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Sample records for solute complexes poorly

  1. Origin of poor doping efficiency in solution processed organic semiconductors.

    Science.gov (United States)

    Jha, Ajay; Duan, Hong-Guang; Tiwari, Vandana; Thorwart, Michael; Miller, R J Dwayne

    2018-05-21

    Doping is an extremely important process where intentional insertion of impurities in semiconductors controls their electronic properties. In organic semiconductors, one of the convenient, but inefficient, ways of doping is the spin casting of a precursor mixture of components in solution, followed by solvent evaporation. Active control over this process holds the key to significant improvements over current poor doping efficiencies. Yet, an optimized control can only come from a detailed understanding of electronic interactions responsible for the low doping efficiencies. Here, we use two-dimensional nonlinear optical spectroscopy to examine these interactions in the course of the doping process by probing the solution mixture of doped organic semiconductors. A dopant accepts an electron from the semiconductor and the two ions form a duplex of interacting charges known as ion-pair complexes. Well-resolved off-diagonal peaks in the two-dimensional spectra clearly demonstrate the electronic connectivity among the ions in solution. This electronic interaction represents a well resolved electrostatically bound state, as opposed to a random distribution of ions. We developed a theoretical model to recover the experimental data, which reveals an unexpectedly strong electronic coupling of ∼250 cm -1 with an intermolecular distance of ∼4.5 Å between ions in solution, which is approximately the expected distance in processed films. The fact that this relationship persists from solution to the processed film gives direct evidence that Coulomb interactions are retained from the precursor solution to the processed films. This memory effect renders the charge carriers equally bound also in the film and, hence, results in poor doping efficiencies. This new insight will help pave the way towards rational tailoring of the electronic interactions to improve doping efficiencies in processed organic semiconductor thin films.

  2. Solution chemistry of lanthanide complexes

    International Nuclear Information System (INIS)

    Brittain, H.G.

    1979-01-01

    Intermolecular energy transfer from Tb 3+ to Eu 3+ , luminescence intensity measurements, potentiometric titrations, differential absorption spectroscopy, and spectroscopic titrations were all used to study the binding of lanthanide ions by serine and threonine. At low pH (3.0 to 6.0) the complexes are mononuclear and ligand is only weakly bound. In the pH interval of 6.0 to 8.5 stronger interaction takes place between the ligand and the metal (with possible coordination of the undissociated hydroxyl group), and self-association of complexes becomes important. Above pH 8.5, base hydrolysis of the complexes leads to highly associated species in solution and shortly above this pH an insoluble precipitate is formed. It was found that energy could be transferred from Tb 3+ to Eu 3+ more efficiently among complexes prepared from racemic ligands than in complexes made from resolved ligand, but this stereoselectivity was only observed at pH values greater than 6.5 and in solutions having a 1:10 ratio of metal-to-ligand. No stereoselectivity was found in solutions having 1:5 ratios, and this observation was explained by the existence of 1:2 metal-ligand complexes existing in solutions having the higher ratio of metal-to-ligand (only 1:1 complexes are then found at lower ratios of metal-to-ligand). (author)

  3. 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.)

  4. Thermodynamic Modeling of Poorly Complexing Metals in Concentrated Electrolyte Solutions: An X-Ray Absorption and UV-Vis Spectroscopic Study of Ni(II) in the NiCl2-MgCl2-H2O System

    Science.gov (United States)

    Zhang, Ning; Brugger, Joël; Etschmann, Barbara; Ngothai, Yung; Zeng, Dewen

    2015-01-01

    Knowledge of the structure and speciation of aqueous Ni(II)-chloride complexes is important for understanding Ni behavior in hydrometallurgical extraction. The effect of concentration on the first-shell structure of Ni(II) in aqueous NiCl2 and NiCl2-MgCl2 solutions was investigated by Ni K edge X-ray absorption (XAS) and UV-Vis spectroscopy at ambient conditions. Both techniques show that no large structural change (e.g., transition from octahedral to tetrahedral-like configuration) occurs. Both methods confirm that the Ni(II) aqua ion (with six coordinated water molecules at R Ni-O = 2.07(2) Å) is the dominant species over the whole NiCl2 concentration range. However, XANES, EXAFS and UV-Vis data show subtle changes at high salinity (> 2 mol∙kg-1 NiCl2), which are consistent with the formation of small amounts of the NiCl+ complex (up to 0.44(23) Cl at a Ni-Cl distance of 2.35(2) Å in 5.05 mol∙kg-1 NiCl2) in the pure NiCl2 solutions. At high Cl:Ni ratio in the NiCl2-MgCl2-H2O solutions, small amounts of [NiCl2]0 are also present. We developed a speciation-based mixed-solvent electrolyte (MSE) model to describe activity-composition relationships in NiCl2-MgCl2-H2O solutions, and at the same time predict Ni(II) speciation that is consistent with our XAS and UV-Vis data and with existing literature data up to the solubility limit, resolving a long-standing uncertainty about the role of chloride complexing in this system. PMID:25885410

  5. Diversity : A poor man's solution to drone takeover

    NARCIS (Netherlands)

    Davanian, Ali; Massacci, Fabio; Allodi, Luca

    2017-01-01

    Drones are the new targets for hackers. On one hand, their widespread use and security weakness have made them very attractive for the attackers. On the other hand, there are a few security solutions for drones. Out of these few, some are just proposals, and fewer are in the early stage of

  6. Poorly crystalline hydroxyapatite: A novel adsorbent for enhanced fulvic acid removal from aqueous solution

    Energy Technology Data Exchange (ETDEWEB)

    Wei, Wei [Department of Environmental Science and Engineering, Nanjing Normal University, Nanjing 210023 (China); Jiangsu Provincial Key Laboratory of Materials Cycling and Pollution Control, Nanjing Normal University, Nanjing 210023 (China); Jiangsu Center for Collaborative Innovation in Geographical Information Resource Development and Application, Nanjing Normal University, Nanjing 210023 (China); Yang, Lei; Zhong, Wenhui; Cui, Jing [Department of Environmental Science and Engineering, Nanjing Normal University, Nanjing 210023 (China); Wei, Zhenggui, E-mail: weizhenggui@gmail.com [Department of Environmental Science and Engineering, Nanjing Normal University, Nanjing 210023 (China); Jiangsu Provincial Key Laboratory of Materials Cycling and Pollution Control, Nanjing Normal University, Nanjing 210023 (China); Jiangsu Center for Collaborative Innovation in Geographical Information Resource Development and Application, Nanjing Normal University, Nanjing 210023 (China)

    2015-03-30

    Graphical abstract: - Highlights: • Poorly crystalline HAP was firstly used for FA removal from aqueous solution. • The maximum adsorption capacity was determined to be 90.20 mg/g at 318 K. • Adsorption kinetics, isotherms and thermodynamic have been studied in detail. • Adsorption mechanism involved surface complexation, electrostatic interaction and hydrogen bonding. - Abstract: In this study, poorly crystalline hydroxyapatite (HAP) was developed as an efficient adsorbent for the removal of fulvic acid (FA) from aqueous solution. Surface functionality, crystallinity, and morphology of the synthetic adsorbent were studied by Fourier-transformation infrared (FT-IR) spectroscopy, powder X-ray diffraction (XRD) and transmission electron microscopy (TEM). The effects of various parameters such as crystallinity of adsorbent, contact time, adsorbent dosage, pH, initial adsorbate concentration, temperature, ionic strength and the presence of alkaline earth metal ions on FA adsorption were investigated. Results indicated that the nanosized HAP calcined at lower temperature was poorly crystalline (X{sub c} = 0.23) and had better adsorption capacity for FA than those (X{sub c} = 0.52, 0.86) calcined at higher temperature. FA removal was increased with increases of adsorbent dosage, temperature, ionic strength and the presence of alkali earth metal ions, but decreased as the pH increased. Kinetic studies showed that pseudo-second-order kinetic model better described the adsorption process. Equilibrium data were best described by Sips models, and the estimated maximum adsorption capacity of poorly crystalline HAP was 90.20 mg/g at 318 K, displaying higher efficiency for FA removal than previously reported adsorbents. FT-IR results revealed that FA adsorption over the adsorbent could be attributed to the surface complexation between the oxygen atom of functional groups of FA and calcium ions of HAP. Regeneration studies indicated that HAP could be recyclable for a long

  7. Poorly crystalline hydroxyapatite: A novel adsorbent for enhanced fulvic acid removal from aqueous solution

    Science.gov (United States)

    Wei, Wei; Yang, Lei; Zhong, Wenhui; Cui, Jing; Wei, Zhenggui

    2015-03-01

    In this study, poorly crystalline hydroxyapatite (HAP) was developed as an efficient adsorbent for the removal of fulvic acid (FA) from aqueous solution. Surface functionality, crystallinity, and morphology of the synthetic adsorbent were studied by Fourier-transformation infrared (FT-IR) spectroscopy, powder X-ray diffraction (XRD) and transmission electron microscopy (TEM). The effects of various parameters such as crystallinity of adsorbent, contact time, adsorbent dosage, pH, initial adsorbate concentration, temperature, ionic strength and the presence of alkaline earth metal ions on FA adsorption were investigated. Results indicated that the nanosized HAP calcined at lower temperature was poorly crystalline (Xc = 0.23) and had better adsorption capacity for FA than those (Xc = 0.52, 0.86) calcined at higher temperature. FA removal was increased with increases of adsorbent dosage, temperature, ionic strength and the presence of alkali earth metal ions, but decreased as the pH increased. Kinetic studies showed that pseudo-second-order kinetic model better described the adsorption process. Equilibrium data were best described by Sips models, and the estimated maximum adsorption capacity of poorly crystalline HAP was 90.20 mg/g at 318 K, displaying higher efficiency for FA removal than previously reported adsorbents. FT-IR results revealed that FA adsorption over the adsorbent could be attributed to the surface complexation between the oxygen atom of functional groups of FA and calcium ions of HAP. Regeneration studies indicated that HAP could be recyclable for a long term. Findings of the present work highlight the potential for using poorly crystalline HAP nanoparticles as an effective and recyclable adsorbent for FA removal from aqueous solution.

  8. URBAN PRO-POOR REGISTRATIONS: COMPLEX-SIMPLE

    African Journals Online (AJOL)

    New Win User

    registrations for the poor and low-literate / corporate social responsibility); ..... legal textbooks, statutory texts, case law texts, customary texts (from a largely ...... by speaking directly to the prosecutor, or an academic who specialises in ethics.

  9. Complex Technical Solution for Renewable Energy

    Directory of Open Access Journals (Sweden)

    Cristian Paul Chioncel

    2010-01-01

    Full Text Available This paper presents a complex technical solution for implementing renewable energy, namely: wind, solar photovoltaic and hydraulics. Because wind and solar photovoltaic energy habe a highly random character, it is required to find solution to store the product energy for unfavorable periods, without wind or solar radiations. This could be achieved using the third type of renewable energy, the hydraulic one, obtained from an hydroelectric pumped storage plant (HPSP, located in the imediate vicinity of the wind and solar photovoltaic plant.

  10. Complex solutions for generalised fitzhughnagumo equation

    International Nuclear Information System (INIS)

    Neirameh, A.

    2014-01-01

    During present investigation, a direct algebraic method on complex solutions of nonlinear partial differential equation is developed and tested in the case of generalized Burgers-Huxley equation. The proposed scheme can be used in a wide class of nonlinear reaction-diffusion equations. These calculations demonstrate that the accuracy of the direct algebraic solutions is quite high even in the case of a small number of grid points. This method is a very reliable, simple, small computation costs, flexible, and convenient alternative method. (author)

  11. Solution of a Complex Least Squares Problem with Constrained Phase.

    Science.gov (United States)

    Bydder, Mark

    2010-12-30

    The least squares solution of a complex linear equation is in general a complex vector with independent real and imaginary parts. In certain applications in magnetic resonance imaging, a solution is desired such that each element has the same phase. A direct method for obtaining the least squares solution to the phase constrained problem is described.

