium ion as a doping element in Gd 2 O 3 . These sub-5-nm lanthanide oxides nanoparticles have been prepared by direct oxide precipitation in high-boiling polyalcohol solutions and characterized by luminescence spectroscopy. PEO/lanthanide oxide nanohybrid films are prepared by radical polymerization of poly(ethylene glycol) methacrylate after introduction of lanthanide oxide particles. As a first result; the obtained films present interesting luminescence properties with a very low lanthanide oxide content (up to 0.29 wt%). Furthermore, these films are still transparent and keep their original mechanical properties. Prior to describe the specific applications to optical use, we report here the dynamic mechanical analysis (DMA), X-ray diffraction (XRD) analysis, transmission electron microscopy (TEM), and luminescent properties of. nanohybrid films

Effect of indium addition in U-Zr metallic fuel on lanthanide migration

Energy Technology Data Exchange (ETDEWEB)

Kim, Yeon Soo, E-mail: yskim@anl.gov [Argonne National Laboratory, 9700 S. Cass Ave, Argonne, IL 60439 (United States); Wiencek, T.; O' Hare, E.; Fortner, J.; Wright, A. [Argonne National Laboratory, 9700 S. Cass Ave, Argonne, IL 60439 (United States); Cheon, J.S.; Lee, B.O. [Korea Atomic Energy Research Institute, 989-111 Daedeok-daero, Yuseong-gu, Daejeon 305-353 (Korea, Republic of)

2017-02-15

Advanced fast reactor concepts to achieve ultra-high burnup (∼50%) require prevention of fuel-cladding chemical interaction (FCCI). Fission product lanthanide accumulation at high burnup is substantial and significantly contributes to FCCI upon migration to the cladding interface. Diffusion barriers are typically used to prevent interaction of the lanthanides with the cladding. A more active method has been proposed which immobilizes the lanthanides through formation of stable compounds with an additive. Theoretical analysis showed that indium, thallium, and antimony are good candidates. Indium was the strongest candidate because of its low reactivity with iron-based cladding alloys. Characterization of the as-fabricated alloys was performed to determine the effectiveness of the indium addition in forming compounds with lanthanides, represented by cerium. Tests to examine how effectively the dopant prevents lanthanide migration under a thermal gradient were also performed. The results showed that indium effectively prevented cerium migration.

Effect of indium addition in U-Zr metallic fuel on lanthanide migration

Energy Technology Data Exchange (ETDEWEB)

Kim, Yeon Soo; Wiencek, T.; O' Hare, E.; Fortner, J.; Wright, A.; Cheon, J. S.; Lee, B. O.

2017-02-01

Advanced fast reactor concepts to achieve ultra-high burnup (~50%) require prevention of fuel-cladding chemical interaction (FCCI). Fission product lanthanide accumulation at high burnup is substantial and significantly contributes to FCCI upon migration to the cladding interface. Diffusion barriers are typically used to prevent interaction of the lanthanides with the cladding. A more active method has been proposed which immobilizes the lanthanides through formation of stable compounds with an additive. Theoretical analysis showed that indium, thallium, and antimony are good candidates. Indium was the strongest candidate because of its low reactivity with iron-based cladding alloys. Characterization of the as-fabricated alloys was performed to determine the effectiveness of the indium addition in forming compounds with lanthanides, represented by cerium. Tests to examine how effectively the dopant prevents lanthanide migration under a thermal gradient were also performed. The results showed that indium effectively prevented cerium migration.

Structure, ferroelectric ordering, and semiempirical quantum calculations of lanthanide based metal-organic framework: [Nd(C4H5O6)(C4H4O6)][3H2O

Science.gov (United States)

Ahmad, Bhat Zahoor; Want, Basharat

2016-04-01

We investigate the structure and ferroelectric behavior of a lanthanide based metal-organic framework (MOF), [Nd(C4H5O6)(C4H4O6)][3H2O]. X-ray crystal structure analyses reveal that it crystallizes in the P41212 space group with Nd centres, coordinated by nine oxygen atoms, forming a distorted capped square antiprismatic geometry. The molecules, bridged by tartrate ligands, form a 2D chiral structure. The 2D sheets are further linked into a 3D porous framework via strong hydrogen-bonding scheme (O-H…O ≈ 2.113 Å). Dielectric studies reveal two anomalies at 295 K and 185 K. The former is a paraelectric-ferroelectric transition, and the later is attributed to the freezing down of the motion of the hydroxyl groups. The phase transition is of second order, and the spontaneous polarization in low temperature phase is attributed to the ordering of protons of hydroxyl groups. The dielectric nonlinearity parameters have been calculated using Landau- Devonshire phenomenological theory. In addition, the most recent semiempirical models, Sparkle/PM7, Sparkle/RM1, and Sparkle/AM1, are tested on the present system to assay the accuracy of semiempirical quantum approaches to predict the geometries of solid MOFs. Our results show that Sparkle/PM7 model is the most accurate to predict the unit cell structure and coordination polyhedron geometry. The semiempirical methods are also used to calculate different ground state molecular properties.

Hybrid organic-inorganic porous semiconductor transducer for multi-parameters sensing.

Science.gov (United States)

Caliò, Alessandro; Cassinese, Antonio; Casalino, Maurizio; Rea, Ilaria; Barra, Mario; Chiarella, Fabio; De Stefano, Luca

2015-07-06

Porous silicon (PSi) non-symmetric multi-layers are modified by organic molecular beam deposition of an organic semiconductor, namely the N,N'-1H,1H-perfluorobutyldicyanoperylene-carboxydi-imide (PDIF-CN2). Joule evaporation of PDIF-CN2 into the PSi sponge-like matrix not only improves but also adds transducing skills, making this solid-state device a dual signal sensor for chemical monitoring. PDIF-CN2 modified PSi optical microcavities show an increase of about five orders of magnitude in electric current with respect to the same bare device. This feature can be used to sense volatile substances. PDIF-CN2 also improves chemical resistance of PSi against alkaline and acid corrosion. © 2015 The Author(s) Published by the Royal Society. All rights reserved.

Complex modular structure of large-scale brain networks

Science.gov (United States)

Valencia, M.; Pastor, M. A.; Fernández-Seara, M. A.; Artieda, J.; Martinerie, J.; Chavez, M.

2009-06-01

Modular structure is ubiquitous among real-world networks from related proteins to social groups. Here we analyze the modular organization of brain networks at a large scale (voxel level) extracted from functional magnetic resonance imaging signals. By using a random-walk-based method, we unveil the modularity of brain webs and show modules with a spatial distribution that matches anatomical structures with functional significance. The functional role of each node in the network is studied by analyzing its patterns of inter- and intramodular connections. Results suggest that the modular architecture constitutes the structural basis for the coexistence of functional integration of distant and specialized brain areas during normal brain activities at rest.

Two- and three-dimensional lanthanide-organic frameworks constructed using 1-hydro-6-oxopyridine-3-carboxylate and oxalate ligands.

Science.gov (United States)

Liu, Cai-Ming; Xiong, Ming; Zhang, De-Qing; Du, Miao; Zhu, Dao-Ben

2009-08-07

6-Hydroxypyridine-3-carboxylic acid (6-HOPy-3-CO(2)H) reacts with Ln(2)O(3) (Ln = Nd, Sm, Eu, Gd) and oxalic acid (H(2)OX) under hydrothermal conditions to generate four novel lanthanide-organic coordination polymeric networks [Ln(2)(1H-6-Opy-3-CO(2))(2)(OX)(2)(H(2)O)(3)] x 2.5 H(2)O (Ln = Nd, 1; Sm, 2; 1H-6-Opy-3-CO(2)(-) = 1-hydro-6-oxopyridine-3-carboxylate) and [Ln(1H-6-Opy-3-CO(2))(OX)(H(2)O)(2)] x H(2)O (Ln = Eu, 3; Gd, 4). The new co-ligand 1H-6-Opy-3-CO(2)(-) anion was generated by the autoisomerization of the single deprotonated 6-HOPy-3-CO(2)(-) anion (from the enol form into the ketone one). 1 and 2 are isomorphous, they possess a three-dimensional architecture constructed from Ln(3+) ions bridged by oxalate anions and two types of 1H-6-Opy-3-CO(2)(-) bridges, showing a three-nodal (4,5)-connected topology (3.4(2).5(2).6(3).7.8)(2)(3.5(3).6(2))(2)(3(2).6.7(2).8) or a simplified uninodal 6-connected topology (3(3).4(6).5(5).6), both topologies are completely new; while only one type of 1H-6-Opy-3-CO(2)(-) bridge is used to construct the two-dimensional layer networks of 3 and 4 besides oxalate bridges, both complexes 3 and 4 are isostructural, exhibiting the honeycomb topology 6(3). The lanthanide contraction effect is believed to play a key role in directing the formation of a particular structure. A magnetic study of 1-3 indicated that the coupling interaction between Ln(3+) ions is weak.

Porous Silica Sol-Gel Glasses Containing Reactive V2O5 Groups

Science.gov (United States)

Stiegman, Albert E.

1995-01-01

Porous silica sol-gel glasses into which reactive vanadium oxide functional groups incorporated exhibit number of unique characteristics. Because they bind molecules of some species both reversibly and selectively, useful as chemical sensors or indicators or as scrubbers to remove toxic or hazardous contaminants. Materials also oxidize methane gas photochemically: suggests they're useful as catalysts for conversion of methane to alcohol and for oxidation of hydrocarbons in general. By incorporating various amounts of other metals into silica sol-gel glasses, possible to synthesize new materials with broad range of new characteristics.

Vanadium extraction from slimes by the lime-bicarbonate method

International Nuclear Information System (INIS)

Lishchenko, T.V.; Vdovina, L.V.; Slobodchikova, R.I.

1978-01-01

Some main parameters of the lime-bicarbonate method of extracting vanadium from residues obtained in washing waters of mazut boilers on thermal stations have been determined. To study the process of vanadium extraction during caking of the residues with lime and subsequent leaching of water-soluble vanadium, a ''Minsk-22'' computer has been used for computation. Analysis of the equation derived has shown that a change in temperature of vanadium leaching, density of pulp, and a kind of heating of the charge affect the process only slightly. It has also been shown that the calcination temperature is expedient to be kept above 850 deg C and consumption temperature is expedient to be kept above 85O deg C and consumption of lime must not exceed 20% of the residues weight. Bicarbonate consumption exerts a decisive influence on completeness of vanadium extraction and must be increased up to >35%; duration of leaching should be raised up to 30-45 minutes. With increasing calcination temperature the duration of leaching decreases. When temperature and duration of calcination increase, the formation of water-soluble vanadium intensifies. With the aid of optimization program seven variants have been chosen, which ensure vanadium extraction into solution by 95-100%

Sensitivity Calculation of Vanadium Self-Powered Neutron Detector

International Nuclear Information System (INIS)

Cha, Kyoon Ho

2011-01-01

Self-powered neutron detector (SPND) is being widely used to monitor the reactor core of the nuclear power plants. The SPND contains a neutron-sensitive metallic emitter surrounded by a ceramic insulator. Currently, the rhodium SPND has been used in many nuclear power plants. The lifetime of rhodium is too short (about 3∼5 years) to operate the nuclear power plant economically. The vanadium (V) SPND is also primarily sensitive to neutrons like rhodium, but is a somewhat slower reaction time as that of a rhodium SPND. The benefit of vanadium over rhodium is its low depletion rate, which is a factor of 7 times less than that of rhodium. For this reason, a vanadium SPND has been being developed to replace the rhodium SPND which is used in OPR1000. Some Monte Carlo simulations were accomplished to calculate the initial sensitivity of vanadium emitter material and alumina (Al 2 O 3 ) insulator with a cylindrical geometry. An MCNP-X code was used to simulate some factors (neutron self shielding factor and electron escape probability from the emitter) necessary to calculate the sensitivity of vanadium detector. The simulation results were compared with some theoretical and experimental values. The method presented here can be used to analyze the optimum design of the vanadium SPND

Convergent evolution of modularity in metabolic networks through different community structures.

Science.gov (United States)

Zhou, Wanding; Nakhleh, Luay

2012-09-14

It has been reported that the modularity of metabolic networks of bacteria is closely related to the variability of their living habitats. However, given the dependency of the modularity score on the community structure, it remains unknown whether organisms achieve certain modularity via similar or different community structures. In this work, we studied the relationship between similarities in modularity scores and similarities in community structures of the metabolic networks of 1021 species. Both similarities are then compared against the genetic distances. We revisited the association between modularity and variability of the microbial living environments and extended the analysis to other aspects of their life style such as temperature and oxygen requirements. We also tested both topological and biological intuition of the community structures identified and investigated the extent of their conservation with respect to the taxonomy. We find that similar modularities are realized by different community structures. We find that such convergent evolution of modularity is closely associated with the number of (distinct) enzymes in the organism's metabolome, a consequence of different life styles of the species. We find that the order of modularity is the same as the order of the number of the enzymes under the classification based on the temperature preference but not on the oxygen requirement. Besides, inspection of modularity-based communities reveals that these communities are graph-theoretically meaningful yet not reflective of specific biological functions. From an evolutionary perspective, we find that the community structures are conserved only at the level of kingdoms. Our results call for more investigation into the interplay between evolution and modularity: how evolution shapes modularity, and how modularity affects evolution (mainly in terms of fitness and evolvability). Further, our results call for exploring new measures of modularity and network

Annual reports in inorganic and general syntheses 1974

CERN Document Server

Niedenzu, Kurt

1975-01-01

Annual Reports in Inorganic and General Syntheses-1974 presents an organized annual summary of synthetic developments in inorganic chemistry and its related areas. The book discusses the chemistry of simple and complex metal hydrides of main groups I, II, and III, boron, aluminium, gallium, indium, thallium, silicon, germanium, tin, lead, phosphorus, arsenic, antimony, bismuth, chalcogens, halogens, and pseudohalogens. The text also describes the chemistry of scandium, yttrium, lanthanides, actinides, titanium, zirconium, hafnium, vanadium, niobium, tantalum, chromium, molybdenum, tungsten, ma

Complexes of Y, La, and lanthanides with m-aminobenzoic acid

International Nuclear Information System (INIS)

Rzaczynska, Z.; Brzyska, W.

1989-01-01

m-Aminobenzoates of Y, La and lanthanides prepared in the reaction of the hydroxides of metal with m-aminobenzoic acid in solution have the general formula Ln(m-C 6 H 4 NH 2 COO) 3 .nH 2 O where n = 4 for Ho, Tm, n = 5 for Y, Sm, Dy, Er, Lu, and n = 6 for La, Nd, Eu, Gd, Tb, Yb. The water molecules in the hydrated compounds are in the outer coordination sphere. On heating in air at 350-410K dehydration occurs and anhydrous m-aminobenzoates Ln(m-C 6 H 4 NH 2 COO) 3 are formed. On the basis of the IR spectra it was found that the metal in hydrated m-aminobenzoate of lanthanides is simultaneously coordinated through amino- and carboxyl groups whereas in anhydrous m-aminobenzoates of lanthanides only trough the bidentate carboxyl group. From X-ray analysis it was stated that the hydrated m-aminobenzoates of lanthanides are isostructural in the whole range Y, La-Lu. (Author)

Design and construction of porous metal–organic frameworks based on flexible BPH pillars

International Nuclear Information System (INIS)

Hao, Xiang-Rong; Yang, Guang-sheng; Shao, Kui-Zhan; Su, Zhong-Min; Yuan, Gang; Wang, Xin-Long

2013-01-01

Three metal–organic frameworks (MOFs), [Co 2 (BPDC) 2 (4-BPH)·3DMF] n (1), [Cd 2 (BPDC) 2 (4-BPH) 2 ·2DMF] n (2) and [Ni 2 (BDC) 2 (3-BPH) 2 (H 2 O)·4DMF] n (3) (H 2 BPDC=biphenyl-4,4′-dicarboxylic acid, H 2 BDC=terephthalic acid, BPH=bis(pyridinylethylidene)hydrazine and DMF=N,N′-dimethylformamide), have been solvothermally synthesized based on the insertion of heterogeneous BPH pillars. Framework 1 has “single-pillared” MOF-5-like motif with inner cage diameters of up to 18.6 Å. Framework 2 has “double pillared” MOF-5-like motif with cage diameters of 19.2 Å while 3 has “double pillared” 8-connected framework with channel diameters of 11.0 Å. Powder X-ray diffraction (PXRD) shows that 3 is a dynamic porous framework. - Graphical abstract: By insertion of flexible BPH pillars based on “pillaring” strategy, three metal–organic frameworks are obtained showing that the porous frameworks can be constructed in a much greater variety. Highlights: ► Frameworks 1 and 2 have MOF-5 like motif. ► The cube-like cages in 1 and 2 are quite large, comparable to the IRMOF-10. ► Framework 1 is “single-pillared” mode while 2 is “double-pillared” mode. ► PXRD and gas adsorption analysis show that 3 is a dynamic porous framework.