  12. Ibandronate metal complexes: solution behavior and antiparasitic activity.

    Science.gov (United States)

    Demoro, Bruno; Rostán, Santiago; Moncada, Mauricio; Li, Zhu-Hong; Docampo, Roberto; Olea Azar, Claudio; Maya, Juan Diego; Torres, Julia; Gambino, Dinorah; Otero, Lucía

    2018-03-01

    To face the high costs of developing new drugs, researchers in both industry and academy are looking for ways to repurpose old drugs for new uses. In this sense, bisphosphonates that are clinically used for bone diseases have been studied as agents against Trypanosoma cruzi, causative parasite of Chagas disease. In this work, the development of first row transition metal complexes (M = Co 2+ , Mn 2+ , Ni 2+ ) with the bisphosphonate ibandronate (iba, H 4 iba representing the neutral form) is presented. The in-solution behavior of the systems containing iba and the selected 3d metal ions was studied by potentiometry. Mononuclear complexes [M(H x iba)] (2-x)- (x = 0-3) and [M(Hiba) 2 ] 4- together with the formation of the neutral polynuclear species [M 2 iba] and [M 3 (Hiba) 2 ] were detected for all studied systems. In the solid state, complexes of the formula [M 3 (Hiba) 2 (H 2 O) 4 ]·6H 2 O were obtained and characterized. All obtained complexes, forming [M(Hiba)] - species under the conditions of the biological studies, were more active against the amastigote form of T. cruzi than the free iba, showing no toxicity in mammalian Vero cells. In addition, the same complexes were selective inhibitors of the parasitic farnesyl diphosphate synthase (FPPS) enzyme showing poor inhibition of the human one. However, the increase of the anti-T. cruzi activity upon coordination could not be explained neither through the inhibition of TcFPPS nor through the inhibition of TcSPPS (T. cruzi solanesyl-diphosphate synthase). The ability of the obtained metal complexes of catalyzing the generation of free radical species in the parasite could explain the observed anti-T. cruzi activity.

  13. Ternary complex formation at mineral/solution interfaces

    International Nuclear Information System (INIS)

    Leckie, J.O.

    1995-01-01

    Adsorption of trace concentrations of radionuclides and heavy metals from aqueous solution is dependent on pH, absorbent and adsorbate concentration, and speciation of the metal in solution. In particular, complexation of metal ions by organic and inorganic ligands can dramatically alter adsorption behavior compared to ligand-free systems. The presence of complexing ligands can cause the formation of ''metal like'' or ''ligand like'' ternary surface complexes depending on whether adsorption of the ternary complex increases or decreases with increasing pH, respectively. Examples of ternary surface complexes behaving ''metal like'' include uranyl-EDTA surface complexes on goethite, neptunyl-EDTA surface complexes on hematite and neptunyl-humic surface complexes on gibbsite. Examples of ''ligand like'' ternary surface complexes include uranyl-carbonato and neptunyl-carbonato surface complexes on iron oxides. The effects of complex solutions and multimineralic systems are discussed. (authors). 39 refs., 16 figs., 8 tabs

  14. Actinide phosphonate complexes in aqueous solutions

    International Nuclear Information System (INIS)

    Nash, K.L.

    1993-01-01

    Complexes formed by actinides with carboxylic acids, polycarboxylic acids, and aminopolycarboxylic acids play a central role in both the basic and process chemistry of the actinides. Recent studies of f-element complexes with phosphonic acid ligands indicate that new ligands incorporating doubly ionizable phosphonate groups (-PO 3 H 2 ) have many properties which are unique chemically, and promise more efficient separation processes for waste cleanup and environmental restoration. Simple diphosphonate ligands form much stronger complexes than isostructural carboxylates, often exhibiting higher solubility as well. In this manuscript recent studies of the thermodynamics and kinetics of f-element complexation by 1,1 and 1,2 diphosphonic acid ligands are described

  15. Supramolecular Complexation of Carbohydrates for the Bioavailability Enhancement of Poorly Soluble Drugs.

    Science.gov (United States)

    Cho, Eunae; Jung, Seunho

    2015-10-27

    In this review, a comprehensive overview of advances in the supramolecular complexes of carbohydrates and poorly soluble drugs is presented. Through the complexation process, poorly soluble drugs could be efficiently delivered to their desired destinations. Carbohydrates, the most abundant biomolecules, have diverse physicochemical properties owing to their inherent three-dimensional structures, hydrogen bonding, and molecular recognition abilities. In this regard, oligosaccharides and their derivatives have been utilized for the bioavailability enhancement of hydrophobic drugs via increasing the solubility or stability. By extension, polysaccharides and their derivatives can form self-assembled architectures with poorly soluble drugs and have shown increased bioavailability in terms of the sustained or controlled drug release. These supramolecular systems using carbohydrate will be developed consistently in the field of pharmaceutical and medical application.

  16. Modelling of spatially complex human-ecosystem, rural-urban and rich-poor interactions

    CSIR Research Space (South Africa)

    Naude, AH

    2008-06-01

    Full Text Available The paper outlines the challenges of modelling and assessing spatially complex human-ecosystem interactions, and the need to simultaneously consider rural-urban and rich-poor interactions. The context for exploring these challenges is South Africa...

  17. Finding practical solutions to complex problems: IDRC's fifth annual ...

    International Development Research Centre (IDRC) Digital Library (Canada)

    2016-04-15

    Apr 15, 2016 ... English · Français ... Finding practical solutions to complex problems: IDRC's fifth annual ... “IDRC staff share a common goal with the researchers they work with – to find low-cost, down-to-earth solutions to complex problems ...

  18. Complexes of pentavalent plutonium in lithium nitrate solutions

    International Nuclear Information System (INIS)

    Mekhail, F.M.; Zaki, M.R.

    1977-01-01

    Pu 0 2 ion can form nitrate complexes in concentrated solution of lithium nitrate of PH 3.5. Spectrophotometric and ion exchange studies revealed the existence of two complexes, presumably the mono-and the dinitro. The rate of adsorption of the dinitrato complex, formed in 4 to 6 M-lithium nitrate solutions, on De-Acidite FF has been investigated and suggested to be diffusion controlled. The adsorption isotherm found to obey satisfactorily Freundlich equation

  19. Complex organic molecules in organic-poor massive young stellar objects

    DEFF Research Database (Denmark)

    Fayolle, Edith C.; Öberg, Karin I.; Garrod, Robin T.

    2015-01-01

    to search for complex organic molecules over 8-16 GHz in the 1 mm atmospheric window toward three MYSOs with known ice abundances, but without luminous molecular hot cores. Results. Complex molecules are detected toward all three sources at comparable abundances with respect to CH3OH to classical hot core......Context. Massive young stellar objects (MYSOs) with hot cores are classic sources of complex organic molecules. The origins of these molecules in such sources, as well as the small-and large-scale differentiation between nitrogen-and oxygen-bearing complex species, are poorly understood. Aims. We...... aim to use complex molecule abundances toward a chemically less explored class of MYSOs with weak hot organic emission lines to constrain the impact of hot molecular cores and initial ice conditions on the chemical composition toward MYSOs. Methods. We use the IRAM 30 m and the Submillimeter Array...

  20. The blue complexes of U in aqueous solutions

    International Nuclear Information System (INIS)

    Musikas, C.

    1976-01-01

    Mixed-valence uranium complexes were synthesized. Hydrolysis of hexavalent U leads to anionic species soluble in aqueous solutions when the UO 2 ++ ions are neutralized by tetraalkylammonium hydroxides. These complexes are polynuclear and the size and interatomic distances found for the polyanions are those of macromolecules. By hydrazine of these complexes, solutions were obtained and their absorption spectra studied. The spectra of U(VI) and U(V) ions are observed, together with new bands attributable to a charge transfer. It may be concluded that the blue complexes of uranium are type II composite-valence complexes for which the delocalization coefficient α can be calculated [fr

  1. Complex Solutions for Complex Needs: Towards Holistic and Collaborative Practice

    Science.gov (United States)

    Beadle, Sally

    2009-01-01

    While the need for holistic health and social service responses is increasingly being articulated in Australia, the discussion is not always matched by improvements in service delivery. This project looked at one service setting where youth workers were encouraged to take a holistic approach to their clients' often-complex needs. Interviews with…

  2. Spherically symmetric solution and a satisfactory energy-momentum complex

    International Nuclear Information System (INIS)

    Nashed, G.G.L.

    2005-01-01

    Mikhail et al. obtained two spherically symmetric solution in Moeller tetrad theory of gravitation. They calculated their energy content and obtained a strange value for the second solution, in spite that the associated metric of these solutions is the same (the Schwarzschild metric). We use another method given bu Gibbons and Hawking to calculate the energy content of these solutions. We also obtained a strange value of energy for the second solution. Studying the requirements of the satisfactory energy-momentum complex given by Moeller we find that the second solution which behaves as 1/√r does not transform as a four-vector under Lorentz transformation

  3. Complex structure of Kerr geometry and rotating 'photon rocket' solutions

    International Nuclear Information System (INIS)

    Burinskii, Alexander

    2003-01-01

    In the frame of the Kerr-Schild approach, we obtain a generalization of the Kerr solution to a nonstationary case corresponding to a rotating source moving with arbitrary acceleration. Similar to the Kerr solution, the solutions obtained have geodesic and shearfree principal null congruence. The current parameters of the solutions are determined by a complex retarded-time construction via a given complex worldline of source. The real part of the complex worldline defines the values of the boost and acceleration while the imaginary part controls the rotation. The acceleration of the source is accompanied by lightlike radiation along the principal null congruence. The solutions obtained generalize to the rotating case the known Kinnersley class of the 'photon rocket' solutions

  4. Phase Equilibria for Complex Polymer Solutions

    DEFF Research Database (Denmark)

    Lindvig, Thomas; Hestkjær, L. L.; Hansen, A. F.

    2002-01-01

    the content of organic solvents. This work presents an investigation of the three polymer models Entropic-FV (EFV). UNIFAC-FV (UFV) and GC-Flory (GCF) for their capability of predicting solvent activity coefficients in binary systems containing complex polymers. It is possible to obtain good predictions...... at finite concentrations and satisfactory predictions at infinite dilution, particularly with the EFV model. The investigation shows that EFV is the most robust and stable of the models, which indicates that it is the most well suited model for further development of methods for predicting the miscibility...

  5. Investigation of complexing of trivalent lanthanoids in aqueous nitrate solutions

    International Nuclear Information System (INIS)

    Kopyrin, A.A.; Proyaev, V.V.; Edinakova, V.

    1985-01-01

    Complexing of trivalent lanthanoids (Ce, Eu) with nitrate-ions in concentrated solutions of lithium and sodium nitrates has been studied in a wide range of ionic forces (1.0-7.0), using the extractional, densimetric and solubility methods. Nitrate complexes registered by the extraction and solubility methods mainly are of second sphere character. During rare earth extraction from concentrated nitrate solutions in the range of nitrate-ion concentrations <= 5 mol/l second sphere neutral nitrate complexes take part in distribution, at higher values of nitrate-ion concentration formation of intrasphere monoligand complexes of lanthanoids should be taken into account

  6. Modeling Complex Chemical Systems: Problems and Solutions

    Science.gov (United States)

    van Dijk, Jan

    2016-09-01

    Non-equilibrium plasmas in complex gas mixtures are at the heart of numerous contemporary technologies. They typically contain dozens to hundreds of species, involved in hundreds to thousands of reactions. Chemists and physicists have always been interested in what are now called chemical reduction techniques (CRT's). The idea of such CRT's is that they reduce the number of species that need to be considered explicitly without compromising the validity of the model. This is usually achieved on the basis of an analysis of the reaction time scales of the system under study, which identifies species that are in partial equilibrium after a given time span. The first such CRT that has been widely used in plasma physics was developed in the 1960's and resulted in the concept of effective ionization and recombination rates. It was later generalized to systems in which multiple levels are effected by transport. In recent years there has been a renewed interest in tools for chemical reduction and reaction pathway analysis. An example of the latter is the PumpKin tool. Another trend is that techniques that have previously been developed in other fields of science are adapted as to be able to handle the plasma state of matter. Examples are the Intrinsic Low Dimension Manifold (ILDM) method and its derivatives, which originate from combustion engineering, and the general-purpose Principle Component Analysis (PCA) technique. In this contribution we will provide an overview of the most common reduction techniques, then critically assess the pros and cons of the methods that have gained most popularity in recent years. Examples will be provided for plasmas in argon and carbon dioxide.

  7. Separation of compounds with multiple -OH groups from dilute aqueous solutions via complexation with organoboronate

    Energy Technology Data Exchange (ETDEWEB)

    Chow, Tina Kuo Fung [Univ. of California, Berkeley, CA (United States)

    1992-05-01

    The complexing extractant agent investigated in this work is 3-nitrophenylboronic acid (NPBA) in its anionic form (NPB). NPBA and Aliquat 336 (quaternary amine) is dissolved in 2-ethyl-l-hexanol, and the extractant is contacted with aq. NaOH. Solutes investigated were 1,2-propanediol, glycerol, fructose, sorbitol and lactic acid. Batch extraction experiments were performed at 25°C. Partition coefficients, distribution ratios and loadings are reported for varying concentrations of solute and NPB. All solutes complexed with NPB-, with all complexes containing only one NPB- per complex. The 1:1 complexation constants for the solutes glycerol, fructose and sorbitol follow trends similar to complexation with B(OH)4- (aq.), i.e. the complexation constants increase with increasing number of -OH groups available for complexation. Assumption of 1:1 complex is not valid for 1, 2-propanediol, which showed overloading (more than one mole of solute complexed to one mole NPB-) at higher concentrations. The -OH group on the NPB- which is left uncomplexed after one solute molecule had bound to the other two -OH groups may be responsible for the overloading. Overloading is also observed in extraction of tactic acid, but through a different mechanism. It was found that TOMA+ can extract lactic acid to an extent comparable to the uptake of lactic acid by NPB-. The complexation is probably through formation of an acid-base ion pair. Losses of NPBA into the aqueous phase could lead to problems, poor economics in industrial separation processes. One way of overcoming this problem would be to incorporate the NPBA onto a solid support.

  8. Complex chemistry of Np(V) in aqueous solutions

    International Nuclear Information System (INIS)

    Inoue, Yasushi

    1989-01-01

    Despite the importance of Np(V) in both the nuclear chemical engineering and the actinoid chemistry, little work has been performed on the complex chemistry of Np(V) in aqueous solutions, since Np(V) reacts less readily with various ligands. The author has directed his effort to understand the chemical behavior of Np(V) in aqueous solutions, especially the determination of the stability constants of Np(V) complexes with various ligands. A part of the results obtained so far is presented in the following order. (1) The synergistic extraction of Np(V) as a method for studying the complex chemistry of Np(V): TTA-MTOA(methyltrioctylammonium chloride), TTA-phen and TTA-TOPO. (2) The determination of the stability constants of Np(V) complexes with 22 organic- and 5 inorganic ligands by means of the solvent extraction. (3) The distribution of the chemical species of Np(V) in solutions under various conditions

  9. Solution structure of the luzopeptin-DNA complex

    International Nuclear Information System (INIS)

    Zhang, Xiaolu; Patel, D.J.

    1991-01-01

    The luzopeptin-d(C-A-T-G) complex (1 drug/duplex) has been generated in aqueous solution and its structure characterized by a combined application of two-dimensional NMR experiments and molecular dynamics calculations. Once equivalent of luzopeptin binds to the self-complementary tetranucleotide duplex with the 2-fold symmetry of the antitumor agent and the DNA oligomer retained on complex formation. The authors have assigned the exchangeable and nonexchangeable proton resonances of luzopeptin and the d(C-A-T-G) duplex in the complex and identified the intermolecular proton-proton NOEs that define the alignment of the antitumor agent at its binding site in duplex DNA. The analysis was greatly aided by a large number of intermolecular NOEs involving exchangeable protons on both the luzopeptin and the DNA in the complex. The formation of cis peptide bonds for luzopeptin in the complex results in an increased separation of the long sides of the rectangular cyclic depsipeptide backbone and reorients in the glycine amide proton so that it can form an intermolecular hydrogen bond with the 2-carbonyl of T3 in the complex. This observation explains, in part, the requirement for Watson-Crick A·T pairs to be sandwiched between the quinolines at the bisintercalation site in the luzopeptin-DNA complex. The NMR studies on the luzopeptin-d(C-A-T-G) complex unequivocally establish that antitumor agents can undergo conformational transitions on complex formation with DNA, and it is the conformation of the drug in the complex that should serve as the starting point for drug design studies. The above structural details on the solution structure of the luzopeptin-DNA complex also explain the sequence selectivity of luzopeptin for bisintercalation at d(C-A)·d(T-G) steps in the d(C-A-T-G) duplex in solution

  10. Supercharging Protein Complexes from Aqueous Solution Disrupts their Native Conformations

    Science.gov (United States)

    Sterling, Harry J.; Kintzer, Alexander F.; Feld, Geoffrey K.; Cassou, Catherine A.; Krantz, Bryan A.; Williams, Evan R.

    2012-02-01

    The effects of aqueous solution supercharging on the solution- and gas-phase structures of two protein complexes were investigated using traveling-wave ion mobility-mass spectrometry (TWIMS-MS). Low initial concentrations of m-nitrobenzyl alcohol ( m-NBA) in the electrospray ionization (ESI) solution can effectively increase the charge of concanavalin A dimers and tetramers, but at higher m-NBA concentrations, the increases in charge are accompanied by solution-phase dissociation of the dimers and up to a ~22% increase in the collision cross section (CCS) of the tetramers. With just 0.8% m-NBA added to the ESI solution of a ~630 kDa anthrax toxin octamer complex, the average charge is increased by only ~4% compared with the "native" complex, but it is sufficiently destabilized so that extensive gas-phase fragmentation occurs in the relatively high pressure regions of the TWIMS device. Anthrax toxin complexes exist in either a prechannel or a transmembrane channel state. With m-NBA, the prechannel state of the complex has the same CCS/charge ratio in the gas phase as the transmembrane channel state of the same complex formed without m-NBA, yet undergoes extensive dissociation, indicating that destabilization from supercharging occurs in the ESI droplet prior to ion formation and is not a result of Coulombic destabilization in the gas phase as a result of higher charging. These results demonstrate that the supercharging of large protein complexes is the result of conformational changes induced by the reagents in the ESI droplets, where enrichment of the supercharging reagent during droplet evaporation occurs.

  11. Behaviors of nitrato complexes of nitrosylruthenium in aqueous solutions

    Energy Technology Data Exchange (ETDEWEB)

    Sugimoto, S [Radia Industry Co. Ltd., Takasaki (Japan)

    1979-11-01

    Nitrato nitrosylruthenium complexes (RuNO(NO/sub 3/)sub(x)(H/sub 2/O)sub(5-x))sup((3-x)+) readily dissociate in aqueous solutions with decrease in pH and increase in electrical conductivity of the solutions. This study aimed to elucidate the behaviours of dissociation of the complexes with time. The change in the amount of undissociated complexes was determined with time. The results indicated that the dissociation was a multi-order reaction involving both protolysis and hydrolysis. The protolysis completed in relatively short period within (several tens of minutes), but it depended on the concentration of the complexes in the solution. The completion of the protolysis and the formation of the resulting dissociation products were observed by absorption spectrometry. The dissociation products, which were assumed as aquohydroxy complexes, underwent the successive step-wise dissociation for a prolonged period as revealed by pH measurements. The rate constants involved in the step-wise dissociation, process were obtained. The degree of dissociation and dissociation constant of the complexes were measured by conductometry.

  12. Behaviors of nitrato complexes of nitrosylruthenium in aqueous solutions

    International Nuclear Information System (INIS)

    Sugimoto, Senichi

    1979-01-01

    Nitrato nitrosylruthenium complexes [RuNO(NO 3 )sub(x)(H 2 O)sub(5-x)]sup((3-x)+) readily dissociate in aqueous solutions with decrease in pH and increase in electrical conductivity of the solutions. This study aimed to elucidate the behaviours of dissociation of the complexes with time. The change in the amount of undissociated complexes was determined with time. The results indicated that the dissociation was a multi-order reaction involving both protolysis and hydrolysis. The protolysis completed in relatively short period within (several tens of minutes), but it depended on the concentration of the complexes in the solution. The completion of the protolysis and the formation of the resulting dissociation products were observed by absorption spectrometry. The dissociation products, which were assumed as aquohydroxy complexes, underwent the successive step-wise dissociation for a prolonged period as revealed by pH measurements. The rate constants involved in the step-wise dissociation, process were obtained. The degree of dissociation and dissociation constant of the complexes were measured by conductometry. (author)

  13. SUBSTANTIATION OF SOLUTIONS PERTAINING TO COMPLEX PRODUCTION RECONSTRUCTION

    Directory of Open Access Journals (Sweden)

    V. Y. Gurinovich

    2011-01-01

    Full Text Available While taking an example of reconstruction and modernization of OJSC «Construction and Mounting Trust No.16, Novopolotsk» the paper substantiates solutions for complex production reconstruction. The production reconstruction is divided in three start-up facilities ensuring continuous finished-product output.

  14. Graphical Solution of the Monic Quadratic Equation with Complex Coefficients

    Science.gov (United States)

    Laine, A. D.

    2015-01-01

    There are many geometrical approaches to the solution of the quadratic equation with real coefficients. In this article it is shown that the monic quadratic equation with complex coefficients can also be solved graphically, by the intersection of two hyperbolas; one hyperbola being derived from the real part of the quadratic equation and one from…

  15. Electron-Poor Polar Intermetallics: Complex Structures, Novel Clusters, and Intriguing Bonding with Pronounced Electron Delocalization.

    Science.gov (United States)

    Lin, Qisheng; Miller, Gordon J

    2018-01-16

    complexity can be realized by small amounts of Li replacing Zn atoms in the parent binary compounds CaZn 2 , CaZn 3 , and CaZn 5 ; their phase formation and bonding schemes can be rationalized by Fermi surface-Brillouin zone interactions between nearly free-electron states. "Cation-rich", electron-poor polar intermetallics have emerged using rare earth metals as the electropositive ("cationic") component together metal/metalloid clusters that mimic the backbones of aromatic hydrocarbon molecules, which give evidence of extensive electronic delocalization and multicenter bonding. Thus, we can identify three distinct, valence electron-poor, polar intermetallic systems that have yielded unprecedented phases adopting novel structures containing complex clusters and intriguing bonding characteristics. In this Account, we summarize our recent specific progress in the developments of novel Au-rich BaAl 4 -type related structures, shown in the "gold-rich grid", lithiation-modulated Ca-Li-Zn phases stabilized by different bonding characteristics, and rare earth-rich polar intermetallics containing unprecedented hydrocarbon-like planar Co-Ge metal clusters and pronounced delocalized multicenter bonding. We will focus mainly on novel structural motifs, bonding analyses, and the role of valence electrons for phase stability.

  16. Complexation in two-component chlortetracycline-melanin solutions

    Science.gov (United States)

    Lapina, V. A.; Pershukevich, P. P.; Dontsov, A. E.; Bel'Kov, M. V.

    2008-01-01

    The spectra and kinetics of fluorescence of two-component solutions of the chlortetracycline (CHTC)-DOPA-melanin (melanin or ME) system in water have been investigated. The data obtained have been compared to similar data for solutions of CHTC-melanosome from bull eye (MB), which contains natural melanin, in K-phosphate buffer at pH 7.4. The overall results indicate the occurrence of complexation between molecules of CHTC and ME as they are being excited. The studies of complexation in the solution of CHTC-MB in the buffer are complicated by the formation of a CHTC-buffer complex. The effect of optical radiation in the range 330-750 nm on the CHTC-ME complex shows selectivity: the greatest change in the spectrum occurs when the wavelength of the exciting radiation coincides with the long-wavelength band maximum of the fluorescence excitation spectrum of the CHTC-ME complex in aqueous solution. In this range, CHTC and especially ME show high photochemical stability. The nature of the radiation effect on the studied compounds in the hard UV range (λ < 330 nm) differs greatly from that in the range 330-750 nm. It is apparently accompanied by significant photochemical transmutations of all system components. By comparing the characteristics of the CHTC-ME systems with those of the related drug doxycycline (DC-ME), the conclusion has been made that the chlorine atom plays a vital role in formation of the short-wavelength band in the fluorescence spectrum of the CHTC-ME complex.

  17. Comparative study on system requirements and success factors of telemedicine solutions in resource-poor settings

    OpenAIRE

    Dawson, Joanna Adobea

    2011-01-01

    Rationale: Attempts to successfully develop telemedicine solutions by specifying the require-ments and critical success factors of these solutions are on-going in sub-Saharan Africa (SSA) countries as a means of improving access to high-quality healthcare. European Space Agency (ESA) (Dario et al. 2005) have explored the challenges and benefits of telemedicine solutions in these regions in the domains of eGovernment such as billing and administrative data management to support the healthcare ...