Effect of vanadium compounds on acid phosphatase activity

OpenAIRE

Vescina, Cecilia M.; Sálice, Viviana C.; Cortizo, Ana María; Etcheverry, Susana B.

1996-01-01

The direct effect of different vanadium compounds on acid phosphatase (ACP) activity was investigated. Vanadate and vanadyl but not pervanadate inhibited the wheat germ ACP activity. These vanadium derivatives did not alter the fibroblast Swiss 3T3 soluble fraction ACP activity. Using inhibitors of tyrosine phosphatases (PTPases), the wheat germ ACP was partially characterized as a PTPase. This study suggests that the inhibitory ability of different vanadium derivatives to modulate ACP activi...

The kinetics of lanthanide complexation by EDTA and DTPA in lactate media.

Science.gov (United States)

Nash, K L; Brigham, D; Shehee, T C; Martin, A

2012-12-28

The interaction of trivalent lanthanide and actinide cations with polyaminopolycarboxylic acid complexing agents in lactic acid buffer systems is an important feature of the chemistry of the TALSPEAK process for the separation of trivalent actinides from lanthanides. To improve understanding of metal ion coordination chemistry in this process, the results of an investigation of the kinetics of lanthanide complexation by ethylenediamine-N,N,N',N'-tetraacetic acid (EDTA) and diethylenetriamine-N,N,N',N'',N''-pentaacetic acid (DTPA) in 0.3 M lactic acid/0.3 M ionic strength solution are reported. Progress of the reaction was monitored using the distinctive visible spectral changes attendant to lanthanide complexation by the colorimetric indicator ligand Arsenazo III, which enables the experiment but plays no mechanistic role. Under the conditions of these experiments, the reactions occur in a time regime suitable for study by stopped-flow spectrophotometric techniques. Experiments have been conducted as a function of EDTA/DTPA ligand concentration, total lactic acid concentration, and pH. The equilibrium perturbation reaction proceeds as a first order approach to equilibrium over a wide range of conditions, allowing the simultaneous determination of complex formation and dissociation rate constants. The rate of the complexation reaction has been determined for the entire lanthanide series (except Pm(3+)). The predominant pathway for lanthanide-EDTA and lanthanide-DTPA dissociation is inversely dependent on the total lactate concentration; the complex formation reaction demonstrates a direct dependence on [H(+)]. Unexpectedly, the rate of the complex formation reaction is seen in both ligand systems to be fastest for Gd(3+). Correlation of these results indicates that in 0.3 M lactate solutions the exchange of lanthanide ions between lactate complexes and the polyaminopolycarboxylate govern the process.

Simultaneous phase and size control of upconversion nanocrystals through lanthanide doping

KAUST Repository

Wang, Feng; Han, Yu; Lim, Chinseong; Lu, Yunhao; Wang, Juan; Xu, Jun; Chen, Hongyu; Zhang, Chun; Hong, Minghui; Liu, Xiaogang

2010-01-01

or hexagonal) and upconversion emission colour (green to blue) through use of trivalent lanthanide dopant ions introduced at precisely defined concentrations. We use first-principles calculations to confirm that the influence of lanthanide doping on crystal

Vanadium carbide coatings: deposition process and properties

International Nuclear Information System (INIS)

Borisova, A.; Borisov, Y.; Shavlovsky, E.; Mits, I.; Castermans, L.; Jongbloed, R.

2001-01-01

Vanadium carbide coatings on carbon and alloyed steels were produced by the method of diffusion saturation from the borax melt. Thickness of the vanadium carbide layer was 5-15 μm, depending upon the steel grade and diffusion saturation parameters. Microhardness was 20000-28000 MPa and wear resistance of the coatings under conditions of end face friction without lubrication against a mating body of WC-2Co was 15-20 times as high as that of boride coatings. Vanadium carbide coatings can operate in air at a temperature of up to 400 o C. They improve fatigue strength of carbon steels and decrease the rate of corrosion in sea and fresh water and in acid solutions. The use of vanadium carbide coatings for hardening of various types of tools, including cutting tools, allows their service life to be extended by a factor of 3 to 30. (author)

Ion-exchange preparation of high-purity vanadium acid from industrial liquors

International Nuclear Information System (INIS)

Sajdakhmedov, U.A.; Arslanov, Sh.S.; Vulikh, A.I.

1994-01-01

The results of investigations on production of special-purity vanadium acid and vanadium oxide directly from process solutions (technical grade liquors) using ionites are presented. Potentiality of thorough purification of vanadium(5) oxide, when producing vanadium acid on the KU-2 cationite with subsequent purification on anionite, is shown. On the basis of the results obtained a principle flowsheet of ion-exchange production of high-purity vanadium(5) oxide from industrial liquors has been developed. 2 refs.; 1 fig.; 4 tabs

Citrate based ''TALSPEAK'' lanthanide-actinide separation process

International Nuclear Information System (INIS)

Del Cul, G.D.; Bond, W.D.; Toth, L.M.; Davis, G.D.; Dai, S.; Metcalf, D.H.

1994-09-01

The potential hazard posed to future generations by long-lived radionuclides such as the transuranic elements (TRU) is perceived as a major problem associated with the use of nuclear power. TRU wastes have to remain isolated from the environment for ''geological'' periods of time. The costs of building, maintaining, and operating a ''geological TRU repository'' can be very high. Therefore, there are significant economical advantages in segregating the relatively low volume of TRU wastes from other nuclear wastes. The chemical behavior of lanthanides and actinides, 4f and 5f elements respectively, is rather similar. As a consequence, the separation of these two groups is difficult. The ''TALSPEAK'' process (Trivalent Actinide Lanthanide Separations by Phosphorus-reagent Extraction from Aqueous Complexes) is one of the few means available to separate the trivalent actinides from the lanthanides. The method is based on the preferential complexation of the trivalent actinides by an aminopolyacetic acid. Cold experiments showed that by using citric acid the deleterious effects produced by impurities such as zirconium are greatly reduced

Ternary complex formation of lanthanides and radiolanthanides with phosphate and serum proteins

International Nuclear Information System (INIS)

Neumaier, B.; Roesch, F.

1999-01-01

Radioyttrium was recently reported to form ternary complexes with phosphate and serum proteins in blood. In the present work it was investigated whether the trivalent radiolanthanides react in a chemically similar way. In systematic binding studies using gel filtration a ternary complex formation between different lanthanides, phosphate and serum proteins could be identified. The tendency to build a ternary compound of the type Ln III - phosphate - serum protein, however, is dependent on the ionic radii of the lanthanides. Whereas the light and transition lanthanides have a strong inclination to build a ternary complex, this tendency is weaker for the heavier ones. Taking into account the high content of phosphate in human blood, the corresponding ternary complexes of radiolanthanides represent an important transport form of these elements in blood. This finding may contribute to an understanding of the nuclear medical observation on the biodistribution of radiolanthanides. The heavy radiolanthanides can be classified as bone seeking metals, whereas the light and transition lanthanide elements accumulate mainly in the liver and the spleen. For the lighter radiolanthanides the corresponding ternary complexes thus represent an important transport form in blood. This physicochemical form of lanthanides mainly results in reticulo endothelial accumulation; on the other hand, the lower tendency of heavier lanthanides leads to preferential skeletal deposition. (orig.)

Layer-by-layer strippable Ag multilayer films fabricated by modular assembly.

Science.gov (United States)

Li, Yan; Chen, Xiaoyan; Li, Qianqian; Song, Kai; Wang, Shihui; Chen, Xiaoyan; Zhang, Kai; Fu, Yu; Jiao, Yong-Hua; Sun, Ting; Liu, Fu-Chun; Han, En-Hou

2014-01-21

We have developed a new method to fabricate multilayer films, which uses prepared thin films as modular blocks and transfer as operation mode to build up multilayer structures. In order to distinguish it from the in situ fabrication manner, this method is called modular assembly in this study. On the basis of such concept, we have fabricated a multilayer film using the silver mirror film as the modular block and poly(lactic acid) as the transfer tool. Due to the special double-layer structure of the silver mirror film, the resulting multilayer film had a well-defined stratified architecture with alternate porous/compact layers. As a consequence of the distinct structure, the interaction between the adjacent layers was so weak that the multilayer film could be layer-by-layer stripped. In addition, the top layer in the film could provide an effective protection on the morphology and surface property of the underlying layers. This suggests that if the surface of the film was deteriorated, the top layer could be peeled off and the freshly exposed surface would still maintain the original function. The successful preparation of the layer-by-layer strippable silver multilayer demonstrates that modular assembly is a feasible and effective method to build up multilayer films capable of creating novel and attractive micro/nanostructures, having great potential in the fabrication of nanodevices and coatings.

Synthesis and luminescent properties of PEO/lanthanide oxide nanoparticle hybrid films

Energy Technology Data Exchange (ETDEWEB)

Goubard, F. [LPPI, Universite de Cergy-Pontoise, 5 Mail Gay-Lussac, Neuville-sur-Oise, 95031 Cergy-Pontoise cedex (France)]. E-mail: fabrice.goubard@u-cergy.fr; Vidal, F. [LPPI, Universite de Cergy-Pontoise, 5 Mail Gay-Lussac, Neuville-sur-Oise, 95031 Cergy-Pontoise cedex (France); Bazzi, R. [LPCML, Universite Lyon 1, 43 Bd. du 11 Novembre 1918, 69622 Villeurbanne (France); Tillement, O. [LPCML, Universite Lyon 1, 43 Bd. du 11 Novembre 1918, 69622 Villeurbanne (France); Nano-H, 23 rue Royal, 69001 Lyon (France); Chevrot, C. [LPPI, Universite de Cergy-Pontoise, 5 Mail Gay-Lussac, Neuville-sur-Oise, 95031 Cergy-Pontoise cedex (France); Teyssie, D. [LPPI, Universite de Cergy-Pontoise, 5 Mail Gay-Lussac, Neuville-sur-Oise, 95031 Cergy-Pontoise cedex (France)

2007-10-15

In this study, we investigate the optical properties of lanthanide oxide nanoparticles dispersed in poly(ethylene oxide) (PEO) network as thermally stable polymeric films. The aim of this work is both to keep a good optical transparency in the visible domain and to obtain luminescent materials after incorporation of nanoparticles. For this purpose, we develop luminescent nanocrystals of oxides containing terbium ion as a doping element in Gd{sub 2}O{sub 3}. These sub-5-nm lanthanide oxides nanoparticles have been prepared by direct oxide precipitation in high-boiling polyalcohol solutions and characterized by luminescence spectroscopy. PEO/lanthanide oxide nanohybrid films are prepared by radical polymerization of poly(ethylene glycol) methacrylate after introduction of lanthanide oxide particles. As a first result; the obtained films present interesting luminescence properties with a very low lanthanide oxide content (up to 0.29 wt%). Furthermore, these films are still transparent and keep their original mechanical properties. Prior to describe the specific applications to optical use, we report here the dynamic mechanical analysis (DMA), X-ray diffraction (XRD) analysis, transmission electron microscopy (TEM), and luminescent properties of. nanohybrid films.

Vanadium research recharged

International Nuclear Information System (INIS)

Luntz, Stephen

2011-01-01

US President Barack Obama has described Maria Skyllas-Kazacos’ research as “one of the coolest things I’ve ever said out loud”. Vanadium redox batteries could be electricity’s ultimate storage mechanism.

2. Intermetallic compounds with lanthanides

International Nuclear Information System (INIS)

Elemans, J.B.A.A.

1975-01-01

Theoretical considerations are given concerning the structures of intermetallic compounds of the lanthanides and thorium (R) on the one hand, and with Fe, Co or Ni (M) on the other. They all derive from the parent composition RM 5 with the CaCu 5 hexagonal structure. This consists of alternate layers in which the M atoms are distinguished as M 1 and M 2 . The other compounds whose structures are studied are obtained by systematic replacement of R by M, or vice versa. In the first type, every third R is replaced by two M's yielding R 2 M 17 compounds. The substitution may be truly random or structured in two ways: so that either the hexagonal structure is maintained or that it is converted into a rhombihedral one. In the second type, one M (in a M 1 position) out of every five is replaced by one R, giving rise to RM 2 compounds which form Laves phases. In the third type, the M 1 's are replaced by R's, resulting in compounds RM 3 . In the fourth type, every third M is replaced by R, yielding R 2 M 7 compounds. With M = Co and R a light lanthanide, the compounds are ferromagnets; with R yttrium, thorium, or a heavy lanthanide, they are ferrimagnets. The preparation of the compounds in an arc-melting apparatus under an Ar-atmosphere followed by annealing is described

Low-temperature direct synthesis of mesoporous vanadium nitrides for electrochemical capacitors

Energy Technology Data Exchange (ETDEWEB)

Lee, Hae-Min [Institute of NT-IT Fusion Technology, Ajou University, 206 Worldcup-ro, Yeongtong-gu, Suwon 16499 (Korea, Republic of); Jeong, Gyoung Hwa [Department of Chemistry, Ulsan National Institute of Science and Technology (UNIST), Banyeon 100, Ulsan 44919 (Korea, Republic of); Kim, Sang-Wook [Department of Molecular Science and Technology, Ajou University, 206 Worldcup-ro, Yeongtong-gu, Suwon 16499 (Korea, Republic of); Kim, Chang-Koo, E-mail: changkoo@ajou.ac.kr [Department of Chemical Engineering and Department of Energy Systems Research, Ajou University, 206 Worldcup-ro, Yeongtong-gu, Suwon 16499 (Korea, Republic of)

2017-04-01

Highlights: • Vanadium nitrides were directly synthesized by a one-step chemical precipitation method. • This method was carried out at a low temperature of 70 °C. • Vanadium nitrides had a specific capacitance of 598 F/g. • The equivalent series resistance of the vanadium nitride electrode was 1.42 Ω after 5000 cycles. - Abstract: Mesoporous vanadium nitrides are directly synthesized by a one-step chemical precipitation method at a low temperature (70 °C). Structural and morphological analyses reveal that vanadium nitride consist of long and slender nanowhiskers, and mesopores with diameters of 2–5 nm. Compositional analysis confirms the presence of vanadium in the VN structure, along with oxidized vanadium. The cyclic voltammetry and charge-discharge tests indicate that the obtained material stores charges via a combination of electric double-layer capacitance and pseudocapacitance mechanisms. The vanadium nitride electrode exhibits a specific capacitance of 598 F/g at a current density of 4 A/g. After 5000 charge-discharge cycles, the electrode has an equivalent series resistance of 1.42 Ω and retains 83% of its initial specific capacitance. This direct low-temperature synthesis of mesoporous vanadium nitrides is a simple and promising method to achieve high specific capacitance and low equivalent series resistance for electrochemical capacitor applications.

Recent advances in porous nanoparticles for drug delivery in antitumoral applications: inorganic nanoparticles and nanoscale metal-organic frameworks.

Science.gov (United States)

Baeza, Alejandro; Ruiz-Molina, Daniel; Vallet-Regí, María

2017-06-01

Nanotechnology has provided new tools for addressing unmet clinical situations, especially in the oncology field. The development of smart nanocarriers able to deliver chemotherapeutic agents specifically to the diseased cells and to release them in a controlled way has offered a paramount advantage over conventional therapy. Areas covered: Among the different types of nanoparticle that can be employed for this purpose, inorganic porous materials have received significant attention in the last decade due to their unique properties such as high loading capacity, chemical and physical robustness, low toxicity and easy and cheap production in the laboratory. This review discuss the recent advances performed in the application of porous inorganic and metal-organic materials for antitumoral therapy, paying special attention to the application of mesoporous silica, porous silicon and metal-organic nanoparticles. Expert opinion: The use of porous inorganic nanoparticles as drug carriers for cancer therapy has the potential to improve the life expectancy of the patients affected by this disease. However, much work is needed to overcome their drawbacks, which are aggravated by their hard nature, exploiting the advantages offered by highly the ordered pore network of these materials.

Adsorption behaviors of trivalent actinides and lanthanides on pyridine resin in lithium chloride aqueous solution

International Nuclear Information System (INIS)

Tatsuya Suzuki

2013-01-01

The adsorption behaviors of trivalent actinides and lanthanides on pyridine resin in lithium chloride aqueous solution were investigated. The adsorbed amounts of lanthanides and the degree of mutual separation of lanthanides increased with an increase in the concentration of lithium chloride in aqueous solution. The group separation of the trivalent actinides and lanthanides was observed. This separation phenomenon is similar in a hydrochloric acid solution. However, the adsorption behavior of lanthanides in lithium chloride is different from their behavior in a hydrochloric acid solution. This fact shows that the adsorption mechanisms of lanthanides in a lithium chloride aqueous solution and in a hydrochloric acid solution are different; the adsorption mechanisms are attributed to the ion exchange in a hydrochloric acid solution, and to the complex formation with pyridine group in a lithium chloride solution. (author)

Fatigue of vanadium--hydrogen alloys

International Nuclear Information System (INIS)

Lee, K.S.; Stoloff, N.S.

1975-01-01

Hydrogen contents near and above the room temperature solubility limit increase the high cycle fatigue life but decrease low cycle life of polycrystalline vanadium. Changes in endurance limit with hydrides may be a consequence of decreased cyclic strain hardening coefficient, n'. 132 ppM hydrogen in solution has only a slightly beneficial effect on stress controlled fatigue life and essentially no effect on low cycle fatigue life. Unalloyed vanadium exhibits profuse striations, while hydrides produce cleavage cracks in fatigued samples. 10 fig

r-PROCESS LANTHANIDE PRODUCTION AND HEATING RATES IN KILONOVAE

Energy Technology Data Exchange (ETDEWEB)

Lippuner, Jonas; Roberts, Luke F., E-mail: jlippuner@tapir.caltech.edu [TAPIR, Walter Burke Institute for Theoretical Physics, California Institute of Technology, MC 350-17, 1200 E California Boulevard, Pasadena CA 91125 (United States)

2015-12-20

r-process nucleosynthesis in material ejected during neutron star mergers may lead to radioactively powered transients called kilonovae. The timescale and peak luminosity of these transients depend on the composition of the ejecta, which determines the local heating rate from nuclear decays and the opacity. Kasen et al. and Tanaka and Hotokezaka pointed out that lanthanides can drastically increase the opacity in these outflows. We use the new general-purpose nuclear reaction network SkyNet to carry out a parameter study of r-process nucleosynthesis for a range of initial electron fractions Y{sub e}, initial specific entropies s, and expansion timescales τ. We find that the ejecta is lanthanide-free for Y{sub e} ≳ 0.22−0.30, depending on s and τ. The heating rate is insensitive to s and τ, but certain, larger values of Y{sub e} lead to reduced heating rates, due to individual nuclides dominating the heating. We calculate approximate light curves with a simplified gray radiative transport scheme. The light curves peak at about a day (week) in the lanthanide-free (-rich) cases. The heating rate does not change much as the ejecta becomes lanthanide-free with increasing Y{sub e}, but the light-curve peak becomes about an order of magnitude brighter because it peaks much earlier when the heating rate is larger. We also provide parametric fits for the heating rates between 0.1 and 100 days, and we provide a simple fit in Y{sub e}, s, and τ to estimate whether or not the ejecta is lanthanide-rich.

r-PROCESS LANTHANIDE PRODUCTION AND HEATING RATES IN KILONOVAE

International Nuclear Information System (INIS)

Lippuner, Jonas; Roberts, Luke F.

2015-01-01

r-process nucleosynthesis in material ejected during neutron star mergers may lead to radioactively powered transients called kilonovae. The timescale and peak luminosity of these transients depend on the composition of the ejecta, which determines the local heating rate from nuclear decays and the opacity. Kasen et al. and Tanaka and Hotokezaka pointed out that lanthanides can drastically increase the opacity in these outflows. We use the new general-purpose nuclear reaction network SkyNet to carry out a parameter study of r-process nucleosynthesis for a range of initial electron fractions Y e , initial specific entropies s, and expansion timescales τ. We find that the ejecta is lanthanide-free for Y e ≳ 0.22−0.30, depending on s and τ. The heating rate is insensitive to s and τ, but certain, larger values of Y e lead to reduced heating rates, due to individual nuclides dominating the heating. We calculate approximate light curves with a simplified gray radiative transport scheme. The light curves peak at about a day (week) in the lanthanide-free (-rich) cases. The heating rate does not change much as the ejecta becomes lanthanide-free with increasing Y e , but the light-curve peak becomes about an order of magnitude brighter because it peaks much earlier when the heating rate is larger. We also provide parametric fits for the heating rates between 0.1 and 100 days, and we provide a simple fit in Y e , s, and τ to estimate whether or not the ejecta is lanthanide-rich

Lanthanide light for biology and medical diagnosis

International Nuclear Information System (INIS)

Bünzli, Jean-Claude G.

2016-01-01

Optical imaging emerges as a vital component of the various techniques needed to meet the stringent requirements of modern bioanalysis and bioimaging. Lanthanide luminescent bioprobes (LLBs) have greatly contributed to this field during the past 35 years because they have definite advantages such as little or no photobleaching and, thanks to time-gated detection, high sensitivity. The review summarizes the numerous tools offered by LLBs under their various forms, coordination compounds, nanoparticles, upconverting nanoparticles and their bioconjugates. It then focuses on biosensing, including point-of-care analysis, and then on both in vitro and in vivo bioimaging with visible and NIR light. The last section compares the performances of LLBs versus those of other commonly used bioprobes (organic dyes, quantum dots, and transition metal complexes). It is concluded that although LLBs will not replace all of existing bioprobes, they add invaluable new specific technologies to the biologist and medical doctor toolboxes. A good deal of improvements are achieved through nanotechnologies, which demonstrates that progresses in biosciences depend on the intersection of different disciplines, photophysics, chemistry, biochemistry, nanotechnology, and materials science. - Highlights: • Lanthanide luminescent bioprobes (LLBs) are indispensable tools in biosciences. • The tools provided by LLBs are summarized. • Main trends in biosensing and point-of-care analysis are presented. • Issues regarding optical bioimaging with visible and NIR light are described. • Characteristics of LLBs, including nanoparticles, are compared to other bioprobes.

Lanthanide light for biology and medical diagnosis

Energy Technology Data Exchange (ETDEWEB)

Bünzli, Jean-Claude G., E-mail: jean-claude.bunzli@epfl.ch [Fujian Institute of Research on the Structure of Matter, Chinese Academy of Sciences, Fuzhou, Fujian 35002 (China); Institute of Chemical Sciences and Engineering, École Polytechnique Fédérale de Lausanne (EPFL), 1015 Lausanne (Switzerland)

2016-02-15

Optical imaging emerges as a vital component of the various techniques needed to meet the stringent requirements of modern bioanalysis and bioimaging. Lanthanide luminescent bioprobes (LLBs) have greatly contributed to this field during the past 35 years because they have definite advantages such as little or no photobleaching and, thanks to time-gated detection, high sensitivity. The review summarizes the numerous tools offered by LLBs under their various forms, coordination compounds, nanoparticles, upconverting nanoparticles and their bioconjugates. It then focuses on biosensing, including point-of-care analysis, and then on both in vitro and in vivo bioimaging with visible and NIR light. The last section compares the performances of LLBs versus those of other commonly used bioprobes (organic dyes, quantum dots, and transition metal complexes). It is concluded that although LLBs will not replace all of existing bioprobes, they add invaluable new specific technologies to the biologist and medical doctor toolboxes. A good deal of improvements are achieved through nanotechnologies, which demonstrates that progresses in biosciences depend on the intersection of different disciplines, photophysics, chemistry, biochemistry, nanotechnology, and materials science. - Highlights: • Lanthanide luminescent bioprobes (LLBs) are indispensable tools in biosciences. • The tools provided by LLBs are summarized. • Main trends in biosensing and point-of-care analysis are presented. • Issues regarding optical bioimaging with visible and NIR light are described. • Characteristics of LLBs, including nanoparticles, are compared to other bioprobes.

Environmental versatility promotes modularity in large scale metabolic networks

OpenAIRE

Samal A.; Wagner Andreas; Martin O.C.

2011-01-01

Abstract Background The ubiquity of modules in biological networks may result from an evolutionary benefit of a modular organization. For instance, modularity may increase the rate of adaptive evolution, because modules can be easily combined into new arrangements that may benefit their carrier. Conversely, modularity may emerge as a by-product of some trait. We here ask whether this last scenario may play a role in genome-scale metabolic networks that need to sustain life in one or more chem...

Synthesis and characterization of lanthanide picrate complexes with 4-picoline-N-oxide (4-pic N O)

International Nuclear Information System (INIS)

Silva, E.M. da.

1991-01-01

The lanthanide picrate complexes with 4-picoline-N-oxide were obtained from ethanolic solutions of the hydrated lanthanide picrate and the ligand. The lanthanide content was determined by complexometric titration with EDTA. Carbon, Nitrogen and Hydrogen were determined by microanalytical procedures. Chemical analysis of the lanthanide picrate complexes are also presented. (author)

Process for recovering yttrium and lanthanides from wet-process phosphoric acid

Energy Technology Data Exchange (ETDEWEB)

Janssen, J.A.; Weterings, C.A.

1983-06-28

Process for recovering yttrium and lanthanides from wet-process phosphoric acid by adding a flocculant to the phosphoric acid, separating out the resultant precipitate and then recovering yttrium and lanthanides from the precipitate. Uranium is recovered from the remaining phosphoric acid.

Pressure effect of the 1H NMR spectra of organic compounds in the presence of lanthanide shift reagents. A formally associative process characterized by volume expansion

International Nuclear Information System (INIS)

Schulman, E.M.; Cheung, C.K.; Merbach, A.E.; Yamada, H.; le Noble, W.J.

1987-01-01

Following the successful application of hydrostatic pressure in mechanistic investigations of organic reactions, chemists have launched a vigorous effort to apply this tool to substitution reactions of coordination compounds. The authors began to study pressure effects in the NMR spectra of keton-lanthanide combination with the hope that the increase shifts anticipated might enhance the utility of the method, perhaps even expand its applicability to new classes of compounds. 5-Phenyl- and 5-tert-butyladamantan-2-one, piperidine, tetrahydrofuran, and cyclopentanol exhibited pressure-reduced lanthanide-induced shifts with Eu(fod) 3 ; Yb(fob) 3 and the shielding reagent Pr(fod) 3 showed the same effect with adamantanone. Solvent variations (CD 2 Cl 2 , CCl 4 ) caused minor changes in the magnitude of these shifts but did not reverse any. With the objective of learning whether these effects are due to a suppressed equilibrium population or to a reduction in the bound shift of the complex, they measured the spectra for a series or equimolar solutions of adamantanone and Eu(fod) 3 in CDCl 3 and used the Bouquant-Chuche equation to calculate both. Reasonable agreement with known atmosphere pressure data was obtained

Gamma ray induced decomposition of lanthanide nitrates

International Nuclear Information System (INIS)

Joshi, N.G.; Garg, A.N.

1992-01-01

Gamma ray induced decomposition of the lanthanide nitrates, Ln(NO 3 ) 3 .xH 2 O where Ln=La, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Tm and Yb has been studied at different absorbed doses up to 600 kGy. G(NO 2 - ) values depend on the absorbed dose and the nature of the outer cation. It has been observed that those lanthanides which exhibit variable valency (Ce and Eu) show lower G-values. An attempt has been made to correlate thermal and radiolytic decomposition processes. (author). 20 refs., 3 figs., 1 tab

Determination of Vanadium Binding Mode on Seawater-Contacted Polyamidoxime Adsorbents

Energy Technology Data Exchange (ETDEWEB)

Zhang, Zhicheng [Lawrence Berkeley National Laboratory (LBNL); Rao, Linfeng [Lawrence Berkeley National Laboratory (LBNL); Abney, Carter W. [Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States); Bryantsev, Vyacheslav [Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States); Ivanov, Aleksandr [Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States)

2017-09-01

Adsorbents developed for the recovery of uranium from seawater display poor selectivity over other transition metals present in the ocean, with vanadium particularly problematic. To improve selectivity, an indispensable step is the positive identification of metal binding environments following actual seawater deployment. In this work we apply x-ray absorption fine structure (XAFS) spectroscopy to directly investigate the vanadium binding environment on seawater-deployed polyamidoxime adsorbents. Comparison of the x-ray absorption near edge spectra (XANES) reveal marked similarities to recently a reported non-oxido vanadium (V) structure formed upon binding with cyclic imidedioxime, a byproduct of generating amidoxime functionalities. Density functional theory (DFT) calculations provided a series of putative vanadium binding environments for both vanadium (IV) and vanadium (V) oxidation states, and with both amidoxime and cyclic imidedioxime. Fits of the extended XAFS (EXAFS) data confirmed vanadium (V) is bound exclusively by the cyclic imidedioxime moiety in a 1:2 metal:ligand fashion, though a modest structural distortion is also observed compared to crystal structure data and computationally optimized geometries which is attributed to morphology effects from the polymer graft chain and the absence of crystal packing interactions. These results demonstrate that improved selectivity for uranium over vanadium can be achieved by suppressing the formation of cyclic imidedioxime during preparation of polyamidoxime adsorbents for seawater uranium recovery.

Synthesis, crystal structures, and luminescent properties of two series' of new lanthanide (III) amino-carboxylate-phosphonates.

Science.gov (United States)

Zhou, Tian-Hua; Yi, Fei-Yan; Li, Pei-Xin; Mao, Jiang-Gao

2010-02-01

Hydrothermal reactions of lanthanide(III) chlorides with 4-HOOC-C(6)H(4)-CH(2)NHCH(2)PO(3)H(2) (H(3)L) at different ligand-to-metal (L/M) ratios afforded nine new lanthanide(III) carboxylate-phosphonates with two types of 3D network structures, namely, LnCl(HL)(H(2)O)(2) (Ln = Sm, 1; Eu, 2; Gd, 3; Tb, 4; Dy, 5; Er, 6) and [Ln(2)(HL)(H(2)L)(L)(H(2)O)(2)].4H(2)O (Ln = Nd, 7; Sm, 8; Eu, 9). Compounds 1-6 are isostructural and feature a 3D network in which the LnO(7)Cl polyhedra are interconnected by bridging CPO(3) tetrahedra into 2D inorganic layers parallel to the bc plane. These layers are further cross-linked by organic groups of the carboxylate-phosphonate ligands via the coordination of the carboxylate groups into a pillared-layered architecture. Compounds 7-9 are also isostructural and feature a 3D open-framework composed of 1D lanthanide(III) phosphonate inorganic slabs which are further bridged by organic groups of the carboxylate-phosphonate liagnds via the coordination of the carboxylate groups, forming large 1D tunnels along the b-axis which are filled by lattice water molecules. Luminescent measurements indicate that compounds 2, 4, and 5 show strong emission bands in red, green, and yellow light region, respectively. Magnetic properties of 2, 3, 5, and 7 have also been studied.

Biocombatibility and in vivo toxicity assessment of multilayered polymer encapsulated lanthanide doped particles

International Nuclear Information System (INIS)

Dhanya, C.R.; Sri Sivakumar; Jaishree, J.; Abraham, Annie

2013-01-01

Layer-by-layer (LbL) deposition technique has led to the development of multilayered multifunctional nanoparticles that can prove to be promising system for directed drug delivery. Recently, surface functionalized Lanthanide doped nanoparticles have been explored as a candidate for biomedical applications like bio-detection, fluorescence imaging and drug delivery. The toxicity behaviors of biomedical devices proposed for therapeutic use in human must be checked for their toxicity behaviors in animal models. Here, we have presented an initial systematic animal toxicity study of polymer encapsulated lanthanide doped particle in Swiss Albino mice. Polymer coated LNPs with concentration of 100 nM in PBS was administered intravenously through tail vein according to body weight (4μl/g). Animal behavior, survival and animal mass, were monitored and evaluated over short-term (one week) and long-term (one month) periods, after which animals were euthanized. Blood was collected for evaluating clinical biochemistry (SGOT and SGPT) and hematological parameters, and tissues (liver and kidney) for organ histology. Results demonstrated normal serum clinical biochemistry in animals for both short and long time exposure. Histological examination of LNP treated mice also showed normal histology of liver and kidney even after one month of administration. Similar results were obtained for hematological evaluation. Results exhibited the systemic nontoxic nature of the polymer encapsulated lanthanide particles and their suitability as a tool for tumor targeted drug delivery. (author)

Vanadium dioxide formed by the sol-gel process

International Nuclear Information System (INIS)

Potember, R.S.; Speck, K.R.; Hu, H.S.

1990-01-01

This patent describes a process for the deposition of a crystalline vanadium dioxide thin film. It comprises: providing a solution comprising a vanadium tetraalkoxide and solvent; allowing hydrolysis and condensation reactions to progressively form a homogeneous sol from the solution, applying a coating of the sol to the substrate; allowing a gel to form from the sol on the substrate by evaporating the solvent; dehydrating the gel by heat treatment under an inert atmosphere to form the crystalline vanadium dioxide film

Vanadium alloys for the radiative divertor program of DIII-D

International Nuclear Information System (INIS)

Smith, J.P.; Johnson, W.R.; Stambaugh, R.D.; Trester, P.W.; Smith, D.; Bloom, E.