  18. Complex formation in aqueous trimethylamine-N-oxide (TMAO) solutions.

    Science.gov (United States)

    Hunger, Johannes; Tielrooij, Klaas-Jan; Buchner, Richard; Bonn, Mischa; Bakker, Huib J

    2012-04-26

    We study aqueous solutions of the amphiphilic osmolyte trimethylamine-N-oxide (TMAO) using broadband dielectric spectroscopy and femtosecond mid-infrared spectroscopy. Both experiments provide strong evidence for distinctively slower rotation dynamics for water molecules interacting with the hydrophobic part of the TMAO molecules. Further, water is found to interact more strongly at the hydrophilic site of the TMAO molecules: we find evidence for the formation of stable, TMAO·2H2O and/or TMAO·3H2O complexes. While this coordination structure seems obvious, the lifetime of these complexes is found to be extraordinarily long (>50 ps). The existence of these long-lived complexes leads to pronounced parallel dipole correlations between water and TMAO, reflected in enhanced amplitudes in the dielectric spectra. The strong interaction between water and TMAO also results in a red-shifted band for the O-D stretching vibration of HDO molecules in an isotopically diluted aqueous TMAO solution. This O-D stretching vibration has a vibrational lifetime of 670 fs, which is significantly shorter than the lifetime of the O-D stretch vibration of bulk-like HDO molecules, presumably due to efficient coupling to vibrational modes of TMAO. The rotational dynamics of these O-D groups are slowed down dramatically, and are limited by the rotation of the whole complex, while the O-D vector oriented away from TMAO probably shows an accelerated reorientation.

  19. Obstacles and solutions to the generation and dissemination of scientific knowledge in poor countries

    Directory of Open Access Journals (Sweden)

    David L Nordstrom

    2012-10-01

    Full Text Available Andreeva recently discussed several “challenges for research in poor countries” (Andreeva, 2012. Below is a list of some of these challenges and my comments.1.For many public health studies in low- or middle-income countries, population surveys are the only affordable means of data collection.Population surveys are valuable sources of health information. For example, surveys have estimated the prevalence, severity, and treatment of mental disorders in various countries, including Ukraine (WHO, 2004. But population surveys can be very expensive, so alternative approaches to data collection should not be overlooked. Some other methods are case-control studies, ecologic studies, and qualitative research designs such as focus groups. A case-control design was used by Donetsk State Medical University to investigate contraceptive practices and factors behind contraceptive preferences of Ukrainian women (Mogilevkina, 2003. For a case control study of diphtheria vaccine efficacy in Ukraine, demographic and vaccination data were gathered from health center records (Tsu, 2000. Focus group methods were used by the Ukraine Institute for Public Health Policy and others to investigate the obstacles to antiretroviral therapy perceived by HIV-infected injection drug users (Mimiaga, 2010 and in a separate study on the topics of everyday understanding of health and the factors influencing it (Abbott, 2006.2.Another challenge faced by survey scientists is related to the validity of self-reported data.Validity is central to all research. According to Bonita et al (2006, page 57, “A study is valid if its results correspond to the truth.” Self-reports can be satisfactory data sources if investigators take sufficient care in their design and use (Schaeffer, 2003. For example, before conducting health surveys in low and middle-income countries with questionnaires that were developed for use in high-income countries, researchers may first want to use focus group

  20. CHEMICAL ABUNDANCES IN NGC 5053: A VERY METAL-POOR AND DYNAMICALLY COMPLEX GLOBULAR CLUSTER

    Energy Technology Data Exchange (ETDEWEB)

    Boberg, Owen M.; Friel, Eileen D.; Vesperini, Enrico [Astronomy Department, Indiana University, Bloomington, IN 47405 (United States)

    2015-05-10

    NGC 5053 provides a rich environment to test our understanding of the complex evolution of globular clusters (GCs). Recent studies have found that this cluster has interesting morphological features beyond the typical spherical distribution of GCs, suggesting that external tidal effects have played an important role in its evolution and current properties. Additionally, simulations have shown that NGC 5053 could be a likely candidate to belong to the Sagittarius dwarf galaxy (Sgr dSph) stream. Using the Wisconsin–Indiana–Yale–NOAO–Hydra multi-object spectrograph, we have collected high quality (signal-to-noise ratio ∼ 75–90), medium-resolution spectra for red giant branch stars in NGC 5053. Using these spectra we have measured the Fe, Ca, Ti, Ni, Ba, Na, and O abundances in the cluster. We measure an average cluster [Fe/H] abundance of −2.45 with a standard deviation of 0.04 dex, making NGC 5053 one of the most metal-poor GCs in the Milky Way (MW). The [Ca/Fe], [Ti/Fe], and [Ba/Fe] we measure are consistent with the abundances of MW halo stars at a similar metallicity, with alpha-enhanced ratios and slightly depleted [Ba/Fe]. The Na and O abundances show the Na–O anti-correlation found in most GCs. From our abundance analysis it appears that NGC 5053 is at least chemically similar to other GCs found in the MW. This does not, however, rule out NGC 5053 being associated with the Sgr dSph stream.

  1. Chemical Abundances in NGC 5053: A Very Metal-poor and Dynamically Complex Globular Cluster

    Science.gov (United States)

    Boberg, Owen M.; Friel, Eileen D.; Vesperini, Enrico

    2015-05-01

    NGC 5053 provides a rich environment to test our understanding of the complex evolution of globular clusters (GCs). Recent studies have found that this cluster has interesting morphological features beyond the typical spherical distribution of GCs, suggesting that external tidal effects have played an important role in its evolution and current properties. Additionally, simulations have shown that NGC 5053 could be a likely candidate to belong to the Sagittarius dwarf galaxy (Sgr dSph) stream. Using the Wisconsin-Indiana-Yale-NOAO-Hydra multi-object spectrograph, we have collected high quality (signal-to-noise ratio ˜ 75-90), medium-resolution spectra for red giant branch stars in NGC 5053. Using these spectra we have measured the Fe, Ca, Ti, Ni, Ba, Na, and O abundances in the cluster. We measure an average cluster [Fe/H] abundance of -2.45 with a standard deviation of 0.04 dex, making NGC 5053 one of the most metal-poor GCs in the Milky Way (MW). The [Ca/Fe], [Ti/Fe], and [Ba/Fe] we measure are consistent with the abundances of MW halo stars at a similar metallicity, with alpha-enhanced ratios and slightly depleted [Ba/Fe]. The Na and O abundances show the Na-O anti-correlation found in most GCs. From our abundance analysis it appears that NGC 5053 is at least chemically similar to other GCs found in the MW. This does not, however, rule out NGC 5053 being associated with the Sgr dSph stream.

  2. Removing barriers to women entrepreneurs’ engagement in decentralized sustainable energy solutions for the poor

    Directory of Open Access Journals (Sweden)

    Yannick Glemarec

    2016-01-01

    Full Text Available  Rapidly falling renewable technology costs and new business models mean that decentralized energy solutions hold great promise to accelerate universal sustainable energy access. Across developing countries, women are typically the primary household energy managers. Close to their customers, women entrepreneurs have the potential to lower customer acquisition and servicing costs and drive these new decentralized solutions. However, they remain under-represented in the industry. This paper attempts to understand the root causes of this gender gap. It formulates the research hypothesis that market transformation policies intended to reduce investment risks to accelerate energy access may not benefit men and women entrepreneurs equally because of the existing structural barriers that women face. To test this hypothesis, the paper conducts a gender sensitive investment barrier and risk analysis, overlaid onto an existing gender neutral taxonomy of investment barriers and risks for decentralized sustainable energy solutions. A key finding is that for women entrepreneurs, existing structural impediments to gender equality translate into additional investment barriers as well as increased likelihood of occurrence and severity of the financial impact of generic investment risks. The paper offers an illustrative theory of change to facilitate a dialogue on the specific interventions needed to address these gender differentiated risks locally. It concludes that market transformation efforts for universal sustainable energy access must include targeted policy measures to ensure equal benefits to men and women entrepreneurs, and optimize the use of public resources to catalyze private investment and reduce poverty.

  3. Derivative spectrophotometry applied to solutions of complex composition

    International Nuclear Information System (INIS)

    Perfil'ev, V.A.

    1986-01-01

    The authors consider not only the basic principles of derivative spectrophotometry but also survey the data on its use in research on the properties of materials, the compositions of compounds, and the structures of complex chemical systems. Recording methods by which derivative spectra can be generated include descriptions of electronic differentiation, computer spectrum differentiation, wavelength modulation, and the two-way derivative method. A section on the advantages of derivative spectrophotometry presents a discussion on features enabling one to determine various substances from their characteristic absorption spectra without performing complicated operations to isolate or separate the components. Other topics include research on the structures of substances and metal-ion complexing in solutions, derivative spectrophotometry in gas analysis, gas determination, and determining organic and compounds

  4. Complex sulphide-barite ore leaching in ferric chloride solution

    Directory of Open Access Journals (Sweden)

    Miroslav Sokić

    2016-06-01

    Full Text Available The results of research on the leaching process of complex sulphide-barite ore were presented in this paper. The leaching process was carried out in a laboratory autoclave by ferric chloride solution. Considering that those minerals are represented in complex structural-textural relationships, it is not possible to extract lead, zinc and copper minerals from ore by flotation methods. The obtained results confirmed possibility of the ore processing directly, by chemical methods. The effect of temperature, time and oxygen partial pressure on the lead, zinc and copper dissolution was studied. The maximal leaching degree was achieved at 100 °C and amount of 91.5 % for Pb, 96.1 % for Zn and 60.7 % for Cu. Leaching at temperatures above 100 °C is impractical.

  5. Solution of problems of automation of elevator complex

    Directory of Open Access Journals (Sweden)

    V. S. Kudryashov

    2018-01-01

    Full Text Available The article is devoted to the solution of automation tasks in the development of the operator's workstation (AWP for controlling the elevator with a capacity of 280 tons per hour as part of the work of LLC "Intelligent Automation Complexes". In the existing elevator complexes, only grain transportation is provided (there are no control systems with automatic grain drying with high accuracy of humidity measurement, automatic generation of grain transportation routes is not provided (for each route, a technical task is required and changes to the control program of the system are required. At the same time, more precise regulation of the flow of grain flows is required (the automatic latches used have only the "open / close" positions. The goal of elevator automation is: to reduce the time of equipment downturn by tracking the operating time of the equipment, the number of accidents and informing the operator about equipment that is susceptible to failure; reduction of the time for setting up and servicing the elevator; improvement of product quality; a decrease in the percentage of rejects, as well as a decrease in the influence of the human factor on the process. The paper provides a brief description of the proposed gate valve control algorithms, the auto-building of the grain drying route, the filtering of the grain moisture readings and the fragments of the operator's workstation program (in indusoft web studio for controlling the elevator complex. The proposed solutions allow: to reduce the time of equipment downtime by 20% and the total service time of the complex; weed out the undried grain for ridding in automatic mode for repeated drying; to improve the quality of products through automatic control of grain overheating; to reduce the production waste by 3%, and also to reduce the influence of the human factor on the process of grain transportation and drying.

  6. Managing the diabetic foot in resource-poor settings: challenges and solutions

    Directory of Open Access Journals (Sweden)

    Abbas ZG

    2017-10-01

    Full Text Available Zulfiqarali G Abbas1,2 1Department of Internal Medicine, Muhimbili University of Health and Allied Sciences, Dar es Salaam, Tanzania; 2Department of Internal Medicine, Abbas Medical Centre, Dar es Salaam, Tanzania Abstract: Diabetes mellitus is one of the most common noncommunicable diseases globally. In Africa, rates of diabetes are increasing, so there is a parallel increase of foot complications. Peripheral neuropathy is the main risk factor for foot ulceration in people with diabetes in developing nations, but peripheral arterial disease is also increasing in number owing to the change in lifestyle and increasing urbanization. Ulceration arising from peripheral neuropathy, peripheral arterial disease, and trauma are highly susceptible to secondary infection and gangrene, and are hence associated with increased morbidity and mortality. Government funding is very limited in many developing countries, and diabetes and its complications impose a heavy burden on health services. In particular, the outcomes of foot complications are often poor, and this is the result of various factors including lack of awareness of the need for foot care among patients, relatives, and health care providers; relatively few professionals with an interest in the diabetic foot and with the training to provide specialist treatment; nonexistent podiatry services; long distances for patients to travel to the clinic; delays among patients in seeking medical care, or the late referral of patients for specialist opinion; and lack of the awareness of the importance of a team approach to care, and the lack of training programs for health care professionals. Many of these can, however, potentially be tackled without exorbitant spending of financial resources. Cost-effective educational efforts should be targeted at both health care workers and patients. These include implementation of sustainable training programs for health care professionals with a special interest in foot

  7. Oosorption in response to poor food: complexity in the trade-off between reproduction and survival

    Science.gov (United States)

    Moore, Patricia J; Attisano, Alfredo

    2011-01-01

    Plasticity in reproductive physiology is one avenue by which environmental signals, such as poor quality food, can be coordinated with adaptive responses. Insects have the ability to resorb oocytes that are not oviposited. Oosorption is proposed to be an adaptive mechanism to optimize fitness in hostile environments, recouping resources that might otherwise be lost, and reinvesting them into future reproductive potential. We tested the hypothesis that oosorption is an evolved mechanism by which females can reallocate resources from current reproductive effort to survival and future reproduction, when conditions for reproduction are poor, by examining the reproductive physiology and life-history outcome under poor quality food in populations of the milkweed bug (Oncopeltus fasciatus) that have adapted to live on sunflower seed. Females fed a diet of pumpkin seeds, known to be a poor host food, had higher levels of ovarian apoptosis (oosorption), lower reproductive output, but no reduction in life span under poor nutrition, as predicted under the oosorption hypothesis. However, the schedule of reproduction was surprising given the “wait to reproduce” assumption of oosorption as early fecundity was unaffected. PMID:22393481

  8. Urban Pro-Poor Registrations: Complex-Simple the Overstrand Project

    African Journals Online (AJOL)

    Low-cost housing which has been disposed of by private owners is extremely difficult for conveyancers to register. The law as it stands is often incapable of giving effect to the business transactions of the poor, thereby creating insecurity of tenure nationwide. The Land Titles Adjustment Act 111 of 1993 is currently the only ...

  9. Separation of compounds with multiple -OH groups from dilute aqueous solutions via complexation with organoboronate. [1,2-propanediol

    Energy Technology Data Exchange (ETDEWEB)

    Chow, Tina Kuo Fung.

    1992-05-01

    The complexing extractant agent investigated in this work is 3-nitrophenylboronic acid (NPBA) in its anionic form (NPB). NPBA and Aliquat 336 (quaternary amine) is dissolved in 2-ethyl-l-hexanol, and the extractant is contacted with aq. NaOH. Solutes investigated were 1,2-propanediol, glycerol, fructose, sorbitol and lactic acid. Batch extraction experiments were performed at 25{degree}C. Partition coefficients, distribution ratios and loadings are reported for varying concentrations of solute and NPB. All solutes complexed with NPB{sup {minus}}, with all complexes containing only one NPB{sup {minus}} per complex. The 1:1 complexation constants for the solutes glycerol, fructose and sorbitol follow trends similar to complexation with B(OH){sub 4}{sup {minus}} (aq.), i.e. the complexation constants increase with increasing number of {minus}OH groups available for complexation. Assumption of 1:1 complex is not valid for 1, 2-propanediol, which showed overloading (more than one mole of solute complexed to one mole NPB{sup {minus}}) at higher concentrations. The {minus}OH group on the NPB{sup {minus}} which is left uncomplexed after one solute molecule had bound to the other two {minus}OH groups may be responsible for the overloading. Overloading is also observed in extraction of tactic acid, but through a different mechanism. It was found that TOMA{sup +} can extract lactic acid to an extent comparable to the uptake of lactic acid by NPB{sup {minus}}. The complexation is probably through formation of an acid-base ion pair. Losses of NPBA into the aqueous phase could lead to problems, poor economics in industrial separation processes. One way of overcoming this problem would be to incorporate the NPBA onto a solid support.

  10. Generation of new solutions of the stationary axisymmetric Einstein equations by a double complex function method

    International Nuclear Information System (INIS)

    Zhong, Z.

    1985-01-01

    A new approach to the solution of certain differential equations, the double complex function method, is developed, combining ordinary complex numbers and hyperbolic complex numbers. This method is applied to the theory of stationary axisymmetric Einstein equations in general relativity. A family of exact double solutions, double transformation groups, and n-soliton double solutions are obtained

  11. Leaching of irradiated polymers: solution characterization and actinides complexation

    International Nuclear Information System (INIS)

    Fromentin, Elodie

    2017-01-01

    The first aim of this work is to study the degradation of an industrial poly-esterurethane (PURm) by radio-oxidation and then by leaching in an alkaline aqueous solution. The second aim is to measure the complexing power of hydro-soluble degradation products (HDP) with actinides. To reach these goals, PURm was first characterized and then radio-oxidized at room temperature with γ rays up to 10 MGy. Second, it was leached at pH 13.3 at different temperature values. Numerous analytical techniques were employed in order to characterize the HDP which were obtained. Europium(III) was used as an analogue of actinides(III) and the behavior of HDP with europium(III) was analyzed by time-resolved luminescence spectroscopy (TRLS). Whatever the dose received by PURm, adipic acid and butane-1,4-diol are the two main HDP in leachates. The leaching data acquired at 40 and 60 C, on the 1 MGy radio-oxidized PURm, correlate with the model given by Yoon et al. (1997). However, the data at room temperature (22 C in average) are not in agreement with the model. Nevertheless, it seems that the plateau which was reached at long-term leaching is the same whatever the temperature used in this study. The results allow to conclude that the predominant mechanism occurring during the leaching of unirradiated and radio-oxidized PURm in an alkaline medium is the hydrolysis of the soft segments ester groups. The complexation of europium(III) by HDP in alkaline medium was demonstrated. The measurement of the complexing power and the identification of ligands was achieved under certain conditions. (author) [fr

  12. A proposed reductionist solution to address the methodological challenges of inconsistent reflexology maps and poor experimental controls in reflexology research: a discussion paper.

    Science.gov (United States)

    Jones, Jenny; Thomson, Patricia; Lauder, William; Leslie, Stephen J

    2013-03-01

    Reflexology is a complex massage intervention, based on the concept that specific areas of the feet (reflex points) correspond to individual internal organs within the body. Reflexologists trained in the popular Ingham reflexology method claim that massage to these points, using massage techniques unique to reflexology, stimulates an increase in blood supply to the corresponding organ. Reflexology researchers face two key methodological challenges that need to be addressed if a specific treatment-related hemodynamic effect is to be scientifically demonstrated. The first is the problem of inconsistent reflexology foot maps; the second is the issue of poor experimental controls. This article proposes a potential experimental solution that we believe can address both methodological challenges and in doing so, allow any specific hemodynamic treatment effect unique to reflexology to experimentally reveal itself.

  13. Urban Pro-Poor Registrations: Complex-Simple the Overstrand Project

    Directory of Open Access Journals (Sweden)

    L Downie

    2011-06-01

    Full Text Available Low-cost housing which has been disposed of by private owners is extremely difficult for conveyancers to register. The law as it stands is often incapable of giving effect to the business transactions of the poor, thereby creating insecurity of tenure nationwide. The Land Titles Adjustment Act 111 of 1993 is currently the only legislation capable of dealing with this impasse. The Overstrand Municipality has provided the staff and infrastructure to run a pilot project under the Act, for which it is awaiting confirmation from the Department of Rural Development and Land Reform. This article discusses the legal issues arising and the potential of such an initiative to provide consumer protection for the low-literate and other vulnerable holders of rights.

  14. Cleaved thioredoxin fusion protein enables the crystallization of poorly soluble ERα in complex with synthetic ligands

    International Nuclear Information System (INIS)

    Cura, Vincent; Gangloff, Monique; Eiler, Sylvia; Moras, Dino; Ruff, Marc

    2007-01-01

    A new crystallization strategy: the presence of cleaved thioredoxin fusion is critical for crystallization of the estrogen nuclear receptor ligand binding domain in complex with synthetic ligands. This novel technique should be regarded as an interesting alternative for crystallization of difficult proteins. The ligand-binding domain (LBD) of human oestrogen receptor α was produced in Escherichia coli as a cleavable thioredoxin (Trx) fusion in order to improve solubility. Crystallization trials with either cleaved and purified LBD or with the purified fusion protein both failed to produce crystals. In another attempt, Trx was not removed from the LBD after endoproteolytic cleavage and its presence promoted nucleation and subsequent crystal growth, which allowed the structure determination of two different LBD–ligand–coactivator peptide complexes at 2.3 Å resolution. This technique is likely to be applicable to other low-solubility proteins

  15. Thermodynamics of Highly Supersaturated Aqueous Solutions of Poorly Water-Soluble Drugs-Impact of a Second Drug on the Solution Phase Behavior and Implications for Combination Products.

    Science.gov (United States)

    Trasi, Niraj S; Taylor, Lynne S

    2015-08-01

    There is increasing interest in formulating combination products that contain two or more drugs. Furthermore, it is also common for different drug products to be taken simultaneously. This raises the possibility of interactions between different drugs that may impact formulation performance. For poorly water-soluble compounds, the supersaturation behavior may be a critical factor in determining the extent of oral absorption. The goal of the current study was to evaluate the maximum achievable supersaturation for several poorly water-soluble compounds alone, and in combination. Model compounds included ritonavir, lopinavir, paclitaxel, felodipine, and diclofenac. The "amorphous solubility" for the pure drugs was determined using different techniques and the change in this solubility was then measured in the presence of differing amounts of a second drug. The results showed that "amorphous solubility" of each component in aqueous solution is substantially decreased by the second component, as long as the two drugs are miscible in the amorphous state. A simple thermodynamic model could be used to predict the changes in solubility as a function of composition. This information is of great value when developing co-amorphous or other supersaturating formulations and should contribute to a broader understanding of drug-drug physicochemical interactions in in vitro assays as well as in the gastrointestinal tract. © 2015 Wiley Periodicals, Inc. and the American Pharmacists Association.

  16. Role of Molecular Interactions for Synergistic Precipitation Inhibition of Poorly Soluble Drug in Supersaturated Drug-Polymer-Polymer Ternary Solution.

    Science.gov (United States)

    Prasad, Dev; Chauhan, Harsh; Atef, Eman

    2016-03-07

    We are reporting a synergistic effect of combined Eudragit E100 and PVP K90 in precipitation inhibition of indomethacin (IND) in solutions at low polymer concentration, a phenomenon that has significant implications on the usefulness of developing novel ternary solid dispersion of poorly soluble drugs. The IND supersaturation was created by cosolvent technique, and the precipitation studies were performed in the absence and the presence of individual and combined PVP K90 and Eudragit E100. The studies were also done with PEG 8000 as a noninteracting control polymer. A continuous UV recording of the IND absorption was used to observe changes in the drug concentration over time. The polymorphic form and morphology of precipitated IND were characterized by Raman spectroscopy and scanning electron microscopy. The change in the chemical shift in solution (1)H NMR was used as novel approach to probe IND-polymer interactions. Molecular modeling was used for calculating binding energy between IND-polymer as another indication of IND-polymer interaction. Spontaneous IND precipitation was observed in the absence of polymers. Eudragit E100 showed significant inhibitory effect on nuclei formation due to stronger interaction as reflected in higher binding energy and greater change in chemical shift by NMR. PVP K90 led to significant crystal growth inhibition due to adsorption on growing IND crystals as confirmed by modified crystal habit of precipitate in the presence of PVP K90. Combination of polymers resulted in a synergistic precipitation inhibition and extended supersaturation. The NMR confirmed interaction between IND-Eudragit E100 and IND-PVP K90 in solution. The combination of polymers showed similar peak shift albeit using lower polymer concentration indicating stronger interactions. The results established the significant synergistic precipitation inhibition effect upon combining Eudragit E100 and PVP K90 due to drug-polymer interaction.

  17. Tuberculosis in ageing: high rates, complex diagnosis and poor clinical outcomes.

    Science.gov (United States)

    Cruz-Hervert, Luis Pablo; García-García, Lourdes; Ferreyra-Reyes, Leticia; Bobadilla-del-Valle, Miriam; Cano-Arellano, Bulmaro; Canizales-Quintero, Sergio; Ferreira-Guerrero, Elizabeth; Báez-Saldaña, Renata; Téllez-Vázquez, Norma; Nava-Mercado, Ariadna; Juárez-Sandino, Luis; Delgado-Sánchez, Guadalupe; Fuentes-Leyra, César Alejandro; Montero-Campos, Rogelio; Martínez-Gamboa, Rosa Areli; Small, Peter M; Sifuentes-Osornio, José; Ponce-de-León, Alfredo

    2012-07-01

    worldwide, the frequency of tuberculosis among older people almost triples that observed among young adults. to describe clinical and epidemiological consequences of pulmonary tuberculosis among older people. we screened persons with a cough lasting more than 2 weeks in Southern Mexico from March 1995 to February 2007. We collected clinical and mycobacteriological information (isolation, identification, drug-susceptibility testing and IS6110-based genotyping and spoligotyping) from individuals with bacteriologically confirmed pulmonary tuberculosis. Patients were treated in accordance with official norms and followed to ascertain treatment outcomes, retreatment, and vital status. eight hundred ninety-three tuberculosis patients were older than 15 years of age; of these, 147 (16.5%) were 65 years of age or older. Individuals ≥ 65 years had significantly higher rates of recently transmitted and reactivated tuberculosis. Older age was associated with treatment failure (OR=5.37; 95% CI: 1.06-27.23; P=0.042), and death due to tuberculosis (HR=3.52; 95% CI: 1.78-6.96; Ptuberculosis is not solely due to the reactivation of latent disease. Untimely and difficult diagnosis and a higher risk of poor outcomes even after treatment completion emphasise the need for specific strategies for this vulnerable group.