1995-10-01

Vanadium alloys provide an attractive solution for fusion power plants as they exhibit a potential for low environmental impact due to low level of activation from neutron fluence and a relatively short half-life. They also have attractive material properties for use in a reactor. General Atomics along with Argonne National Laboratory (ANL) and Oak Ridge National Laboratory (ORNL), has developed a plan to utilize vanadium alloys as part of the Radiative Divertor Project (RDP) modification for the DIII-D tokamak. The goal for using vanadium alloys is to provide a meaningful step towards developing advanced materials for fusion power applications by demonstrating the in-service behavior of a vanadium alloy (V-4Cr-4Ti) in a tokamak in conjunction with developing essential fabrication technology for the manufacture of full-scale vanadium alloy components. A phased approach towards utilizing vanadium in DIII-D is being used starting with small coupons and samples, advancing to a small component, and finally a portion of the new double-null, slotted divertor will be fabricated from vanadium alloy product forms. A major portion of the program is research and development to support fabrication and resolve key issues related to environmental effects

COMPLEXES POLYMETALLIQUES DE LANTHANIDES (III) POUR LE DEVELOPPEMENT DE NOUVEAUX MATERIAUX LUMINESCENTS

OpenAIRE

Marchal , Claire

2008-01-01

The incorporation of f elements in highly organized polymetallic complexes is of great interest in supramolecularchemistry and allows the combination of their nanoscopic size with the magnetic or optical properties of the metal ions. However due to the difficulty in controlling the coordination environment of these ions, the assembly of lanthanide-based polynuclear architectures has lagged behind that of other systems. These factors make the rational design for the construction of supramolecu...

A highly permeable and enhanced surface area carbon-cloth electrode for vanadium redox flow batteries

Science.gov (United States)

Zhou, X. L.; Zhao, T. S.; Zeng, Y. K.; An, L.; Wei, L.

2016-10-01

In this work, a high-performance porous electrode, made of KOH-activated carbon-cloth, is developed for vanadium redox flow batteries (VRFBs). The macro-scale porous structure in the carbon cloth formed by weaving the carbon fibers in an ordered manner offers a low tortuosity (∼1.1) and a broad pore distribution from 5 μm to 100 μm, rendering the electrode a high hydraulic permeability and high effective ionic conductivity, which are beneficial for the electrolyte flow and ion transport through the porous electrode. The use of KOH activation method to create nano-scale pores on the carbon-fiber surfaces leads to a significant increase in the surface area for redox reactions from 2.39 m2 g-1 to 15.4 m2 g-1. The battery assembled with the present electrode delivers an energy efficiency of 80.1% and an electrolyte utilization of 74.6% at a current density of 400 mA cm-2, as opposed to an electrolyte utilization of 61.1% achieved by using a conventional carbon-paper electrode. Such a high performance is mainly attributed to the combination of the excellent mass/ion transport properties and the high surface area rendered by the present electrode. It is suggested that the KOH-activated carbon-cloth electrode is a promising candidate in redox flow batteries.

Correlation of retention of lanthanide and actinide complexes with stability constants and their speciation

Energy Technology Data Exchange (ETDEWEB)

Datta, A.; Sivaraman, N.; Viswanathan, K.S.; Ghosh, Suddhasattwa; Srinivasan, T.G.; Vasudeva Rao, P.R. [Indira Gandhi Centre for Atomic Research, Kalpakkam (India). Chemistry Group

2013-03-01

The present study describes a correlation that is developed from retention of lanthanide and actinide complexes with the stability constant. In these studies, an ion-pairing reagent, camphor-10-sulphonic acid (CSA) was used as the modifier and organic acids such as {alpha}-hydroxy isobutyric acid ({alpha}-HIBA), mandelic acid, lactic acid and tartaric acid were used as complexing reagent for elution. From these studies, a correlation has been established between capacity factor of a metal ion, concentration of ion-pairing reagent and complexing agent with the stability constant of metal complex. Based on these studies, it has been shown that the stability constant of lanthanide and actinide complexes can be estimated using a single lanthanide calibrant. Validation of the method was carried out with the complexing agents such as {alpha}-HIBA and lactic acid. It was also demonstrated that data from a single chromatogram can be used for estimation of stability constant at various ionic strengths. These studies also demonstrated that the method can be applied for estimation of stability constant of actinides with a ligand whose value is not reported yet, e.g., ligands of importance in the lanthanide-actinide separations, chelation therapy etc. The chromatographic separation method is fast and the estimation of stability constant can be done in a very short time, which is a significant advantage especially in dealing with radioactive elements. The stability constant data was used to derive speciation data of plutonium in different oxidation states as well as that of americium with {alpha}-HIBA. The elution behavior of actinides such as Pu and Am from reversed phase chromatographic technique could be explained based on these studies. (orig.)

Experimental method for investigating helium effects in irradiated vanadium

International Nuclear Information System (INIS)

Smith, D.L.; Matsui, H.; Greenwood, L.; Loomis, B.

1987-10-01

Analyses have been performed which indicate that an effective method for experimentally investigating helium effects in neutron irradiated vanadium base alloys can be developed. The experimental procedure involves only modest modifications to existing procedures currently used for irradiation testing of vanadium-base alloys in the FFTF reactor. Helium is generated in the vanadium alloy by decay of tritium which is either preinjected or generated within the test capsule. Calculations indicate that nearly constant He/dpa ratios of desired magnitude can be attained by proper selection of experimental parameters. The proposed method could have a major impact on the development of vanadium base alloys for fusion reactor applications. 8 refs., 4 figs

Thermodecomposition of lanthanides (III) and ytrium (III) glucoheptonates

International Nuclear Information System (INIS)

Giolito, J.

1987-01-01

The lanthanides (III) and yttrium (III) glucoheptonates as well the D-glucoheptono 1-4 lactone were studied using common analytical methods, elemental microanalysis of carbon and hydrogen, thermogravimetry and differential scanning calorimetry. These compounds were prepared from the reaction between the lanthanides (III) and yttrium (III) hydroxides and glucoheptonic acid aqueous solution obtained by means of the delta lactone hydrolysis of this acid. After stoichiometric reaction the compounds were precipitated by the addition of absolute ethanol, washed with the same solvent and dried in desiccator. Thermogravimetric the (TG) curves of the lanthanides glucoheptonates of the ceric group present thermal profiles with enough differences permitting an easy caracterization of each compound and the yttrium (III) glucoheptonate TG curve showed a great similarity with the erbium (III) compound TG curve. The differential scanning calometry (DSC) curves showed endothermic and exothermic peaks by their shape, height and position (temperature) permit an easy and rapid identification of each compound specially if DSC and TG curves were examined simultaneously. (author) [pt

Performance of a vanadium redox flow battery with a VANADion membrane

International Nuclear Information System (INIS)

Zhou, X.L.; Zhao, T.S.; An, L.; Zeng, Y.K.; Zhu, X.B.

2016-01-01

Highlights: • Performance of the VANADion membrane in flow batteries is evaluated. • The battery with present membrane shows good rate capability. • The battery with present membrane offers good capacity retention. • The high performance and low cost make the membrane promising in VRFBs. - Abstract: Conventional vanadium redox flow batteries (VRFBs) using Nafion 115 suffered from issues associated with high ohmic resistance and high capital cost. In this work, we report a commercial membrane (VANADion), consisting of a porous layer and a dense Nafion layer, as a promising alternative to Nafion 115. In the dual-layer structure, the porous layer (∼210 μm) can offer a high ionic conductivity and the dense Nafion layer (∼20 μm) can depress the convective flow of electrolyte through the membrane. By comparing with the conventional Nafion 115 in a VRFB, it is found that the change from the conventional Nafion 115 to the composite one results in an increase in the energy efficiency from 71.3% to 76.2% and an increase in the electrolyte utilization from 54.1% to 68.4% at a current density of as high as 240 mA cm"−"2. In addition, although two batteries show the comparable cycling performance at current densities ranging from 80 mA cm"−"2 to 240 mA cm"−"2, the composite membrane is estimated to be significantly cheaper than the conventional Nafion 115 due to the fact that the porous layer is rather cost-effective and the dense Nafion layer is rather thin. The impressive combination of desirable performance and low cost makes this composite membrane highly promising in the VRFB applications.

Vanadium-base alloys for fusion reactor applications

International Nuclear Information System (INIS)

Smith, D.L.; Loomis, B.A.; Diercks, D.R.

1984-10-01

Vanadium-base alloys offer potentially significant advantages over other candidate alloys as a structural material for fusion reactor first wall/blanket applications. Although the data base is more limited than that for the other leading candidate structural materials, viz., austenitic and ferritic steels, vanadium-base alloys exhibit several properties that make them particularly attractive for the fusion reactor environment. This paper presents a review of the structural material requirements, a summary of the materials data base for selected vanadium-base alloys, and a comparison of projected performance characteristics compared to other candidate alloys. Also, critical research and development (R and D) needs are defined

Vanadium-base alloys for fusion reactor applications

Energy Technology Data Exchange (ETDEWEB)

Smith, D.L.; Loomis, B.A.; Diercks, D.R.

1984-10-01

Vanadium-base alloys offer potentially significant advantages over other candidate alloys as a structural material for fusion reactor first wall/blanket applications. Although the data base is more limited than that for the other leading candidate structural materials, viz., austenitic and ferritic steels, vanadium-base alloys exhibit several properties that make them particularly attractive for the fusion reactor environment. This paper presents a review of the structural material requirements, a summary of the materials data base for selected vanadium-base alloys, and a comparison of projected performance characteristics compared to other candidate alloys. Also, critical research and development (R and D) needs are defined.

Improved Structural Design and CO₂ Capture of Porous Hydroxy-Rich Polymeric Organic Frameworks

Energy Technology Data Exchange (ETDEWEB)

Kidder, Michelle K. [Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States); Earl, Lyndsey D. [Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States); de Almeida, Valmor F. [Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States)

2016-04-16

Polymeric organic frameworks (POFs) are tunable and robust porous materials with potential applications for gas capture, catalysis, and separations technologies. A series of new porous POFs have been synthesized from the reaction of phloroglucinol or resorcinol derivatives with aryl aldehyde precursors. The monomers have various molecular shapes including linear, bent, trigonal, and tetrahedral geometries. Depending on the size and geometric matching of the monomers, the polymers are dominantly microporous with some mesoporous character or they are non-porous. In addition to standard spectroscopic and surface characterization, the materials were screened as adsorbents for carbon dioxide capture at low pressure (0-1 bar). The best performing material (POF 1D) has a CO₂ capture capacity of 9.0 wt. % (2.04 mmol g^-1) at 298 K and 1 bar which is comparable to other polymeric organic frameworks. Isosteric heats of adsorption for POF 1A, POF 2A, and POF 2B were found to be dependent on the weight percent of CO₂ adsorbed: this suggests there are both chemisorptive and physisorptive components of CO₂ capture by the POFs.

Hydrogeochemistry of uranium, daughter products and associated elements (lanthanides), application to ore prospection

International Nuclear Information System (INIS)

Toulhoat, P.

1987-09-01

The behavior in ground water of uranium, daughter products with long half life (U 234 , Th 230 , Ra 226 ) and stable (radiogenic lead) and lanthanides is studied by two complementary methods: 1) In situ multielement tracing in fracturated granitic rocks and porous sedimentary rocks of low permeability allowing to understand interactions between hydrodynamics and geochemistry. 2) Study of the properties of U 234 and Pb 236 which are mineralization tracers and are relatively independent of redox conditions, on the contrary U 238 has a low solubility in reducing medium. Three areas are studied: Bazois and Lodeve basin (France) and Cigar Lake (Canada). Radioactive disequilibriums are thoroughly studied when required by ore/rock interaction. Adsorption-desorption phenomena are of great importance in proposed prospection models. If prospection models based on alpha activity ratio U 234 /U 238 and lead isotope ratio in ground water can be applied, an integrated prospection model requires more in situ and laboratory experiments [fr

Forming a three-dimensional porous organic network via solid-state explosion of organic single crystals.

Science.gov (United States)

Bae, Seo-Yoon; Kim, Dongwook; Shin, Dongbin; Mahmood, Javeed; Jeon, In-Yup; Jung, Sun-Min; Shin, Sun-Hee; Kim, Seok-Jin; Park, Noejung; Lah, Myoung Soo; Baek, Jong-Beom

2017-11-17

Solid-state reaction of organic molecules holds a considerable advantage over liquid-phase processes in the manufacturing industry. However, the research progress in exploring this benefit is largely staggering, which leaves few liquid-phase systems to work with. Here, we show a synthetic protocol for the formation of a three-dimensional porous organic network via solid-state explosion of organic single crystals. The explosive reaction is realized by the Bergman reaction (cycloaromatization) of three enediyne groups on 2,3,6,7,14,15-hexaethynyl-9,10-dihydro-9,10-[1,2]benzenoanthracene. The origin of the explosion is systematically studied using single-crystal X-ray diffraction and differential scanning calorimetry, along with high-speed camera and density functional theory calculations. The results suggest that the solid-state explosion is triggered by an abrupt change in lattice energy induced by release of primer molecules in the 2,3,6,7,14,15-hexaethynyl-9,10-dihydro-9,10-[1,2]benzenoanthracene crystal lattice.

Recent progress on gas tungsten arc welding of vanadium alloys

Energy Technology Data Exchange (ETDEWEB)

King, J.F.; Grossbeck, M.L.; Goodwin, G.M.; Alexander, D.J. [Oak Ridge National Lab., TN (United States)

1997-04-01

This is a progress report on a continuing research project to acquire a fundamental understanding of the metallurgical processes in the welding of vanadium alloys. It also has the goal of developing techniques for welding structural vanadium alloys. The alloy V-4Cr-4Ti is used as a representative alloy of the group; it is also the prime candidate vanadium alloy for the U.S. Fusion Program at the present time. However, other alloys of this class were used in the research as necessary. The present work focuses on recent findings of hydrogen embrittlement found in vanadium alloy welds. It was concluded that the atmosphere in the inert gas glove box was insufficient for welding 6mm thick vanadium alloy plates.

Absorption of hydrogen by vanadium-palladium alloys

International Nuclear Information System (INIS)

Artman, D.; Lynch, J.F.; Flanagan, T.B.

1976-01-01

Pressure composition isotherms (273-373 K) have been determined for the absorption of hydrogen by a series of six palladium alloys (f.c.c) in the composition range from 1 to 8 at.% vanadium. At a given hydrogen content, the equilibrium hydrogen pressure progressively increases with vanadium content. Thermodynamic parameters for the absorption of hydrogen are reported at infinite dilution of hydrogen and for the formation of the nonstoichiometric hydride from the hydrogen-saturated alloy. The relative, partial molar enthalpy of solution of hydrogen at infinite dilution increases slightly with vanadium content. The presence of vanadium, which absorbs hydrogen itself in its normal b.c.c. structure, greatly inhibits the ability of palladium to absorb hydrogen. For example, the isobaric solubility of hydrogen (1 atm, 298K) decreases from H/Pd=0.7 (palladium) to 0.024 (V(6%)-Pd). The lattice expansion due to the presence of interstitial hydrogen has been determined by X-ray diffraction. From these data it can be concluded that the formation of two non-stoichiometric hydride phases does not occur at vanadium contents greater that 5 at.% (298 K). Electrical resistance has been measured as a function of the hydrogen content of the alloys. The electrical resistance increases more markedly with hydrogen content for these alloys than for any of the palladium alloys previously examined. (Auth.)

Preparation of porous titanium oxide films onto indium tin oxide for application in organic photovoltaic devices

Energy Technology Data Exchange (ETDEWEB)

Macedo, Andreia G. [Laboratorio de Dispositivos Nanoestruturados, Departamento de Fisica, Universidade Federal do Parana, Curitiba, Parana (Brazil); Mattos, Luana L.; Spada, Edna R.; Serpa, Rafael B.; Campos, Cristiani S. [Laboratorio de Sistemas Nanoestruturados, Departamento de Fisica, Universidade Federal de Santa Catarina, Florianopolis, Santa Catarina (Brazil); Grova, Isabel R.; Ackcelrud, Leni [Laboratorio de Polimeros Paulo Scarpa, Departamento de Quimica, Universidade Federal do Parana, Curitiba, Parana (Brazil); Reis, Francoise T.; Sartorelli, Maria L. [Laboratorio de Sistemas Nanoestruturados, Departamento de Fisica, Universidade Federal de Santa Catarina, Florianopolis, Santa Catarina (Brazil); Roman, Lucimara S., E-mail: lsroman@fisica.ufpr.br [Laboratorio de Dispositivos Nanoestruturados, Departamento de Fisica, Universidade Federal do Parana, Curitiba, Parana (Brazil)

2012-05-01

In this work, porous ordered TiO{sub 2} films were prepared through sol gel route by using a monolayer of polystyrene spheres as template on indium-tin oxide/glass substrate. These films were characterized by SEM, AFM, Raman spectroscopy, UV-vis absorbance and XRD. The UV-vis absorbance spectrum show a pseudo band gap (PBG) with maxima at 460 nm arising from the light scattering and partial or total suppression of the photon density of states, this PBG can be controlled by the size of the pore. We also propose the use of this porous film as electron acceptor electrode in organic photovoltaic cells; we show that devices prepared with porous titania displayed higher efficiencies than devices using compact titania films as electrode. Such behaviour was observed in both bilayer and bulk heterojunction devices.

Preparation of porous titanium oxide films onto indium tin oxide for application in organic photovoltaic devices

International Nuclear Information System (INIS)

Macedo, Andreia G.; Mattos, Luana L.; Spada, Edna R.; Serpa, Rafael B.; Campos, Cristiani S.; Grova, Isabel R.; Ackcelrud, Leni; Reis, Françoise T.; Sartorelli, Maria L.; Roman, Lucimara S.

2012-01-01

In this work, porous ordered TiO 2 films were prepared through sol gel route by using a monolayer of polystyrene spheres as template on indium-tin oxide/glass substrate. These films were characterized by SEM, AFM, Raman spectroscopy, UV-vis absorbance and XRD. The UV-vis absorbance spectrum show a pseudo band gap (PBG) with maxima at 460 nm arising from the light scattering and partial or total suppression of the photon density of states, this PBG can be controlled by the size of the pore. We also propose the use of this porous film as electron acceptor electrode in organic photovoltaic cells; we show that devices prepared with porous titania displayed higher efficiencies than devices using compact titania films as electrode. Such behaviour was observed in both bilayer and bulk heterojunction devices.

Thermodynamical properties of liquid lanthanides-A variational approach

Energy Technology Data Exchange (ETDEWEB)

Patel, H. P. [Department of Physics, Veer Narmad South Gujarat University, Surat 395 007, Gujarat (India); Department of Applied Physics, S. V. National Institute of Technology, Surat 395 007, Gujarat (India); Thakor, P. B., E-mail: pbthakor@rediffmail.com [Department of Physics, Veer Narmad South Gujarat University, Surat 395 007, Gujarat (India); Sonvane, Y. A. [Department of Applied Physics, S. V. National Institute of Technology, Surat 395 007, Gujarat (India)

2015-06-24

Thermodynamical properties like Entropy (S), Internal energy (E) and Helmholtz free energy (F) of liquid lanthanides using a variation principle based on the Gibbs-Bogoliubuv (GB) inequality with Percus Yevick hard sphere reference system have been reported in the present investigation. To describe electron-ion interaction we have used our newly constructed parameter free model potential along with Sarkar et al. local field correction function. Lastly, we conclude that our newly constructed model potential is capable to explain the thermodynamical properties of liquid lanthanides.

Lanthanide complexes that respond to changes in cyanide concentration in water

Energy Technology Data Exchange (ETDEWEB)

Routledge, Jack D.; Zhang, Xuejian; Connolly, Michael; Tropiano, Manuel; Blackburn, Octavia A.; Beer, Paul D.; Aldridge, Simon; Faulkner, Stephen [Inorganic Chemistry Laboratory, Department of Chemistry, University of Oxford (United Kingdom); Kenwright, Alan M. [Department of Chemistry, Durham University (United Kingdom)

2017-06-26

Cyanide ions are shown to interact with lanthanide complexes of phenacylDO3A derivatives in aqueous solution, giving rise to changes in the luminescence and NMR spectra. These changes are the consequence of cyanohydrin formation, which is favored by the coordination of the phenacyl carbonyl group to the lanthanide center. These complexes display minimal affinity for fluoride and can detect cyanide at concentrations less than 1 μm. By contrast, lanthanide complexes with DOTAM derivatives display no affinity for cyanide in water, but respond to changes in fluoride concentration. (copyright 2017 Wiley-VCH Verlag GmbH and Co. KGaA, Weinheim)

Lanthanide complexes that respond to changes in cyanide concentration in water

International Nuclear Information System (INIS)

Routledge, Jack D.; Zhang, Xuejian; Connolly, Michael; Tropiano, Manuel; Blackburn, Octavia A.; Beer, Paul D.; Aldridge, Simon; Faulkner, Stephen; Kenwright, Alan M.

2017-01-01

Cyanide ions are shown to interact with lanthanide complexes of phenacylDO3A derivatives in aqueous solution, giving rise to changes in the luminescence and NMR spectra. These changes are the consequence of cyanohydrin formation, which is favored by the coordination of the phenacyl carbonyl group to the lanthanide center. These complexes display minimal affinity for fluoride and can detect cyanide at concentrations less than 1 μm. By contrast, lanthanide complexes with DOTAM derivatives display no affinity for cyanide in water, but respond to changes in fluoride concentration. (copyright 2017 Wiley-VCH Verlag GmbH and Co. KGaA, Weinheim)

Characterization of vanadium flow battery

Energy Technology Data Exchange (ETDEWEB)

Bindner, H.; Ekman, C.; Gehrke, O.; Isleifsson, F.

2010-10-15

This report summarizes the work done at Risoe DTU testing a vanadium flow battery as part of the project 'Characterisation of Vanadium Batteries' (ForskEl project 6555) with the partners PA Energy A/S and OI Electric A/S under the Danish PSO energy research program. A 15kW/120kWh vanadium battery has been installed as part of the distributed energy systems experimental facility, SYSLAB, at Risoe DTU. A test programme has been carried out to get hands-on experience with the technology, to characterize the battery from a power system point of view and to assess it with respect to integration of wind energy in the Danish power system. The battery has been in operation for 18 months. During time of operation the battery has not shown signs of degradation of performance. It has a round-trip efficiency at full load of approximately 60% (depending on temperature and SOC). The sources of the losses are power conversion in cell stacks/electrolyte, power converter, and auxiliary power consumption from pumps and controller. The response time for the battery is limited at 20kW/s by the ramp rate of the power converter. The battery can thus provide power and frequency support for the power system. Vanadium battery is a potential technology for storage based services to the power system provided investment and O and M cost are low enough and long term operation is documented. (Author)

Multicolor emission from large-area porous thin films constructed of nanowires of small organic molecules

International Nuclear Information System (INIS)

Wang Zhechen; Ding Xunlei; Ma Yanping; Xue Wei; He Shenggui; Xiao Wenchang

2008-01-01

We describe a facile low-temperature physical vapor deposition approach to fabricate porous network thin films constructed of nanowires of small organic molecules on a large area. Supermolecular assemblies of pyrene nanowires based on a combination of van der Waals forces and π-π stacking tend to hierarchically self-assemble to form uniform porous films using our techniques. The morphology of the films is studied and we also study several reasons influencing the process of assembly such as evaporation temperature, deposition temperature, and different kinds of substrate. The deposition temperature is determined to be the main reason for hierarchical aggregation. Typically prepared films exhibit unique optical properties, that is, multicolor red-green-blue emissions. This novel method can be applied to other organic molecular systems and may be potentially used to place nanoscaled building blocks directly on solid surfaces for fabricating large-area nanostructure-based flat screens.

Multicolor emission from large-area porous thin films constructed of nanowires of small organic molecules

Science.gov (United States)

Wang, Zhe-Chen; Xiao, Wen-Chang; Ding, Xun-Lei; Ma, Yan-Ping; Xue, Wei; He, Sheng-Gui

2008-12-01

We describe a facile low-temperature physical vapor deposition approach to fabricate porous network thin films constructed of nanowires of small organic molecules on a large area. Supermolecular assemblies of pyrene nanowires based on a combination of van der Waals forces and π-π stacking tend to hierarchically self-assemble to form uniform porous films using our techniques. The morphology of the films is studied and we also study several reasons influencing the process of assembly such as evaporation temperature, deposition temperature, and different kinds of substrate. The deposition temperature is determined to be the main reason for hierarchical aggregation. Typically prepared films exhibit unique optical properties, that is, multicolor red-green-blue emissions. This novel method can be applied to other organic molecular systems and may be potentially used to place nanoscaled building blocks directly on solid surfaces for fabricating large-area nanostructure-based flat screens.

On sub-modularization and morphological heterogeneity in modular robotics

DEFF Research Database (Denmark)

Lyder, A. H.; Stoy, K.; Garciá, R. F. M.

2012-01-01

Modular robots are a kind of robots built from mechatronic modules, which can be assembled in many different ways allowing the modular robot to assume a wide range of morphologies and functions. An important question in modular robotics is to which degree modules should be heterogeneous....... In this paper we introduce two contributing factors to heterogeneity namely morphological heterogeneity and sub-functional modularization. Respectively, the ideas are to create modules with significantly different morphologies and to spread sub-functionality across modules. Based on these principles we design...... and implement the Thor robot and evaluate it by participating in the ICRA Planetary Robotic Contingency Challenge. The Thor robot demonstrates that sub-functional modularity and morphological heterogeneity may increase the versatility of modular robots while reducing the complexity of individual modules, which...

Circularly Polarized Luminescence from Inorganic Materials: Encapsulating Guest Lanthanide Oxides in Chiral Silica Hosts.

Science.gov (United States)

Sugimoto, Masumi; Liu, Xin-Ling; Tsunega, Seiji; Nakajima, Erika; Abe, Shunsuke; Nakashima, Takuya; Kawai, Tsuyoshi; Jin, Ren-Hua

2018-05-02

Recently, circularly polarized luminescence (CPL)-active systems have become a very hot and interesting subject in chirality- and optics-related areas. The CPL-active systems are usually available by two approaches: covalently combining a luminescent centre to chiral motif or associating the guest of luminescent probe to a chiral host. However, all the chiral components in CPL materials were organic, although the luminescent components were alternatively organics or inorganics. Herein, the first totally inorganic CPL-active system by "luminescent guest-chiral host" strategy is proposed. Luminescent sub-10 nm lanthanide oxides (Eu 2 O 3 or Tb 2 O 3 ) nanoparticles (guests) were encapsulated into chiral non-helical SiO 2 nanofibres (host) through calcination of chiral SiO 2 hybrid nanofibres, trapping Eu 3+ (or Tb 3+ ). These lanthanide oxides display circular dichroism (CD) optical activity in the ultraviolet wavelength and CPL signals around at 615 nm for Eu 3+ and 545 nm for Tb 3+ . This work has implications for inorganic-based CPL-active systems by incorporation of various luminescent guests within chiral inorganic hosts. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Functional annotation of hierarchical modularity.

Directory of Open Access Journals (Sweden)

Kanchana Padmanabhan

Full Text Available In biological networks of molecular interactions in a cell, network motifs that are biologically relevant are also functionally coherent, or form functional modules. These functionally coherent modules combine in a hierarchical manner into larger, less cohesive subsystems, thus revealing one of the essential design principles of system-level cellular organization and function-hierarchical modularity. Arguably, hierarchical modularity has not been explicitly taken into consideration by most, if not all, functional annotation systems. As a result, the existing methods would often fail to assign a statistically significant functional coherence score to biologically relevant molecular machines. We developed a methodology for hierarchical functional annotation. Given the hierarchical taxonomy of functional concepts (e.g., Gene Ontology and the association of individual genes or proteins with these concepts (e.g., GO terms, our method will assign a Hierarchical Modularity Score (HMS to each node in the hierarchy of functional modules; the HMS score and its p-value measure functional coherence of each module in the hierarchy. While existing methods annotate each module with a set of "enriched" functional terms in a bag of genes, our complementary method provides the hierarchical functional annotation of the modules and their hierarchically organized components. A hierarchical organization of functional modules often comes as a bi-product of cluster analysis of gene expression data or protein interaction data. Otherwise, our method will automatically build such a hierarchy by directly incorporating the functional taxonomy information into the hierarchy search process and by allowing multi-functional genes to be part of more than one component in the hierarchy. In addition, its underlying HMS scoring metric ensures that functional specificity of the terms across different levels of the hierarchical taxonomy is properly treated. We have evaluated our

Modular co-evolution of metabolic networks

Directory of Open Access Journals (Sweden)

Yu Zhong-Hao

2007-08-01

Full Text Available Abstract Background The architecture of biological networks has been reported to exhibit high level of modularity, and to some extent, topological modules of networks overlap with known functional modules. However, how the modular topology of the molecular network affects the evolution of its member proteins remains unclear. Results In this work, the functional and evolutionary modularity of Homo sapiens (H. sapiens metabolic network were investigated from a topological point of view. Network decomposition shows that the metabolic network is organized in a highly modular core-periphery way, in which the core modules are tightly linked together and perform basic metabolism functions, whereas the periphery modules only interact with few modules and accomplish relatively independent and specialized functions. Moreover, over half of the modules exhibit co-evolutionary feature and belong to specific evolutionary ages. Peripheral modules tend to evolve more cohesively and faster than core modules do. Conclusion The correlation between functional, evolutionary and topological modularity suggests that the evolutionary history and functional requirements of metabolic systems have been imprinted in the architecture of metabolic networks. Such systems level analysis could demonstrate how the evolution of genes may be placed in a genome-scale network context, giving a novel perspective on molecular evolution.

Effective core potential methods for the lanthanides

International Nuclear Information System (INIS)

Cundari, T.R.; Stevens, W.J.

1993-01-01

In this paper a complete set of effective core potentials (ECPs) and valence basis sets for the lanthanides (Ce to Lu) are derived. These ECPs are consistent not only within the lanthanide series, but also with the third-row transition metals which bracket them. A 46-electron core was chosen to provide the best compromise between computational savings and chemical accuracy. Thus, the 5s and 5p are included as ''outer'' core while all lower energy atomic orbitals (AOs) are replaced with the ECP. Generator states were chosen from the most chemically relevant +3 and +2 oxidation states. The results of atomic calculations indicate that the greatest error vs highly accurate numerical potential/large, even-tempered basis set calculations results from replacement of the large, even-tempered basis sets with more compact representations. However, the agreement among atomic calculations remains excellent with both basis set sizes, for a variety of spin and oxidation states, with a significant savings in time for the optimized valence basis set. It is expected that the compact representation of the ECPs and valence basis sets will eventually encourage their use by computational chemists to further explore the bonding and reactivity of lanthanide complexes

Wet sample digestion for quantification of vanadium(V) in serum by electrothermal atomic absorption spectrometry

International Nuclear Information System (INIS)

Heinemann, G.; Vogt, W.; Jacob, K.

1999-01-01

Three types of pressure digestion systems used prior to the determination of the ultratrace element vanadium by electrothermal atomic absorption spectrometry were evaluated: The high-pressure ashing (HPA) system, the DAB III pressure digestion system and the pressurized microwave digestion (PMD) system. Complete sample digestion and no loss of graphite tube sensitivity as well as reliable vanadium values could only be achieved with HPA digests of freeze-dried serum. The mean recovery rate was 98% and no loss of tube sensitivity could be observed. Using non-lyophilized serum the mean recovery rate was 70%. The DAB III digestion system, vicarious for closed pressure digestion in steel bombs with an allowable temperature up to about 200C, cannot be recommended to mineralize human biological material for vanadium determinations, because the remaining not completely decomposed organic compounds extracted together with the vanadium-cupferron complex caused a marked carbon-buildup and formation of carbides in the graphite tube were found to change the shape of the absorption signals distinctly, and to decline the tube sensitivity strongly (about 25%) so that reliable results cannot be achieved. The recovery rate was too low in general (about 50%). In addition, a subsequent treatment of the DAB III digests with perchloric acid was unsuccessful. The PMD system proved to be not suited, because the samples became highly contaminated by vanadium possibly from the titan seal. (Copyright (c) 1999 Elsevier Science B.V., Amsterdam. All rights reserved.)

Acute toxicity of vanadium to the threespine stickleback, Gasterosteus aculeatus

Energy Technology Data Exchange (ETDEWEB)

Gravenmier, J.J.; Johnston, D.W.; Arnold, W.R. [Blasland Bouck & Lee Inc, Petaluma, CA (US)

2005-02-15

Vanadium is widely distributed, occurring in many types of minerals, coal, and petroleum. Anthropogenic sources of vanadium originate from the production, processing, and wastes of these materials. The aquatic toxicity of vanadium to fish species is not well characterized. This study focused on the three-spined stickleback, Gasterosteus aculeatus, a small and widely distributed euryhaline species of fish. The three-spined stickleback is used as an effluent-monitoring species in both Canada and the United States. Five 96-h static renewal acute toxicity tests were performed in moderately hard water with adult fish. The geometric mean and range of the five 96-h LC{sup 50}s based on measured concentrations of total vanadium in the test solution were 3.17 and 2.35-4.07 mg V/L, respectively. A conservative estimation of a safe concentration of vanadium that would not affect survival of adult three-spined sticklebacks over a 96-h exposure period in moderately hard water is approximately 0.30 mg V/L. A comparison with other fish species previously tested suggests that the three-spined stickleback is intermediate in sensitivity to vanadium. Information reported from this study may be useful in effluent toxicity identification evaluations and ecological risk assessments related to vanadium.

TiAl doping by vanadium: ab initio study

International Nuclear Information System (INIS)

Smirnova, E.A.; Isaev, Eh.I.; Vekilov, Yu.Kh.

2004-01-01

Tetragonality degree in TiAl and vanadium doping effect on it were studied using the methods of calculation based on approximation of coherent potential and ab initio pseudopotentials. It is shown that vanadium substitution for Ti sublattice atoms entails increase in tetragonality degree but with substitution of the atoms in aluminium sublattice the tetragonality of the TiAl:V alloy decreases and at the content of vanadium about 8 at. % the lattice becomes actually cubical. In its turn, it may result in increase in TiAl ductility, the alloy being brittle at low temperatures [ru

Post-Synthesis Functionalization of Porous Organic Polymers for CO2 Capture

KAUST Repository

Al Otaibi, Mona S.