  18. A direct algebraic method applied to obtain complex solutions of some nonlinear partial differential equations

    International Nuclear Information System (INIS)

    Zhang Huiqun

    2009-01-01

    By using some exact solutions of an auxiliary ordinary differential equation, a direct algebraic method is described to construct the exact complex solutions for nonlinear partial differential equations. The method is implemented for the NLS equation, a new Hamiltonian amplitude equation, the coupled Schrodinger-KdV equations and the Hirota-Maccari equations. New exact complex solutions are obtained.

  19. Quantitative Multiplex Immunohistochemistry Reveals Myeloid-Inflamed Tumor-Immune Complexity Associated with Poor Prognosis

    Directory of Open Access Journals (Sweden)

    Takahiro Tsujikawa

    2017-04-01

    Full Text Available Here, we describe a multiplexed immunohistochemical platform with computational image processing workflows, including image cytometry, enabling simultaneous evaluation of 12 biomarkers in one formalin-fixed paraffin-embedded tissue section. To validate this platform, we used tissue microarrays containing 38 archival head and neck squamous cell carcinomas and revealed differential immune profiles based on lymphoid and myeloid cell densities, correlating with human papilloma virus status and prognosis. Based on these results, we investigated 24 pancreatic ductal adenocarcinomas from patients who received neoadjuvant GVAX vaccination and revealed that response to therapy correlated with degree of mono-myelocytic cell density and percentages of CD8+ T cells expressing T cell exhaustion markers. These data highlight the utility of in situ immune monitoring for patient stratification and provide digital image processing pipelines to the community for examining immune complexity in precious tissue sections, where phenotype and tissue architecture are preserved to improve biomarker discovery and assessment.

  20. Contribution to the study of pseudohalides complexes of tervalent, lanthanides and actinides in solution

    International Nuclear Information System (INIS)

    Cuillerdier, Christine.

    1981-10-01

    Some complexes formed with halides or pseudohalides (iodide, cyanide, azide and thiocyanate) and tervalent lanthanides and actinides have been studied in solution. Methods like solvent extraction, polarography have been used to measure inner plus outer sphere complexation and spectroscopic methods have been chosen to study inner sphere complexes only. It has been found that inner sphere complexe of americium and neodymium with cyanide exist in aqueous solutions. Tervalent actinides form stronger inner sphere complexes with azide than lanthanide in solution. Thiocyanate complexes appear to be inner sphere and N-bonded [fr

  1. Complexing in aqueous solutions of rare earth n-aminobenzoates

    International Nuclear Information System (INIS)

    Efremova, G.I.; Buchkova, R.T.; Lapitskaya, A.V.; Pirkes, S.B.

    1977-01-01

    Complexing in the system ''ion of a rare-earth metal - n-aminobenzoic acid'' has been investigated by the pH-metric method in the pH range of 3.5-5.5. In the La-Eu series, the stability of n-aminobenzoate complexes increases and attains the maximum value in the complex Eu (lg Ksub(st)=2.66). In the Gd-Lu series the stability of the complex particles decreases monotonically

  2. Amodified probabilistic genetic algorithm for the solution of complex constrained optimization problems

    OpenAIRE

    Vorozheikin, A.; Gonchar, T.; Panfilov, I.; Sopov, E.; Sopov, S.

    2009-01-01

    A new algorithm for the solution of complex constrained optimization problems based on the probabilistic genetic algorithm with optimal solution prediction is proposed. The efficiency investigation results in comparison with standard genetic algorithm are presented.

  3. Forward osmosis for oily wastewater reclamation: Multi-charged oxalic acid complexes as draw solutes

    KAUST Repository

    Ge, Qingchun

    2017-06-11

    Forward osmosis (FO) has demonstrated its merits in hybrid FO seawater desalination. However, FO may have a potential for other applications if suitable draw solutes are available. In this study, a series of novel draw solutes based on oxalic acid (OA)-transitional metal complexes are presented. Influential factors of FO performance have been systematically investigated by varying the transitional metals, cations of the complex draw solutes as well as the experimental conditions. Compared to NaCl and other recently synthesized draw solutes, the OA complexes show superior FO performance in terms of high water fluxes up to 27.5 and 89.1 LMH under the respective FO and PRO (pressure retarded osmosis) modes, both with negligible reverse solute fluxes. The features of octahedral geometry, abundant hydrophilic groups and ionic species are crucial for the OA complexes as appropriate draw solutes with satisfactory FO performance. Among the synthesized OA complexes, the ammonium salt of chromic complex (NH4-Cr-OA) outperforms others due to the presence of more ionic species in its complex system. NH4-Cr-OA also performs better than the typical NaCl draw solute in FO oily wastewater treatment with higher water recovery and negligible reverse fluxes. Dilute solutions of OA complexes have been reconcentrated through membrane distillation (MD) and reused to new round of FO processes. The OA complexes have demonstrated their suitability and superiority as a novel class of draw solutes for the FO process in this study.

  4. Ligand Rearrangements of Organometallic Complexes inSolution

    Energy Technology Data Exchange (ETDEWEB)

    Shanoski, Jennifer E. [Univ. of California, Berkeley, CA (United States)

    2006-01-01

    Many chemical reactions utilize organometallic complexes as catalysts. These complexes find use in reactions as varied as bond activation, polymerization, and isomerization. This thesis outlines the construction of a new ultrafast laser system with an emphasis on the generation of tunable mid-infrared pulses, data collection, and data analysis.

  5. 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

  6. NMR studies of structures of lanthanide dicarboxylate complexes in solution

    International Nuclear Information System (INIS)

    Choppin, G.R.; Kullberg, L.

    PMR pand 13 C shift data were measured for complexes of Pr(III), Eu(III) and Yb(III) with ethylene 1,2-dioxydiacetate (EDODA), ethylene 1,2-dithiodiacetate (EDSDA), and ethylene, 1,2-diaminodiacetate (EDDA). Solubility problems limited analysis of the EDSDA and EDDA data to qualitative evaluation. In the EDSDA complexes, the data indicate that the sulfur atoms do not participate in bonding to the lanthanide cations. Moreover, both carboxylate groups seem to bind Pr and Eu while Yb interacts with only a single carboxylate group. The EDDA complexes are tetradentate with long lived (NMR scale) Ln-N bonds. Shift theory allowed more quantitative analysis of the EDODA complexes. They are tetradentate with a puckered chelate ring and Ln-O(ether) distances of 2.3 A

  7. Decontamination of soils by irrigation with solutions containing complexing agents

    International Nuclear Information System (INIS)

    Pimpl, M.; Schuettelkopf, H.

    1982-01-01

    Experiments in laboratory scale were performed to increase the mobility of Pu, Am, and Cm in soil. Soil columns of 30 cm in diameter and 40 cm of length were contaminated on the surface with 5 μCi of Pu, Am, and Cm, applied as nitrates. By irrigation with 0.1 M DTPA-solution the actinides were mobilized and migrated with the irrigation solution through the columns. The migration velocity was measured and compared to the calculated one. Conclusions for the application of this procedure in field experiments are drawn. (author)

  8. Graphical Representation of Complex Solutions of the Quadratic Equation in the "xy" Plane

    Science.gov (United States)

    McDonald, Todd

    2006-01-01

    This paper presents a visual representation of complex solutions of quadratic equations in the xy plane. Rather than moving to the complex plane, students are able to experience a geometric interpretation of the solutions in the xy plane. I am also working on these types of representations with higher order polynomials with some success.

  9. Copper complexation by tannic acid in aqueous solution

    NARCIS (Netherlands)

    Kraal, P.; Jansen, B.; Nierop, K.G.J.; Verstraten, J.M.

    2006-01-01

    The speciation of titrated copper in a dissolved tannic acid (TA) solution with an initial concentration of 4 mmol organic carbon ((OC)/l was investigated in a nine-step titration experiment (Cu/oC molar ratio = 0.0030-0.0567). We differentiated between soluble and insoluble Cu species by 0.45 mu m

  10. Chemical solution deposition techniques for epitaxial growth of complex oxides

    NARCIS (Netherlands)

    ten Elshof, Johan E.; Koster, G.; Huijben, Mark; Rijnders, G.

    2015-01-01

    The chemical solution deposition (CSD) process is a wet-chemical process that is employed to fabricate a wide variety of amorphous and crystalline oxide thin films. This chapter describes the typical steps in a CSD process and their influence on the final microstructure and properties of films, and

  11. Oxalic acid complexes: Promising draw solutes for forward osmosis (FO) in protein enrichment

    KAUST Repository

    Ge, Qingchun; Chung, Neal Tai-Shung

    2015-01-01

    Highly soluble oxalic acid complexes (OACs) were synthesized through a one-pot reaction. The OACs exhibit excellent performance as draw solutes in FO processes with high water fluxes and negligible reverse solute fluxes. Efficient protein enrichment was achieved. The diluted OACs can be recycled via nanofiltration and are promising as draw solutes.

  12. Solution of generalized shifted linear systems with complex symmetric matrices

    International Nuclear Information System (INIS)

    Sogabe, Tomohiro; Hoshi, Takeo; Zhang, Shao-Liang; Fujiwara, Takeo

    2012-01-01

    We develop the shifted COCG method [R. Takayama, T. Hoshi, T. Sogabe, S.-L. Zhang, T. Fujiwara, Linear algebraic calculation of Green’s function for large-scale electronic structure theory, Phys. Rev. B 73 (165108) (2006) 1–9] and the shifted WQMR method [T. Sogabe, T. Hoshi, S.-L. Zhang, T. Fujiwara, On a weighted quasi-residual minimization strategy of the QMR method for solving complex symmetric shifted linear systems, Electron. Trans. Numer. Anal. 31 (2008) 126–140] for solving generalized shifted linear systems with complex symmetric matrices that arise from the electronic structure theory. The complex symmetric Lanczos process with a suitable bilinear form plays an important role in the development of the methods. The numerical examples indicate that the methods are highly attractive when the inner linear systems can efficiently be solved.

  13. Method of stripping plutonium from tributyl phosphate solution which contains dibutyl phosphate-plutonium stable complexes

    International Nuclear Information System (INIS)

    Ochsenfeld, W.; Schmieder, H.

    1976-01-01

    Fast breeder fuel elements which have been highly burnt-up are reprocessed by extracting uranium and plutonium into an organic solution containing tributyl phosphate. The tributyl phosphate degenerates at least partially into dibutyl phosphate and monobutyl phosphate, which form stable complexes with tetravalent plutonium in the organic solution. This tetravalent plutonium is released from its complexed state and stripped into aqueous phase by contacting the organic solution with an aqueous phase containing tetravalent uranium. 6 claims, 1 drawing figure

  14. Complexities of coalition building: leaders' successes, strategies, struggles, and solutions.

    Science.gov (United States)

    Mizrahi, T; Rosenthal, B B

    2001-01-01

    Government and private funding initiatives are promoting coalitions, collaborations, and other interorganizational approaches to address complex community, social services, and health issues. Social work organizers and administrators are increasingly leading coalitions themselves or representing their organizations in collaborative planning and problem solving, often without understanding how to manage the complexities involved in interorganizational relationships. This article reports on aspects of a larger quantitative and qualitative research project that studied coalition dynamics, operations, and outcomes. Coalition leaders interviewed defined success in multiple ways. Competent leadership was the factor most often identified with coalition success.

  15. Electron transfer reactions of metal complexes in solution

    International Nuclear Information System (INIS)

    Sutin, N.

    1977-01-01

    A few representative electron-transfer reactions are selected and their kinetic parameters compared with the predictions of activated complex models. Since Taube has presented an elegant treatment of intramolecular electron-transfer reactions, emphasis is on bimolecular reactions. The latter electron-transfer reactions are more complicated to treat theoretically since the geometries of their activated complexes are not as well known as for the intramolecular case. In addition in biomolecular reactions, the work required to bring the two reactants together needs to be calculated. Since both reactants generally carry charges this presents a non-trivial problem at the ionic strengths usually used to study bimolecular electron transfer

  16. The different-ligand complexing of europium with complexones and β-diketones in micellar solution

    International Nuclear Information System (INIS)

    Svetlova, I.E.; Dobrynina, N.A.; Smirnova, N.S.; Martynenko, L.I.; Evseev, A.M.; Savitskij, A.P.