2014-07-01

Solid porous materials are network materials that contain space void. Porous Organic Polymers (POPs) are porous materials, which are constructed from organic building blocks and exhibit large surface area with low densities. Due to these characteristics, POPs have attracted attentions because of their potential use in application such as gas storage and chemical separation. This thesis presents a study of the synthesis of novel POP being a network based on 2,5- dibromobenzaldehyde and 1,3,5-triethynylbenzene linked together via Sonogashira- Hagihara (SH) coupling. This network showed a relatively good surface area of 770 m2/g and total pore volume of 0.59 cc/g. In addition, it proved to be chemically and thermally stable, maintaining the thermal stability up to 350oC. In addition to synthesize novel aldehyde-POP network, it was also possible to post synthetically modify a network via one-step post synthetic functionalization by amine. Ethelynediamine (EDA), Diethylenetriamine (DETA), and Tris(2-aminoethyl)amine (Tris-amine) are three different amines used for aldehyde-POP functionalization. The produced networks were aminated via different amine species substitution the aldehyde group present within the network. Modification to these networks resulted in a decrease in surface area from 770 m2.g-1 to 333 m2.g-1, 162 m2.g-1, and 211 m2.g-1 in respective to EDA, DETA, and Tris-amine. Although the surface areas were decreased, the CO2 adsorption was enhanced as evidenced by the increase of Qst (i.e., from 25 to 45 kJ.mol-1 for DETA at low coverage). Our findings are expected to strengthen existing research areas of the influence of different type of amines (e.g aromatic amine) on CO2 adsorption. Although amine grafting has been studied in other systems (e.g., PAFs and MOFs), we are the first to reported amine functionalized POPs using a novel one-step amine grafting PSM procedure. Future research might extend to study the interaction between CO2 and amine species under

Separation of Am from lanthanides by a synergistic mixture of purified Cyanex 301 and TBP

International Nuclear Information System (INIS)

Xinghai Wang; Yongjun Zhu; Rongzhou Jiao

2002-01-01

The dependence of the distribution ratios of 241 Am and lanthanides between purified Cyanex 301 (HBTMPDTP)-TBP-kerosene/nitrate solution on pH, lanthanide concentration in aqueous phase and degree of saponification of HBTMPDTP was investigated. The distribution ratios of 241 Am and lanthanides increase with pH and degree of saponification of HBTMPDTP and decrease with lanthanides concentration. Countercurrent multistage extraction consisting of 7 extraction, 3 washing and 2 stripping stages showed that more than 99,99% of 241 Am and less than 0.04% of lanthanides were extracted. The pH 1/2 value of Am was 2.45 compared to 3.16 in case of HBTMPDTP-kerosene extraction. (author)

Hot-pressed silicon nitride with various lanthanide oxides as sintering additives

Science.gov (United States)

Ueno, K.; Toibana, Y.

1984-01-01

The effects of addition of various lanthanide oxides and their mixture with Y2O3 on the sintering of Si3N4 were investigated. The addition of simple and mixed lanthanide oxides promoted the densification of Si3N4 in hot-pressing at 1800 C under 300-400kg/ centimeters squared for 60 min. The crystallization of yttrium and lanthanide-silicon oxynitrides which was observed inn the sintered body containing yttrium-lanthanide mixed oxides as additives led to the formation of a highly refractory Si3N4 ceramic having a bending strength of 82 and 84 kg/millimeters squared at room temperature and 1300 C respectively. In a Y2O3+La2O3 system, a higher molar ratio of La2O3 to Y2O3 gave a higher hardness and strength at high temperatures. It was found that 90 min was an optimum sintering time for the highest strength.

Does habitat variability really promote metabolic network modularity?

Science.gov (United States)

Takemoto, Kazuhiro

2013-01-01

The hypothesis that variability in natural habitats promotes modular organization is widely accepted for cellular networks. However, results of some data analyses and theoretical studies have begun to cast doubt on the impact of habitat variability on modularity in metabolic networks. Therefore, we re-evaluated this hypothesis using statistical data analysis and current metabolic information. We were unable to conclude that an increase in modularity was the result of habitat variability. Although horizontal gene transfer was also considered because it may contribute for survival in a variety of environments, closely related to habitat variability, and is known to be positively correlated with network modularity, such a positive correlation was not concluded in the latest version of metabolic networks. Furthermore, we demonstrated that the previously observed increase in network modularity due to habitat variability and horizontal gene transfer was probably due to a lack of available data on metabolic reactions. Instead, we determined that modularity in metabolic networks is dependent on species growth conditions. These results may not entirely discount the impact of habitat variability and horizontal gene transfer. Rather, they highlight the need for a more suitable definition of habitat variability and a more careful examination of relationships of the network modularity with horizontal gene transfer, habitats, and environments.

Effects of hydrogen on fatigue of vanadium and niobium. Annual report

International Nuclear Information System (INIS)

Stoloff, N.S.; Chung, D.W.

1977-01-01

The fatigue behavior of unalloyed vanadium and niobium as well as their alloys with hydrogen is described. The response of vanadium-hydrogen alloys to cyclic loading is shown to depend markedly upon the presence or absence of notches, the hydrogen level, method of test, and frequency. In general, hydrides improve high cycle life of unnotched alloys, but are detrimental in the presence of a notch. Low test frequencies also lead to reduced fatigue lives. Stress-assisted hydride growth in previously hydrided alloys has been noted both in fatigue and in delayed failure experiments. Unalloyed vanadium and solid solution vanadium-hydrogen alloys do not undergo delayed failure. Preliminary tests on unalloyed niobium and several niobium-vanadium alloys reveal improvements in stress-controlled fatigue life and decreased low cycle life, in agreement with previous observations on vanadium-hydrogen alloys

Vanadium supply and demand outlook. Final report

International Nuclear Information System (INIS)

1978-01-01

A review has been made of the reserves and resources for vanadium minerals in the United States and foreign countries. Foreign sources are presently used to provide a substantial part of national demand because of price advantages. There are so many functioning foreign sources for vanadium that it is difficult to conceive of circumstances that would shut all of them off. The basis for the national stockpile is described. A recommendation is made to add the 65V-35Al alloy as a component of the stockpile for titanium alloy production in a national emergency. Estimated consumption growth rates to 1990 vary from one to five percent per year depending on the end product involved. Fission reactor use of vanadium-base alloys has not developed because of technical problems. In the chemical field, a slow steady growth of five to six percent per year is projected. Technical preferences for vanadium in various steel applications will continue although other alloying alternatives are generally available. Overall environmental effects do not appear to be a serious industrial problem

An NMR strategy for fragment-based ligand screening utilizing a paramagnetic lanthanide probe

International Nuclear Information System (INIS)

Saio, Tomohide; Ogura, Kenji; Shimizu, Kazumi; Yokochi, Masashi; Burke, Terrence R.; Inagaki, Fuyuhiko

2011-01-01

A nuclear magnetic resonance-based ligand screening strategy utilizing a paramagnetic lanthanide probe is presented. By fixing a paramagnetic lanthanide ion to a target protein, a pseudo-contact shift (PCS) and a paramagnetic relaxation enhancement (PRE) can be observed for both the target protein and its bound ligand. Based on PRE and PCS information, the bound ligand is then screened from the compound library and the structure of the ligand–protein complex is determined. PRE is an isotropic paramagnetic effect observed within 30 Å from the lanthanide ion, and is utilized for the ligand screening in the present study. PCS is an anisotropic paramagnetic effect providing long-range (∼40 Å) distance and angular information on the observed nuclei relative to the paramagnetic lanthanide ion, and utilized for the structure determination of the ligand–protein complex. Since a two-point anchored lanthanide-binding peptide tag is utilized for fixing the lanthanide ion to the target protein, this screening method can be generally applied to non-metal-binding proteins. The usefulness of this strategy was demonstrated in the case of the growth factor receptor-bound protein 2 (Grb2) Src homology 2 (SH2) domain and its low- and high-affinity ligands.

Electrospray mass spectrometry for actinides and lanthanide speciation

International Nuclear Information System (INIS)

Moulin, C.; Amekraz, B.; Colette, S.; Doizi, D.; Jacopin, C.; Lamouroux, C.; Plancque, G.

2006-01-01

Electrospray mass spectrometry (ES-MS) is a new speciation technique that has the great interest to be able to probe the element, the ligand and the complex in order to reach the speciation. This paper will focus on the use of ES-MS for the speciation of actinides/lanthanides on several systems of interest in various fields such as the interaction between DTPA (decorporant) and europium, HEBP and uranium, BTP (new extracting agent) and lanthanides with comparison with known chemistry as well as whenever possible with other speciation techniques

The vanadium/oxygen system in the analysis of sodium for oxygen

International Nuclear Information System (INIS)

Walker, J.A.J.; Price, W.B.

1981-05-01

An investigation of the V-O-Na system at 1023 K is described for oxygen in sodium contents of 5 to 25 ppm. Electron spectroscopy combined with depth profiling is used to determine the vanadium/oxygen ratios inwards from the surface of vanadium foil and these ratios are compared with theoretical predictions. The validity of the vanadium wire technique as an analytical method is examined and a model for the vanadium oxidation is suggested. (author)

Sparkle/PM7 Lanthanide Parameters for the Modeling of Complexes and Materials.

Science.gov (United States)

Dutra, José Diogo L; Filho, Manoel A M; Rocha, Gerd B; Freire, Ricardo O; Simas, Alfredo M; Stewart, James J P

2013-08-13

The recently published Parametric Method number 7, PM7, is the first semiempirical method to be successfully tested by modeling crystal structures and heats of formation of solids. PM7 is thus also capable of producing results of useful accuracy for materials science, and constitutes a great improvement over its predecessor, PM6. In this article, we present Sparkle Model parameters to be used with PM7 that allow the prediction of geometries of metal complexes and materials which contain lanthanide trications. Accordingly, we considered the geometries of 224 high-quality crystallographic structures of complexes for the parameterization set and 395 more for the validation of the parameterization for the whole lanthanide series, from La(III) to Lu(III). The average unsigned error for Sparkle/PM7 for the distances between the metal ion and its coordinating atoms is 0.063Å for all lanthanides, ranging from a minimum of 0.052Å for Tb(III) to 0.088Å for Ce(III), comparable to the equivalent errors in the distances predicted by PM7 for other metals. These distance deviations follow a gamma distribution within a 95% level of confidence, signifying that they appear to be random around a mean, confirming that Sparkle/PM7 is a well-tempered method. We conclude by carrying out a Sparkle/PM7 full geometry optimization of two spatial groups of the same thulium-containing metal organic framework, with unit cells accommodating 376 atoms, of which 16 are Tm(III) cations; the optimized geometries were in good agreement with the crystallographic ones. These results emphasize the capability of the use of the Sparkle Model for the prediction of geometries of compounds containing lanthanide trications within the PM7 semiempirical model, as well as the usefulness of such semiempirical calculations for materials modeling. Sparkle/PM7 is available in the software package MOPAC2012, at no cost for academics and can be obtained from http://openmopac.net.

Process of coke less without waste treatment of direct vanadium allowing steel melting

International Nuclear Information System (INIS)

Lisienko, V.G.; Droujinina, O.G.; Morozova, V.A.; Ladigina, N.V.; Yusfin, Yu.S.; Parenkev, A.E.

2003-01-01

The development of new methods of steel production are now conducted with the purpose of energy consumption and harmful emissions reduction. The choice of technology and equipment in this case plays a marginal role. It is well known that vanadium alloying steel has increased service properties. The known classical scheme of vanadium steel melting is very power-intensive, as includes such power-intensive processes as blast furnace process and chemical processing of vanadium slag therewith sintering and by-product coke processes are accompanied by significant harmful emissions. In so doing the vanadium losses may run to 60%. In view of requests of environment protection and economical efficiency the new process of coke less without wastes processing of vanadium-bearing raw material with direct vanadium allowing of steel - LP-process is developed. Its purpose is the melting on the basis of vanadium-bearing titanomagnetite of vanadium allowing steel with increase of vanadium concentration in steel and diminution of vanadium losses without application coke and natural gas with use of any coals and carbon-bearing wastes. LP-process consists of three aggregates and corresponding processes: process of liquid-phase reduction, process of vanadium-bearing pellets metallization in the shaft furnace, and process of alloying steel melting in the arc electric furnace. The obtained results have shown, that the LP-process is more energy saving on a comparison with other methods of vanadium allowing steel production. (Original)

Metal-adeninate vertices for the construction of an exceptionally porous metal-organic framework.

Science.gov (United States)

An, Jihyun; Farha, Omar K; Hupp, Joseph T; Pohl, Ehmke; Yeh, Joanne I; Rosi, Nathaniel L

2012-01-03

Metal-organic frameworks comprising metal-carboxylate cluster vertices and long, branched organic linkers are the most porous materials known, and therefore have attracted tremendous attention for many applications, including gas storage, separations, catalysis and drug delivery. To increase metal-organic framework porosity, the size and complexity of linkers has increased. Here we present a promising alternative strategy for constructing mesoporous metal-organic frameworks that addresses the size of the vertex rather than the length of the organic linker. This approach uses large metal-biomolecule clusters, in particular zinc-adeninate building units, as vertices to construct bio-MOF-100, an exclusively mesoporous metal-organic framework. Bio-MOF-100 exhibits a high surface area (4,300 m(2) g(-1)), one of the lowest crystal densities (0.302 g cm(-3)) and the largest metal-organic framework pore volume reported to date (4.3 cm(3) g(-1)).

TEM investigation of ductile iron alloyed with vanadium.

Science.gov (United States)

Dymek, S; Blicharski, M; Morgiel, J; Fraś, E

2010-03-01

This article presents results of the processing and microstructure evolution of ductile cast iron, modified by an addition of vanadium. The ductile iron was austenitized closed to the solidus (1095 degrees C) for 100 h, cooled down to 640 degrees C and held on at this temperature for 16 h. The heat treatment led to the dissolution of primary vanadium-rich carbides and their subsequent re-precipitation in a more dispersed form. The result of mechanical tests indicated that addition of vanadium and an appropriate heat treatment makes age hardening of ductile iron feasible. The precipitation processes as well as the effect of Si content on the alloy microstructure were examined by scanning and transmission electron microscopy. It was shown that adjacent to uniformly spread out vanadium-rich carbides with an average size of 50 nm, a dispersoid composed of extremely small approximately 1 nm precipitates was also revealed.

Structure, ferroelectric ordering, and semiempirical quantum calculations of lanthanide based metal-organic framework: [Nd(C4H5O6)(C4H4O6)][3H2O

International Nuclear Information System (INIS)

Ahmad, Bhat Zahoor; Want, Basharat

2016-01-01

We investigate the structure and ferroelectric behavior of a lanthanide based metal-organic framework (MOF), [Nd(C 4 H 5 O 6 )(C 4 H 4 O 6 )][3H 2 O]. X-ray crystal structure analyses reveal that it crystallizes in the P4 1 2 1 2 space group with Nd centres, coordinated by nine oxygen atoms, forming a distorted capped square antiprismatic geometry. The molecules, bridged by tartrate ligands, form a 2D chiral structure. The 2D sheets are further linked into a 3D porous framework via strong hydrogen-bonding scheme (O-H…O ≈ 2.113 Å). Dielectric studies reveal two anomalies at 295 K and 185 K. The former is a paraelectric-ferroelectric transition, and the later is attributed to the freezing down of the motion of the hydroxyl groups. The phase transition is of second order, and the spontaneous polarization in low temperature phase is attributed to the ordering of protons of hydroxyl groups. The dielectric nonlinearity parameters have been calculated using Landau– Devonshire phenomenological theory. In addition, the most recent semiempirical models, Sparkle/PM7, Sparkle/RM1, and Sparkle/AM1, are tested on the present system to assay the accuracy of semiempirical quantum approaches to predict the geometries of solid MOFs. Our results show that Sparkle/PM7 model is the most accurate to predict the unit cell structure and coordination polyhedron geometry. The semiempirical methods are also used to calculate different ground state molecular properties.

2,2',-bipyridine and 1,10-phenanthroline complexes of lanthanide(III) trifluoroacetates

International Nuclear Information System (INIS)

Misra, S.N.; Singh, M.

1983-01-01

The syntheses and characterization of lanthanide(III) triflloroacetate complexes with 2,2'-bipyridine and 1,10-phenanthroline are reported. Lanthanide(III) trifluoroacetates yield compounds of the type Ln(CF 3 COO) 3 .bipy or phen with 2,2'-bipyridine and 1,10-phenanthroline. Their properties and structures have been studied using chemical analyses. electronic and infrared spectra. Thermal analysis of a few complexes have also been done. The infrared data show that the trifluoroacetate group acts as a bidentate ligand making the coordination number of lanthanide eight. (author)

A novel comprehensive utilization of vanadium slag: As gamma ray shielding material

Energy Technology Data Exchange (ETDEWEB)

Dong, Mengge [School of Metallurgy, Northeastern University, Shenyang 110004 (China); Liaoning Key Laboratory of Metallurgical Resources Recycling Science, Shenyang 110004 (China); Xue, Xiangxin, E-mail: xuexx@mail.neu.edu.cn [School of Metallurgy, Northeastern University, Shenyang 110004 (China); Liaoning Key Laboratory of Metallurgical Resources Recycling Science, Shenyang 110004 (China); Yang, He; Liu, Dong [School of Metallurgy, Northeastern University, Shenyang 110004 (China); Liaoning Key Laboratory of Metallurgical Resources Recycling Science, Shenyang 110004 (China); Wang, Chao [Institute of Metal Research, Chinese Academy of Sciences, Shenyang 110016 (China); Li, Zhefu [Institute of Applied Physics, Chinese Academy of Sciences, Shanghai 201800 (China)

2016-11-15

Highlights: • A novel comprehensive utilization method for vanadium slag is proposed. • Shielding properties of vanadium slag are better than ordinary concrete. • HVL of vanadium slag is between Lead and concrete to shield {sup 60}Co gamma ray. • HVL of composite is higher than concrete when adding amount of vanadium slag is 900. • Composite can be used as injecting mortar for cracks developed in concrete shields. - Abstract: New exploration of vanadium slag as gamma ray shielding material was proposed, the shielding properties of vanadium slag was higher than concrete when the energy of photons was in 0.0001 MeV–100000 MeV. Vanadium slag/epoxy resin composites were prepared, shielding and material properties of materials were tested by {sup 60}Co gamma ray, simultaneous DSC-TGA, electronic universal testing machine and scanning electron microscopy, respectively. The results showed that the shielding properties of composite would be better with the increase of vanadium slag addition amount. The HVL (half value layer thickness) of vanadium slag was between Lead and concrete while composite was higher than concrete when the addition amount of vanadium slag was 900 used as material to shield {sup 60}Co gamma ray, also the resistance temperature of composite was about 215 °C and the bending strength was over 10 MPa. The composites could be used as injecting mortar for cracks developed in biological concrete shields, coating for the floor of the nuclear facilities, and shielding materials by itself.

Measuring Modularity in Open Source Code Bases

Directory of Open Access Journals (Sweden)

Roberto Milev

2009-03-01

Full Text Available Modularity of an open source software code base has been associated with growth of the software development community, the incentives for voluntary code contribution, and a reduction in the number of users who take code without contributing back to the community. As a theoretical construct, modularity links OSS to other domains of research, including organization theory, the economics of industry structure, and new product development. However, measuring the modularity of an OSS design has proven difficult, especially for large and complex systems. In this article, we describe some preliminary results of recent research at Carleton University that examines the evolving modularity of large-scale software systems. We describe a measurement method and a new modularity metric for comparing code bases of different size, introduce an open source toolkit that implements this method and metric, and provide an analysis of the evolution of the Apache Tomcat application server as an illustrative example of the insights gained from this approach. Although these results are preliminary, they open the door to further cross-discipline research that quantitatively links the concerns of business managers, entrepreneurs, policy-makers, and open source software developers.

Numerical modeling of an all vanadium redox flow battery.

Energy Technology Data Exchange (ETDEWEB)

Clausen, Jonathan R.; Brunini, Victor E.; Moffat, Harry K.; Martinez, Mario J.

2014-01-01

We develop a capability to simulate reduction-oxidation (redox) flow batteries in the Sierra Multi-Mechanics code base. Specifically, we focus on all-vanadium redox flow batteries; however, the capability is general in implementation and could be adopted to other chemistries. The electrochemical and porous flow models follow those developed in the recent publication by [28]. We review the model implemented in this work and its assumptions, and we show several verification cases including a binary electrolyte, and a battery half-cell. Then, we compare our model implementation with the experimental results shown in [28], with good agreement seen. Next, a sensitivity study is conducted for the major model parameters, which is beneficial in targeting specific features of the redox flow cell for improvement. Lastly, we simulate a three-dimensional version of the flow cell to determine the impact of plenum channels on the performance of the cell. Such channels are frequently seen in experimental designs where the current collector plates are borrowed from fuel cell designs. These designs use a serpentine channel etched into a solid collector plate.

Effect of Organic Vapour on Porous Alumina Based Moisture Sensor in Dry Gases

Directory of Open Access Journals (Sweden)

Saakshi DHANEKAR

2009-08-01

Full Text Available A capacitive porous alumina based trace moisture sensor in the range of 50 to 500 ppm (V was fabricated by low cost sol-gel technique. The cross-sensitivities due to the presence of organic vapours like ethanol, methanol, acetone and benzene were studied. The change in response and recovery time with ppm for moisture sensing was also calculated. The experimental results conclude that moisture sensor is responsive to the polar organic vapours but has almost negligible response to the nonpolar molecules like benzene. Response of the sensor to the organic vapours as compared to the moisture sensitivity is very less. The effect of ambient temperature was found to be negligible.

Hierarchy of modular graph identities

Energy Technology Data Exchange (ETDEWEB)

D’Hoker, Eric; Kaidi, Justin [Mani L. Bhaumik Institute for Theoretical Physics, Department of Physics and Astronomy,University of California,Los Angeles, CA 90095 (United States)

2016-11-09

The low energy expansion of Type II superstring amplitudes at genus one is organized in terms of modular graph functions associated with Feynman graphs of a conformal scalar field on the torus. In earlier work, surprising identities between two-loop graphs at all weights, and between higher-loop graphs of weights four and five were constructed. In the present paper, these results are generalized in two complementary directions. First, all identities at weight six and all dihedral identities at weight seven are obtained and proven. Whenever the Laurent polynomial at the cusp is available, the form of these identities confirms the pattern by which the vanishing of the Laurent polynomial governs the full modular identity. Second, the family of modular graph functions is extended to include all graphs with derivative couplings and worldsheet fermions. These extended families of modular graph functions are shown to obey a hierarchy of inhomogeneous Laplace eigenvalue equations. The eigenvalues are calculated analytically for the simplest infinite sub-families and obtained by Maple for successively more complicated sub-families. The spectrum is shown to consist solely of eigenvalues s(s−1) for positive integers s bounded by the weight, with multiplicities which exhibit rich representation-theoretic patterns.

Hierarchy of modular graph identities

International Nuclear Information System (INIS)

D’Hoker, Eric; Kaidi, Justin

2016-01-01

The low energy expansion of Type II superstring amplitudes at genus one is organized in terms of modular graph functions associated with Feynman graphs of a conformal scalar field on the torus. In earlier work, surprising identities between two-loop graphs at all weights, and between higher-loop graphs of weights four and five were constructed. In the present paper, these results are generalized in two complementary directions. First, all identities at weight six and all dihedral identities at weight seven are obtained and proven. Whenever the Laurent polynomial at the cusp is available, the form of these identities confirms the pattern by which the vanishing of the Laurent polynomial governs the full modular identity. Second, the family of modular graph functions is extended to include all graphs with derivative couplings and worldsheet fermions. These extended families of modular graph functions are shown to obey a hierarchy of inhomogeneous Laplace eigenvalue equations. The eigenvalues are calculated analytically for the simplest infinite sub-families and obtained by Maple for successively more complicated sub-families. The spectrum is shown to consist solely of eigenvalues s(s−1) for positive integers s bounded by the weight, with multiplicities which exhibit rich representation-theoretic patterns.

Hydrometallurgic treatment of a mineral containing uranium, vanadium and phosphorus

International Nuclear Information System (INIS)

Echenique, Patricia; Fruchtenicht, Fernando; Gil, Daniel; Vigo, Daniel; Bouza, Angel; Vert, Gabriela; Becquart, Elena

1987-01-01

A preliminary study of a mineral has been made towards the hydrometallurgy separation of uranium, vanadium and phosphorus. After the ore dressing, work on sulfuric acid with oxidation leaching has been made, to get the uranium, vanadium and phosphorus in solution. For the separation and purification of these elements, two alternative solvent extraction methods have been tested. One of them has been the extraction of uranium and vanadium and a selective stripping of both elements. The second one has been the selective extraction of uranium and vanadium at different aqueous solutions pH. In both methods, the same reagent has been used: di(2-ethylhexyl) phosphoric acid, kerosene as diluent with two different synergistic agents: TOPO (tri-n-octyl phosphine oxide) and TBP (tri-n-butyl phosphate). Batch studies have been made to determine the equilibrium isotherms for uranium and vanadium. A continuous countercurrent simulation method has been used to get the best phase ratio and to test different stripping agents. For the first method, an important loss of uranium and vanadium at the feed solution conditioning for the extraction step has been observed. For the second method, a good recovery of uranium has been reached, but there has been losses of vanadium in pH adjustment. Nevertheless, among these processes, the last seems to work better in this mineral hydrometallurgy. (Author) [es

Oxidation of methyl heterocyclic compounds on vanadium oxide catalysts

International Nuclear Information System (INIS)

Shimanskaya, M.V.; Lejtis, L.A.; Iovel', I.G.; Gol'dberg, Yu.Sh.; Skolmejstere, R.A.; Golender, L.O.

1985-01-01

Data on vapor-phase oxidation of methyl derivatives of thiophene, Δ 2 - thiazo line, pyridine, pyrazine and pyramidine on oxide vanadium-molybdenum catalysts to corresponding heterylaldehydes are generalized. The dependence of catalytic properties of oxide vanadium-molybdenum systems in oxidation reactions of methylheterocyclic compounds on V:Mo ratio in the catalyst is revealed. It is shown that heterocyclic compounds are coordinated by a heteroatom on Lewis centres of V-Mo-O-catalyst primarily with partially reduced vanadium ions

Lanthanide tris(β-diketonates) as useful probes for chirality determination of biological amino alcohols in vibrational circular dichroism: ligand to ligand chirality transfer in lanthanide coordination sphere.

Science.gov (United States)

Miyake, Hiroyuki; Terada, Keiko; Tsukube, Hiroshi

2014-06-01

A series of lanthanide tris(β-diketonates) functioned as useful chirality probes in the vibrational circular dichroism (VCD) characterization of biological amino alcohols. Various chiral amino alcohols induced intense VCD signals upon ternary complexation with racemic lanthanide tris(β-diketonates). The VCD signals observed around 1500 cm(-1) (β-diketonate IR absorption region) correlated well with the stereochemistry and enantiomeric purity of the targeted amino alcohol, while the corresponding monoalcohol, monoamine, and diol substrates induced very weak VCD signals. The high-coordination number and dynamic property of the lanthanide complex offer an effective chirality VCD probing of biological substrates. © 2014 Wiley Periodicals, Inc.

Lanthanide and actinide separation studies using liquid chromatography

International Nuclear Information System (INIS)

Datta, Arpita; Sivaraman, N.; Srinivasan, T.G.; Vasudeva Rao, P.R.

2011-01-01

Gradient elution procedure for isolation of individual lanthanides was studied extensively at our laboratory using monolith support. A large number of gradients were developed by varying the concentrations of CSA, α-HIBA, mobile phase pH and mobile phase flow rate. In a typical gradient run, the concentration of CSA and mobile phase flow rate were kept constant and only α-HIBA concentration was varied. Based on these studies, a binary gradient elution method was developed for the rapid separation of lanthanides, from La to Lu in about 2.8 min, with a mobile phase CSA, α-HIBA and pH being 0.03M, 0.05 to 0.15M and 3.4-3.8 respectively. The direct injection of dissolver solution from FBTR spent fuel into HPLC was investigated and the results are shown. The lanthanides present in dissolver solution were mutually separated as well as resolved from uranium and plutonium under dynamic ion exchange conditions using the monolithic column. The concentration of La, Ce, Pr, Nd and Sm were determined in the dissolver solution using a calibration plot

Design and construction of porous metal-organic frameworks based on flexible BPH pillars

Energy Technology Data Exchange (ETDEWEB)

Hao, Xiang-Rong; Yang, Guang-sheng; Shao, Kui-Zhan [Institute of Functional Material Chemistry, Faculty of Chemistry, Northeast Normal University, Changchun 130024, Jilin (China); Su, Zhong-Min, E-mail: zmsu@nenu.edu.cn [Institute of Functional Material Chemistry, Faculty of Chemistry, Northeast Normal University, Changchun 130024, Jilin (China); Yuan, Gang; Wang, Xin-Long [Institute of Functional Material Chemistry, Faculty of Chemistry, Northeast Normal University, Changchun 130024, Jilin (China)

2013-02-15

Three metal-organic frameworks (MOFs), [Co{sub 2}(BPDC){sub 2}(4-BPH){center_dot}3DMF]{sub n} (1), [Cd{sub 2}(BPDC){sub 2}(4-BPH){sub 2}{center_dot}2DMF]{sub n} (2) and [Ni{sub 2}(BDC){sub 2}(3-BPH){sub 2} (H{sub 2}O){center_dot}4DMF]{sub n} (3) (H{sub 2}BPDC=biphenyl-4,4 Prime -dicarboxylic acid, H{sub 2}BDC=terephthalic acid, BPH=bis(pyridinylethylidene)hydrazine and DMF=N,N Prime -dimethylformamide), have been solvothermally synthesized based on the insertion of heterogeneous BPH pillars. Framework 1 has 'single-pillared' MOF-5-like motif with inner cage diameters of up to 18.6 A. Framework 2 has 'double pillared' MOF-5-like motif with cage diameters of 19.2 A while 3 has 'double pillared' 8-connected framework with channel diameters of 11.0 A. Powder X-ray diffraction (PXRD) shows that 3 is a dynamic porous framework. - Graphical abstract: By insertion of flexible BPH pillars based on 'pillaring' strategy, three metal-organic frameworks are obtained showing that the porous frameworks can be constructed in a much greater variety. Highlights: Black-Right-Pointing-Pointer Frameworks 1 and 2 have MOF-5 like motif. Black-Right-Pointing-Pointer The cube-like cages in 1 and 2 are quite large, comparable to the IRMOF-10. Black-Right-Pointing-Pointer Framework 1 is 'single-pillared' mode while 2 is 'double-pillared' mode. Black-Right-Pointing-Pointer PXRD and gas adsorption analysis show that 3 is a dynamic porous framework.

Service Modularity

DEFF Research Database (Denmark)

Avlonitis, Viktor; Hsuan, Juliana

2015-01-01

The purpose of this research is to investigate the studies on service modularity with a goal of informing service science and advancing contemporary service systems research. Modularity, a general systems property, can add theoretical underpinnings to the conceptual development of service science...... in general and service systems in particular. Our research is guided by the following question: how can modularity theory inform service system design? We present a review of the modularity literature and associated concepts. We then introduce the contemporary service science and service system discourse...

Comparison of damage microstructures in neutron-irradiated vanadium and iron

International Nuclear Information System (INIS)

Horton, L.L.; Farrell, K.

1983-01-01

The cavity morphology and dislocation loop geometry in bcc vanadium are compared with the previously reported observations for neutron-irradiated iron. The specimens were vanadium (V) with 100 wppM of interstitial impurities and vanadium with boron carbide additions (V-B 4 C) which were irradiated to approx. 1 dpa in the same Oak Ridge Research Reactor capsules as the iron specimens

Magnetic dipole moments of odd-odd lanthanides

International Nuclear Information System (INIS)

Sharma, S.D.; Gandhi, R.

1988-01-01

Magnetic dipole moments of odd-odd lanthanides. Collective model of odd-odd nuclei is applied to predict the magnetic dipole moments, (μ) of odd-odd lanthanides. A simplified version of expression for μ based on diagonalisation of Hamiltonian (subsequent use of eigenvectors to compute μ) is developed for cases of ground state as well as excited states using no configuration mixing and is applied to the cases of odd-odd lanthanides. The formulae applied to the eleven (11) cases of ground states show significant improvement over the results obtained using shell model. Configuration mixing and coriolis coupling is expected to cause further improvement in the results. On comparing the earlier work in this direction the present analysis has clarified that in the expression μ the projection factors have different signs for the case I=Ωp - Ωn and I=Ωn - Ωp, and sign of μ is negative in general in the second case while it is positive in all others of spin projection alignments. Although the general expression holds for excited states as well but in lanthanide region, the experimental reports of magnetic dipole moments of excite states (band heads of higher rational sequences) are not available except in case of five (5) neutron resonance states which cannot be handled on the basis of the present approach with no configuration mixing. Although in the present discussion, the model could not be applied to excited states but the systematics of change in its magnitude with increasing spin at higher rational states is very well understood. The particle part supressed under faster rotation of the nuclear core and thus finally at higher spin I, the value μ is given by μ=g c I (same as in case of even-even nuclei). These systematics are to be verified whenever enough data for higher excited states are available. (author). 11 refs

Studies on trivalent lanthanide complexes of bis-vanillin p-phenylenediamine

International Nuclear Information System (INIS)

Shahma, Abu; Ahmad, Naseer

1983-01-01

The coordination interaction of lanthanide(III) chlorides with bis-vanillin o-phenylenediamine was studied by Ansari and Ahmad (1977). It was thought fruitful to compare these with the complexes of trivalent lanthanide ions with bis-vanillin p-phenylenediamine. The newly synthesized complexes were subjected to elemental, thermogravimetric and differential thermal analyses and their melting points, magnetic susceptibilities, molar conductances determined and infrared and electronic spectra taken. (author)

Lanthanide doped strontium-barium cesium halide scintillators

Science.gov (United States)

Bizarri, Gregory; Bourret-Courchesne, Edith; Derenzo, Stephen E.; Borade, Ramesh B.; Gundiah, Gautam; Yan, Zewu; Hanrahan, Stephen M.; Chaudhry, Anurag; Canning, Andrew

2015-06-09

The present invention provides for a composition comprising an inorganic scintillator comprising an optionally lanthanide-doped strontium-barium, optionally cesium, halide, useful for detecting nuclear material.