    1989-01-01

    Method of pH-metric titration with mathematical simulation was used to study the effect of nonionic surfactant (polyoxyethyleneoctylphenyl este) on stability of europium complexes with cyclohexanediaminetetraacetic and ethylenediaminetetraacetic acids. Optimal conditions for ternary complex formation in the system Eu 3+ -complexone-β-diketone at pH 7.0-9.0 were found. Complex-compositions were determined and their stability constants were calculated. It is shown that complex stability decreases by several orders in micellar solutions, tecause β-diketone introduction to the solution decreases thermodynamic stability of complexes

  17. Detailed solution to a complex kinematics chain manipulator

    International Nuclear Information System (INIS)

    March-Leuba, S.; Jansen, J.F.; Kress, R.L.; Babcock, S.M.

    1992-01-01

    This paper presents a relatively simple method based on planar geometry to analyze the inverse kinematics for closed kinematics chain (CKC) mechanisms. Although the general problem and method of approach are well defined, the study of the inverse kinematics of a closed-chain mechanism is a very complicated one. The current methodology allows closed-form solutions to be found, if a solution exists, for the displacements and velocities of all manipulator joints. Critical design parameters can be identified and optimized by using symbolic models. This paper will focus on planar closed-chain structures extended with a rotational base. However, with open and CKC mechanisms combined in different planes, the extension to the case is straightforward. Further, real-time algorithms are developed that can be handled by existing microprocessor technology. To clarify the methodology, the Soldier Robot Interface Project (SRIP) manipulator is analyzed, and a graphic simulation is presented as a verification of the results. This manipulator has 17 links, 24 one-degree-of-freedom (DOF) joints, and 7 CKC loops working in a plane and a rotational base, which determine its 3 DOFs. The SRIP manipulator allows a decoupled linear motion along the vertical or horizontal directions using only one of its linear actuators. The symbolic solution for the inverse kinematics allows optimization to be performed to further decouple the Cartesian motions by changing link lengths of the manipulator. The conclusion achieved by the optimization is that only two link lengths need to be changed to tune the manipulator for a perfect decoupling at each area of the workspace

  18. Actinide-specific complexing agents: their structural and solution chemistry

    International Nuclear Information System (INIS)

    Raymond, K.N.; Freeman, G.E.; Kappel, M.J.

    1983-07-01

    The synthesis of a series of tetracatecholate ligands designed to be specific for Pu(IV) and other actinide(IV) ions has been achieved. Although these compounds are very effective as in vivo plutonium removal agents, potentiometric and voltammetric data indicate that at neutral pH full complexation of the Pu(IV) ion by all four catecholate groups does not occur. Spectroscopic results indicate that the tetracatecholates, 3,4,3-LICAMS and 3,4,3-LICAMC, complex Am(III). The Am(IV)/(III)-catecholate couple (where catecholate = 3,4,3-LICAMS or 3,4,3-LICAMC) is not observed, but may not be observable due to the large currents associated with ligand oxidation. However, within the potential range where ligand oxidation does not occur, these experiments indicate that the reduction potential of free Am(IV)/(III) is probably greater than or equal to + 2.6 V vs NHE or higher. Proof of the complexation of americium in the trivalent oxidation state by 3,4,3-LICAMS and 3,4,3-LICAMC elimates the possibility of tetracatholates stabilizing Am(IV) in vivo

  19. Forward osmosis for oily wastewater reclamation: Multi-charged oxalic acid complexes as draw solutes.

    Science.gov (United States)

    Ge, Qingchun; Amy, Gary Lee; Chung, Tai-Shung

    2017-10-01

    Forward osmosis (FO) has demonstrated its merits in hybrid FO seawater desalination. However, FO may have a potential for other applications if suitable draw solutes are available. In this study, a series of novel draw solutes based on oxalic acid (OA)-transitional metal complexes are presented. Influential factors of FO performance have been systematically investigated by varying the transitional metals, cations of the complex draw solutes as well as the experimental conditions. Compared to NaCl and other recently synthesized draw solutes, the OA complexes show superior FO performance in terms of high water fluxes up to 27.5 and 89.1 LMH under the respective FO and PRO (pressure retarded osmosis) modes, both with negligible reverse solute fluxes. The features of octahedral geometry, abundant hydrophilic groups and ionic species are crucial for the OA complexes as appropriate draw solutes with satisfactory FO performance. Among the synthesized OA complexes, the ammonium salt of chromic complex (NH 4 -Cr-OA) outperforms others due to the presence of more ionic species in its complex system. NH 4 -Cr-OA also performs better than the typical NaCl draw solute in FO oily wastewater treatment with higher water recovery and negligible reverse fluxes. Dilute solutions of OA complexes have been reconcentrated through membrane distillation (MD) and reused to new round of FO processes. The OA complexes have demonstrated their suitability and superiority as a novel class of draw solutes for the FO process in this study. Copyright © 2017 Elsevier Ltd. All rights reserved.

  20. Complexation of Np(V) in aqueous solutions

    International Nuclear Information System (INIS)

    Askarieh, M.M.; Hansford, M.I.; Staunton, S.; Rees, L.V.C.

    1992-01-01

    Various parameters affecting the diffusion coefficient of neptunium (V) in clay systems have been studied; e.g. clay mineralogy, the charge compensating cation in the clay, the ionic strength of a background perchlorate solution and the presence of three organic ligands. Several well established techniques have been employed to obtain stability constants for the neptunium systems; Np(V)/EDTA and Np(V)/citrate, Np(V)/Aldrich Humic Acid (AHA), Np(V)/Gorleben Humic Acid (GHA) and for the uranium systems U(VI)/EDTA, U(VI)/citrate and U(VI)/AHA. The experimental techniques employed were UV/visible spectroscopy, polarography, solvent extraction and ion exchange. (Author)

  1. Complexation of Np(V) in aqueous solutions

    International Nuclear Information System (INIS)

    Askarieh, M.M.; Hansford, M.I.; Staunton, S.; Rees, L.V.C.

    1993-01-01

    Various parameters affecting the diffusion coefficient of neptunium (V) in clay systems have been studied; e.g. clay mineralogy, the charge compensating cation in the clay, the ionic strength of a background perchlorate solution and the presence of three organic ligands. Several well established techniques have been employed to obtain stability constants for the neptunium systems; Np(V) EDTA and Np(V)/citrate, Np(V)/Aldrich Humic Acid (AHA), Np(V)/Gorleben Hulic Acid (GHA) and for the uranium systems U(VI)/EDTA, U(VI)/citrate and U(VI)/AHA. The experimental techniques employed were UV/visible spectroscopy, polarography, solvent extraction and ion exchange. (author). 50 refs., 24 figs., 9 tabs

  2. Coulometric titration of niobium in EDTA complexing solution

    International Nuclear Information System (INIS)

    Pannu, S.S.

    1976-01-01

    Constant current coulometry of Nb in EDTA was studied employing both potentiometric and amperometric end-point techniques. The titrations were based on the oxidation of Nb(IV)-EDTA with electrogenerated Fe(III) at a graphite anode. The rate of disproportionation of Nb(IV)-EDTA was found to be slow enough not to effect the accuracy sought for the titration. The coulometric titration of Nb in EDTA was found to be more accurate than in 1F sulfuric acid. The mean error in the titrations of 4.76 to 19.65 of Nb in a volume of about 100 ml of 0.02 to 0.04F EDTA was 0.13%. It was found that Ta may be tolerated to a ratio of 1:4, Ta:Nb, in a solution containing 13 mg of Nb. (author)

  3. Distributed Cooperation Solution Method of Complex System Based on MAS

    Science.gov (United States)

    Weijin, Jiang; Yuhui, Xu

    To adapt the model in reconfiguring fault diagnosing to dynamic environment and the needs of solving the tasks of complex system fully, the paper introduced multi-Agent and related technology to the complicated fault diagnosis, an integrated intelligent control system is studied in this paper. Based on the thought of the structure of diagnostic decision and hierarchy in modeling, based on multi-layer decomposition strategy of diagnosis task, a multi-agent synchronous diagnosis federation integrated different knowledge expression modes and inference mechanisms are presented, the functions of management agent, diagnosis agent and decision agent are analyzed, the organization and evolution of agents in the system are proposed, and the corresponding conflict resolution algorithm in given, Layered structure of abstract agent with public attributes is build. System architecture is realized based on MAS distributed layered blackboard. The real world application shows that the proposed control structure successfully solves the fault diagnose problem of the complex plant, and the special advantage in the distributed domain.

  4. Influence of complexing on physicochemical properties of polymer-salt solutions

    International Nuclear Information System (INIS)

    Ostroushko, A.A.; Yushkova, S.M.; Koridze, N.V.; Skobkoreva, N.V.; Zhuravleva, L.I.; Palitskaya, T.A.; Antropova, S.V.; Ostroushko, I.P.; AN SSSR, Moscow

    1993-01-01

    Using the methods of spectrophotometry, viscosimetry, conductometry the influence of salt-polymer complexing processes on physicochemical prperties of aqueous solutions of yttrium, barium, copper nitrates and formates with polyvinyl alcohol was studied. Change of dynamic viscosity, specific electric conductivity of solutions in the process of complexing was shown. Thermal effects of salt-polymer interaction were measured. It is shown that decrease of transition temperature of polymer to plastic state in films, temperature and effective activation energy of salt decomposition is also connected with complexing. Effective values of surface tension on the boundary with air are measured. Coefficients of cation diffusion in polymer-salt solutions are estimated

  5. Error Estimates for Approximate Solutions of the Riccati Equation with Real or Complex Potentials

    Science.gov (United States)

    Finster, Felix; Smoller, Joel

    2010-09-01

    A method is presented for obtaining rigorous error estimates for approximate solutions of the Riccati equation, with real or complex potentials. Our main tool is to derive invariant region estimates for complex solutions of the Riccati equation. We explain the general strategy for applying these estimates and illustrate the method in typical examples, where the approximate solutions are obtained by gluing together WKB and Airy solutions of corresponding one-dimensional Schrödinger equations. Our method is motivated by, and has applications to, the analysis of linear wave equations in the geometry of a rotating black hole.

  6. A new approach to study cadmium complexes with oxalic acid in soil solution.

    Science.gov (United States)

    Dytrtová, Jana Jaklová; Jakl, Michal; Sestáková, Ivana; Zins, Emilie-Laure; Schröder, Detlef; Navrátil, Tomáš

    2011-05-05

    This study presents a new analytical approach for the determination of heavy metals complexed to low-molecular-weight-organic acids in soil solutions, which combines the sensitivity of differential pulse anodic stripping voltammetry (DPASV) with the molecular insight gained by electrospray ionization mass spectrometry (ESI-MS). The combination of these analytical methods allows the investigation of such complexes in complex matrixes. On the voltammograms of the soil solutions, in addition to the expected complexes of oxalic acid with cadmium and lead, respectively, also peaks belonging to mixed complexes of cadmium, lead, and oxalic acid (OAH(2)) were observed. In order to verify the possible formation of complexes with OAH(2), aqueous solutions of OAH(2) with traces of Cd(II) were investigated as model systems. Signals corresponding to several distinct molecular complexes between cadmium and oxalic acid were detected in the model solutions using negative-ion ESI-MS, which follow the general formula [Cd(n)(X,Y)((2n+1))](-), where n is the number of cadmium atoms, X=Cl(-), and Y=OAH(-). Some of these complexes were also identified in the ESI mass spectra taken from the soil solutions. Copyright © 2011 Elsevier B.V. All rights reserved.

  7. A new approach to study cadmium complexes with oxalic acid in soil solution

    International Nuclear Information System (INIS)

    Jaklova Dytrtova, Jana; Jakl, Michal; Sestakova, Ivana; Zins, Emilie-Laure; Schroeder, Detlef; Navratil, Tomas

    2011-01-01

    This study presents a new analytical approach for the determination of heavy metals complexed to low-molecular-weight-organic acids in soil solutions, which combines the sensitivity of differential pulse anodic stripping voltammetry (DPASV) with the molecular insight gained by electrospray ionization mass spectrometry (ESI-MS). The combination of these analytical methods allows the investigation of such complexes in complex matrixes. On the voltammograms of the soil solutions, in addition to the expected complexes of oxalic acid with cadmium and lead, respectively, also peaks belonging to mixed complexes of cadmium, lead, and oxalic acid (OAH 2 ) were observed. In order to verify the possible formation of complexes with OAH 2 , aqueous solutions of OAH 2 with traces of Cd(II) were investigated as model systems. Signals corresponding to several distinct molecular complexes between cadmium and oxalic acid were detected in the model solutions using negative-ion ESI-MS, which follow the general formula [Cd n (X,Y) (2n+1) ] - , where n is the number of cadmium atoms, X = Cl - , and Y = OAH - . Some of these complexes were also identified in the ESI mass spectra taken from the soil solutions.