Potentiometric titrations of molybdenum and vanadium in aqueous and mixed so lvents

International Nuclear Information System (INIS)

Das, S.K.; Dhaneshwar, R.G.

1990-01-01

Potentiometric titration method was developed for molybdenum, employing different electrode systems. Molybdenum(VI) is reduced to molybdenum(V) by ferrous solution in presence of phosphoric acid and then titrated with potassium dichromate. It was found that ferrous concentration should be five times more than molybdenum and phosphoric acid should be 1.0 ml for 0.1N titration and 0.5 ml for lower concentration titrations. The method is also applicable to vanadium titrations. Employing Au/SCE and Pt/SCE systems, it was observed that generally curve heights obtained for platinum electrode are higher than those for gold electrode. Also for both the electrode systems, the curve heights for vanadium titrations were found to be more than those for molybdenum. Lower limits of titrations for Au/SCE system are 0.01N for molybdenum and 0.0001N for vanadium, whereas for Pt/SCE system, the lower limits obtained were 0.01N for both molybdenum and vanadium titrations. In order to improve the sensitivities of the method, the bimetallic electrode systems Au/Pt and Pt/Au were employed. Au/Pt system was found to give better results than Pt/Au systems. Addition of organic solvent was found to have beneficial effects for titrations of 0.001N and below. Methanol was found to be a better solvent than ethanol. Molybdenum titrations, at 0.0001N level could be performed in methanol with Au/Pt system, which is to b e generally preferred than Pt/Au system. (author). 7 refs., 3 tabs

A charge-polarized porous metal-organic framework for gas chromatographic separation of alcohols from water.

Science.gov (United States)

Sun, Jian-Ke; Ji, Min; Chen, Cheng; Wang, Wu-Gen; Wang, Peng; Chen, Rui-Ping; Zhang, Jie

2013-02-25

A bipyridinium ligand with a charge separated skeleton has been introduced into a metal-organic framework to yield a porous material with charge-polarized pore space, which exhibits selective adsorption for polar guest molecules and can be further used in gas chromatography for the separation of alcohol-water mixtures.

Low-temperature direct synthesis of mesoporous vanadium nitrides for electrochemical capacitors

Science.gov (United States)

Lee, Hae-Min; Jeong, Gyoung Hwa; Kim, Sang-Wook; Kim, Chang-Koo

2017-04-01

Mesoporous vanadium nitrides are directly synthesized by a one-step chemical precipitation method at a low temperature (70 °C). Structural and morphological analyses reveal that vanadium nitride consist of long and slender nanowhiskers, and mesopores with diameters of 2-5 nm. Compositional analysis confirms the presence of vanadium in the VN structure, along with oxidized vanadium. The cyclic voltammetry and charge-discharge tests indicate that the obtained material stores charges via a combination of electric double-layer capacitance and pseudocapacitance mechanisms. The vanadium nitride electrode exhibits a specific capacitance of 598 F/g at a current density of 4 A/g. After 5000 charge-discharge cycles, the electrode has an equivalent series resistance of 1.42 Ω and retains 83% of its initial specific capacitance. This direct low-temperature synthesis of mesoporous vanadium nitrides is a simple and promising method to achieve high specific capacitance and low equivalent series resistance for electrochemical capacitor applications.

Graded/Gradient Porous Biomaterials

Directory of Open Access Journals (Sweden)

Xigeng Miao

2009-12-01

Full Text Available Biomaterials include bioceramics, biometals, biopolymers and biocomposites and they play important roles in the replacement and regeneration of human tissues. However, dense bioceramics and dense biometals pose the problem of stress shielding due to their high Young’s moduli compared to those of bones. On the other hand, porous biomaterials exhibit the potential of bone ingrowth, which will depend on porous parameters such as pore size, pore interconnectivity, and porosity. Unfortunately, a highly porous biomaterial results in poor mechanical properties. To optimise the mechanical and the biological properties, porous biomaterials with graded/gradient porosity, pores size, and/or composition have been developed. Graded/gradient porous biomaterials have many advantages over graded/gradient dense biomaterials and uniform or homogenous porous biomaterials. The internal pore surfaces of graded/gradient porous biomaterials can be modified with organic, inorganic, or biological coatings and the internal pores themselves can also be filled with biocompatible and biodegradable materials or living cells. However, graded/gradient porous biomaterials are generally more difficult to fabricate than uniform or homogenous porous biomaterials. With the development of cost-effective processing techniques, graded/gradient porous biomaterials can find wide applications in bone defect filling, implant fixation, bone replacement, drug delivery, and tissue engineering.

Nanostructured Electrocatalysts for All-Vanadium Redox Flow Batteries.

Science.gov (United States)

Park, Minjoon; Ryu, Jaechan; Cho, Jaephil

2015-10-01

Vanadium redox reactions have been considered as a key factor affecting the energy efficiency of the all-vanadium redox flow batteries (VRFBs). This redox reaction determines the reaction kinetics of whole cells. However, poor kinetic reversibility and catalytic activity towards the V(2+)/V(3+) and VO(2+)/VO2(+) redox couples on the commonly used carbon substrate limit broader applications of VRFBs. Consequently, modified carbon substrates have been extensively investigated to improve vanadium redox reactions. In this Focus Review, recent progress on metal- and carbon-based nanomaterials as an electrocatalyst for VRFBs is discussed in detail, without the intention to provide a comprehensive review on the whole components of the system. Instead, the focus is mainly placed on the redox chemistry of vanadium ions at a surface of various metals, different dimensional carbons, nitrogen-doped carbon nanostructures, and metal-carbon composites. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Effect of Organic Substrates on the Photocatalytic Reduction of Cr(VI by Porous Hollow Ga2O3 Nanoparticles

Directory of Open Access Journals (Sweden)

Jin Liu

2018-04-01

Full Text Available Porous hollow Ga2O3 nanoparticles were successfully synthesized by a hydrolysis method followed by calcination. The prepared samples were characterized by field emission scanning electron microscope, transmission electron microscope, thermogravimetry and differential scanning calorimetry, UV-vis diffuse reflectance spectra and Raman spectrum. The porous structure of Ga2O3 nanoparticles can enhance the light harvesting efficiency, and provide lots of channels for the diffusion of Cr(VI and Cr(III. Photocatalytic reduction of Cr(VI, with different initial pH and degradation of several organic substrates by porous hollow Ga2O3 nanoparticles in single system and binary system, were investigated in detail. The reduction rate of Cr(VI in the binary pollutant system is markedly faster than that in the single Cr(VI system, because Cr(VI mainly acts as photogenerated electron acceptor. In addition, the type and concentration of organic substrates have an important role in the photocatalytic reduction of Cr(VI.

Effect of Organic Substrates on the Photocatalytic Reduction of Cr(VI) by Porous Hollow Ga2O3 Nanoparticles

Science.gov (United States)

Liu, Jin; Gan, Huihui; Wu, Hongzhang; Zhang, Xinlei; Zhang, Jun; Li, Lili; Wang, Zhenling

2018-01-01

Porous hollow Ga2O3 nanoparticles were successfully synthesized by a hydrolysis method followed by calcination. The prepared samples were characterized by field emission scanning electron microscope, transmission electron microscope, thermogravimetry and differential scanning calorimetry, UV-vis diffuse reflectance spectra and Raman spectrum. The porous structure of Ga2O3 nanoparticles can enhance the light harvesting efficiency, and provide lots of channels for the diffusion of Cr(VI) and Cr(III). Photocatalytic reduction of Cr(VI), with different initial pH and degradation of several organic substrates by porous hollow Ga2O3 nanoparticles in single system and binary system, were investigated in detail. The reduction rate of Cr(VI) in the binary pollutant system is markedly faster than that in the single Cr(VI) system, because Cr(VI) mainly acts as photogenerated electron acceptor. In addition, the type and concentration of organic substrates have an important role in the photocatalytic reduction of Cr(VI). PMID:29690548

Tackling capacity fading in vanadium flow batteries with amphoteric membranes

Science.gov (United States)

Oldenburg, Fabio J.; Schmidt, Thomas J.; Gubler, Lorenz

2017-11-01

Capacity fading and poor electrolyte utilization caused by electrolyte imbalance effects are major drawbacks for the commercialization of vanadium flow batteries (VFB). The influence of membrane type (cationic, anionic, amphoteric) on these effects is studied by determining the excess and net flux of each vanadium ion in an operating VFB assembled with a cation exchange membrane (CEM), Nafion® NR212, an anion exchange membrane (AEM), Fumatech FAP-450, and an amphoteric ion exchange membrane (AIEM) synthesized in-house. It is shown that the net vanadium flux, accompanied by water transport, is directed towards the positive side for the CEM and towards the negative side for the AEM. The content of cation and anion exchange groups in the AIEM is adjusted via radiation grafting to balance the vanadium flux between the two electrolyte sides. With the AIEM the net vanadium flux is significantly reduced and capacity fading due to electrolyte imbalances can be largely eliminated. The membrane's influence on electrolyte imbalance effects is characterized and quantified in one single charge-discharge cycle by analyzing the content of the four different vanadium species in the two electrolytes. The experimental data recorded herewith conclusively explains the electrolyte composition after 80 cycles.

Modular Trough Power Plant Cycle and Systems Analysis

Energy Technology Data Exchange (ETDEWEB)

Price, H.; Hassani, V.

2002-01-01

This report summarizes an analysis to reduce the cost of power production from modular concentrating solar power plants through a relatively new and exciting concept that merges two mature technologies to produce distributed modular electric power in the range of 500 to 1,500 kWe. These are the organic Rankine cycle (ORC) power plant and the concentrating solar parabolic (CSP) trough technologies that have been developed independent of each other over many years.

Novel open-framework architectures in lanthanide phosphonates

Science.gov (United States)

Groves, John A.; Stephens, Nicholas F.; Wright, Paul A.; Lightfoot, Philip

2006-03-01

Two novel three-dimensional lanthanide coordination polymers have been prepared hydrothermally with the phosphonic acid N,N-piperazine bis(methylenephosphonic acid), H 2O 3PCH 2N(C 2H 4) 2NCH 2PO 3H 2 ( LH 4). The structures of Gd 2( LH 2) 3ṡ3H 2O (I) and Nd 2( LH 2) 3ṡ9H 2O (II) have been characterised by single crystal X-ray techniques. One-dimensional 'lanthanide-phosphate' chains are a key feature in both structures, although there are major structural differences between the chains, with (I) displaying octahedral GdO 6 coordination and (II) showing eight-coordinate NdO 8 polyhedra. In each case, three-dimensional connectivity is completed by coordination of the phosphonate group resulting in open framework structures encapsulating loosely bound water molecules. Isostructural Y 3+ and Yb 3+ analogues of (I) have been prepared, suggesting that cation size is a key factor in controlling the differing reaction products. In the case of Y 2( LH 2) 3ṡ5H 2O, isostructural to (I), it is shown that the extra-framework water molecules may be removed reversibly without framework collapse. Structural relationships to other known lanthanide phosphonates are discussed.

Tuning the sensitivity of lanthanide-activated NIR nanothermometers in the biological windows

NARCIS (Netherlands)

Cortelletti, P.; Skripka, A.; Facciotti, C.; Pedroni, M.; Caputo, G.; Pinna, N.; Quintanilla, M.; Benayas, A.; Vetrone, F.; Speghini, A.

2018-01-01

Lanthanide-activated SrF2 nanoparticles with a multishell architecture were investigated as optical thermometers in the biological windows. A ratiometric approach based on the relative changes in the intensities of different lanthanide (Nd3+ and Yb3+) NIR emissions was applied to investigate the

Determination of stability constants of lanthanide complexes with tetracycline

International Nuclear Information System (INIS)

Saiki, Mitiko

1975-01-01

The stability constants of complexes compounds formed with tetracycline and lanthanides elements were determined for all lanthanides except promethium. The experimental procedure used was solvent extraction of the lanthanides labelled with their radioactive isotopes. It was shown that the formed complexes are mononuclear and that no hydroxo complexes or negatively charged complexes are formed in the experimental conditions of this work. Four methods of calculation were used for all complexes studied: the method of the average number of ligands, the method of limiting value, the method of two parameters and the method of weighted least squares. A comparison was made of the graphical methods with the method of least squares, showing the convenience of preceding least squares calculation by the graphical methods, in order to verify eventual mistakes of numerical data. It was shown the advantage of using radioisotopes of the elements for such a study, specially if the solvent extraction technique is used to-get the experimental data. (author)

Effectively suppressing vanadium permeation in vanadium redox flow battery application with modified Nafion membrane with nacre-like nanoarchitectures

Science.gov (United States)

Zhang, Lesi; Ling, Ling; Xiao, Min; Han, Dongmei; Wang, Shuanjin; Meng, Yuezhong

2017-06-01

A novel self-assembled composite membrane, Nafion-[PDDA/ZrP]n with nacre-like nanostructures was successfully fabricated by a layer-by-layer (LbL) method and used as proton exchange membrane for vanadium redox flow battery applications. Poly(diallyldimethylammonium chloride) (PDDA) with positive charges and zirconium phosphate (ZrP) nanosheets with negative charges can form ultra-thin nacre-like nanostructure on the surface of Nafion membrane via the ionic crosslinking of tightly folded macromolecules. The lamellar structure of ZrP nanosheets and Donnan exclusion effect of PDDA can greatly decrease the vanadium ion permeability and improve the selectivity of proton conductivity. The fabricated Nafion-[PDDA/ZrP]4 membrane shows two orders of magnitude lower vanadium ion permeability (1.05 × 10-6 cm2 min-1) and 12 times higher ion selectivity than those of pristine Nafion membrane at room temperature. Consequently, the performance of vanadium redox flow batteries (VRFBs) assembled with Nafion-[PDDA/ZrP]3 membrane achieved a highly coulombic efficiency (CE) and energy efficiency (EE) together with a very slow self-discharge rate. When comparing with pristine Nafion VRFB, the CE and EE values of Nafion-[PDDA/ZrP]3 VRFB are 10% and 7% higher at 30 mA cm-2, respectively.

Thermal conductivity of high purity vanadium

International Nuclear Information System (INIS)

Jung, W.D.

1975-01-01

The thermal conductivity, Seebeck coefficient, and electrical resistivity of four high-purity vanadium samples were measured over the temperature range 5 to 300 0 K. The highest purity sample had a resistance ratio (rho 273 /rho 4 . 2 ) of 1524. The highest purity sample had a thermal conductivity maximum of 920 W/mK at 9 0 K and had a thermal conductivity of 35 W/mK at room temperature. At low temperatures, the thermal resistivity was limited by the scattering of electrons by impurities and phonons. The thermal resistivity of vanadium departed from Matthiessen's rule at low temperatures. The electrical resistivity and Seebeck coefficient of high purity vanadium showed no anomalous behavior above 130 0 K. The intrinsic electrical resistivity at low temperatures was due primarily to interband scattering of electrons. The Seebeck coefficient was positive from 10 to 240 0 K and had a maximum which was dependent upon sample purity

Unraveling the disease consequences and mechanisms of modular structure in animal social networks

Science.gov (United States)

Sah, Pratha; Leu, Stephan T.; Cross, Paul C.; Hudson, Peter J.; Bansal, Shweta

2017-01-01

Disease risk is a potential cost of group living. Although modular organization is thought to reduce this cost in animal societies, empirical evidence toward this hypothesis has been conflicting. We analyzed empirical social networks from 43 animal species to motivate our study of the epidemiological consequences of modular structure in animal societies. From these empirical studies, we identified the features of interaction patterns associated with network modularity and developed a theoretical network model to investigate when and how subdivisions in social networks influence disease dynamics. Contrary to prior work, we found that disease risk is largely unaffected by modular structure, although social networks beyond a modular threshold experience smaller disease burden and longer disease duration. Our results illustrate that the lowering of disease burden in highly modular social networks is driven by two mechanisms of modular organization: network fragmentation and subgroup cohesion. Highly fragmented social networks with cohesive subgroups are able to structurally trap infections within a few subgroups and also cause a structural delay to the spread of disease outbreaks. Finally, we show that network models incorporating modular structure are necessary only when prior knowledge suggests that interactions within the population are highly subdivided. Otherwise, null networks based on basic knowledge about group size and local contact heterogeneity may be sufficient when data-limited estimates of epidemic consequences are necessary. Overall, our work does not support the hypothesis that modular structure universally mitigates the disease impact of group living.