  8. A new approach to study cadmium complexes with oxalic acid in soil solution

    Energy Technology Data Exchange (ETDEWEB)

    Jaklova Dytrtova, Jana, E-mail: dytrtova@uochb.cas.cz [Institute of Organic Chemistry and Biochemistry of the AS CR, v.v.i., Flemingovo namesti 2, 16610 Prague 6 (Czech Republic); Jakl, Michal [Department of Agro-Environmental Chemistry and Plant Nutrition, Faculty of Agrobiology, Food and Natural Resources, Czech University of Life Sciences, Kamycka 129, 16521 Prague - Suchdol (Czech Republic); Sestakova, Ivana [J. Heyrovsky Institute of Physical Chemistry of the AS CR, v.v.i., Dolejskova 3, 182 23 Prague 8 (Czech Republic); Zins, Emilie-Laure; Schroeder, Detlef [Institute of Organic Chemistry and Biochemistry of the AS CR, v.v.i., Flemingovo namesti 2, 16610 Prague 6 (Czech Republic); Navratil, Tomas [J. Heyrovsky Institute of Physical Chemistry of the AS CR, v.v.i., Dolejskova 3, 182 23 Prague 8 (Czech Republic)

    2011-05-05

    This study presents a new analytical approach for the determination of heavy metals complexed to low-molecular-weight-organic acids in soil solutions, which combines the sensitivity of differential pulse anodic stripping voltammetry (DPASV) with the molecular insight gained by electrospray ionization mass spectrometry (ESI-MS). The combination of these analytical methods allows the investigation of such complexes in complex matrixes. On the voltammograms of the soil solutions, in addition to the expected complexes of oxalic acid with cadmium and lead, respectively, also peaks belonging to mixed complexes of cadmium, lead, and oxalic acid (OAH{sub 2}) were observed. In order to verify the possible formation of complexes with OAH{sub 2}, aqueous solutions of OAH{sub 2} with traces of Cd(II) were investigated as model systems. Signals corresponding to several distinct molecular complexes between cadmium and oxalic acid were detected in the model solutions using negative-ion ESI-MS, which follow the general formula [Cd{sub n}(X,Y){sub (2n+1)}]{sup -}, where n is the number of cadmium atoms, X = Cl{sup -}, and Y = OAH{sup -}. Some of these complexes were also identified in the ESI mass spectra taken from the soil solutions.

  9. Fuzzy logic: A "simple" solution for complexities in neurosciences?

    Science.gov (United States)

    Godil, Saniya Siraj; Shamim, Muhammad Shahzad; Enam, Syed Ather; Qidwai, Uvais

    2011-02-26

    Fuzzy logic is a multi-valued logic which is similar to human thinking and interpretation. It has the potential of combining human heuristics into computer-assisted decision making, which is applicable to individual patients as it takes into account all the factors and complexities of individuals. Fuzzy logic has been applied in all disciplines of medicine in some form and recently its applicability in neurosciences has also gained momentum. This review focuses on the use of this concept in various branches of neurosciences including basic neuroscience, neurology, neurosurgery, psychiatry and psychology. The applicability of fuzzy logic is not limited to research related to neuroanatomy, imaging nerve fibers and understanding neurophysiology, but it is also a sensitive and specific tool for interpretation of EEGs, EMGs and MRIs and an effective controller device in intensive care units. It has been used for risk stratification of stroke, diagnosis of different psychiatric illnesses and even planning neurosurgical procedures. In the future, fuzzy logic has the potential of becoming the basis of all clinical decision making and our understanding of neurosciences.

  10. Reproductive plasticity of Hypostomus affinis (Siluriformes: Loricariidae as a mechanism to adapt to a reservoir with poor habitat complexity

    Directory of Open Access Journals (Sweden)

    Silvana Duarte

    2011-10-01

    Full Text Available In this work we describe the gonad morphology and spawning season of Hypostomus affinis (Steindachner, 1877 in a tropical reservoir based on 55 males and 125 females. Our aim was to assess eventual adaptations in reproductive tactics developed by this riverine species inhabiting an oligotrophic reservoir with low habitat complexity, few rocks and few other preferred consolidated substrata. We described the stages of cells of reproductive lineage, gonadal development and some reproductive traits which were compared with information in the available literature. Cells from the spermatogenic lineage were spermatogonia, spermatocytes, spermatids and spermatozoa, and cells from the oocytarian lineage were primary oocytes, previtelogenic oocytes, cortical vesicle oocytes and yolk globules or vitellogenic. Five stages were described for the males/females according to the distribution of oocytes and spermatogenic lineage cells: resting; initial maturation; advanced maturation; partially spent/spawned; totally spent/spawn. Females outnumbered males and reached larger size. Synchronic ovary development in two groups was found with diameter of mature oocytes ranging from 2 to 3.35 mm. Indication of early maturation, a longer reproductive period and the production of smaller eggs in small clutches seems to be features of the reservoir population not found in riverine systems. Such changes in tactics may indicate a shift to an opportunistic strategy, helping the population to withstand environmental constraints and to succeed in this oligotrophic and poorly structured reservoir.

  11. Spatial structure of transition metal complexes in solution determined by EXAFS spectroscopy

    Energy Technology Data Exchange (ETDEWEB)

    Erenburg, S.B. E-mail: simon@che.nsk.su; Bausk, N.V.; Zemskova, S.M.; Mazalov, L.N

    2000-06-21

    CdK EXAFS, ZnK and CuK EXAFS and XANES spectra were measured for solutions of cadmium, zinc and copper dialkyldithiocarbamates in organic solvents with varying donating abilities: tributylphosphine, methylene chloride, benzene, dibutylsulfide, pyridine, dimethylsulfoxide and for some model compounds. The parameters of the local surroundings of the Cd, Zn and Cu atoms for complex forms in solutions were determined using EXAFS spectroscopy. Spatial structure models of the complex forms in a metal chelate - nonaqueous solvent system are suggested.

  12. Spatial structure of transition metal complexes in solution determined by EXAFS spectroscopy

    International Nuclear Information System (INIS)

    Erenburg, S.B.; Bausk, N.V.; Zemskova, S.M.; Mazalov, L.N.

    2000-01-01

    CdK EXAFS, ZnK and CuK EXAFS and XANES spectra were measured for solutions of cadmium, zinc and copper dialkyldithiocarbamates in organic solvents with varying donating abilities: tributylphosphine, methylene chloride, benzene, dibutylsulfide, pyridine, dimethylsulfoxide and for some model compounds. The parameters of the local surroundings of the Cd, Zn and Cu atoms for complex forms in solutions were determined using EXAFS spectroscopy. Spatial structure models of the complex forms in a metal chelate - nonaqueous solvent system are suggested

  13. Origin of supercharging in electrospray ionization of noncovalent complexes from aqueous solution.

    Science.gov (United States)

    Sterling, Harry J; Williams, Evan R

    2009-10-01

    The use of m-nitrobenzyl alcohol (m-NBA) to enhance charging of noncovalent complexes formed by electrospray ionization from aqueous solutions was investigated. Addition of up to 1% m-NBA can result in a significant increase in the average charging of complexes, ranging from approximately 13% for the homo-heptamer of NtrC4-RC (317 kDa; maximum charge state increases from 42+ to 44+) to approximately 49% for myoglobin (17.6 kDa; maximum charge state increases from 9+ to 16+). Charge state distributions of larger complexes obtained from heated solutions to which no m-NBA was added are remarkably similar to those containing small amounts of m-NBA. Dissociation of the complexes through identical channels both upon addition of higher concentrations of m-NBA and heating is observed. These results indicate that the enhanced charging upon addition of m-NBA to aqueous electrospray solutions is a result of droplet heating owing to the high boiling point of m-NBA, which results in a change in the higher-order structure and/or dissociation of the complexes. For monomeric proteins and small complexes, the enhancement of charging is lower for heated aqueous solutions than from solutions with m-NBA because rapid folding of proteins from heated solutions that do not contain m-NBA can occur after the electrospray droplet is formed and is evaporatively cooled.

  14. Forward osmosis for oily wastewater reclamation: Multi-charged oxalic acid complexes as draw solutes

    KAUST Repository

    Ge, Qingchun; Amy, Gary L.; Chung, Neal Tai-Shung

    2017-01-01

    Cl and other recently synthesized draw solutes, the OA complexes show superior FO performance in terms of high water fluxes up to 27.5 and 89.1 LMH under the respective FO and PRO (pressure retarded osmosis) modes, both with negligible reverse solute fluxes

  15. Exact Solutions of Five Complex Nonlinear Schrödinger Equations by Semi-Inverse Variational Principle

    International Nuclear Information System (INIS)

    Najafi Mohammad; Arbabi Somayeh

    2014-01-01

    In this paper, we establish exact solutions for five complex nonlinear Schrödinger equations. The semi-inverse variational principle (SVP) is used to construct exact soliton solutions of five complex nonlinear Schrödinger equations. Many new families of exact soliton solutions of five complex nonlinear Schrödinger equations are successfully obtained. (general)

  16. The first example of intensive luminescence of LMCT state based on metal complexes in solution

    International Nuclear Information System (INIS)

    Lukova, G.V.; Vasil'ev, V.P.; Smirnov, V.A.; Huhn, W.

    2007-01-01

    A bridge complex rac-C 6 H 10 (IndH 4 ) 2 ZrC 2 , featuring a unique long-living luminescence in liquid solutions at 20 deg C, has been prepared for the first time by catalytic hydrogenation of bis-indinyl complex C 6 H 10 (Ind) 2 Zr 2 Cl 2 . It has been identified that quantum yields of luminescence of the complex solutions at room temperature are the greatest ones for the known compounds possessing emission states of charge transfer from ligand to metal. Linear correlations of quantum yield of metal complex luminescence in a solution with steric features of the solvent molecules have been detected for the first time [ru

  17. Uranium (VI) complexing by macrocyclic or chelating ligands in aqueous solutions stability, formation kinetics, polarographic properties

    International Nuclear Information System (INIS)

    Brighli, M.

    1984-07-01

    Stability of chelates (with EDTA,N,N ethylenediamine diacetic acid EDDA nitrilotriacetic acid NTA and iminodiacetic acid) of UO 2 2+ and UO 4 species of uranium VI is studied in aqueous solution (NaClO 4 3M at 25 deg celcius). Structure in solution are proposed and discussed for mononuclear species. Only complexing kinetics (formation and acid hydrolysis) of UO 4 with EDDA and NTA are studied by spectrophotometry (other reactions are too fast). Besides UO 2 2+ complexes are formed with crown ethers I5C5 and I8C6 in aqueous solution (TEA ClO 4 M/10 at 25 deg celcius. Complexes are probably stabilized by solvation. Results are confirmed by voltametry and reduction mechanisms of UO 2 2+ and its complexes on mercury drop are proposed. 143 refs [fr

  18. Structure of diphosphine complexes of Co(II) in solutions of organic compounds

    International Nuclear Information System (INIS)

    Saraev, V.V.; Mandyuk, I.M.; Ratovskii, G.V.; Dmitrieva, T.V.; Shmidt, F.K.

    1987-01-01

    The structure of the dichloride complexes of cobalt(II) with 1,2-bis(diphenylphosphino)ethane (DPPE) and 1,1-bis(diphenylphosphino)methane (DPPM) in organic solvents has been investigated by ESR and electronic spectroscopy. It has been shown that the low-spin complex Co(DPPE) 2 Cl 2 exists in dichloroethane and ethanol solutions in the form of a trigonal bipyramid. Cobalt dichloride reacts with DPPM to form 1:1 and 1:2 complexes, between which there is an equilibrium in a dichloroethane solution. The equilibrium is displaced under the action of the free diphosphine toward the formation of the 1:2 complex. Elimination of the diphosphine from the coordination sphere of cobalt occurs in an ethanol solution

  19. Behaviours of trinitratonitrosyl complexes of ruthenium in dilute nitric acid solutions

    Energy Technology Data Exchange (ETDEWEB)

    Sugimoto, S [Radia Industry Co. Ltd., Takasaki (Japan)

    1979-07-01

    This study aimed to elucidate the protolysis and condensation processes of the Ru complexes in relation to the concentration of nitric acid. The compositions of the dissociated and undissociated complexes were determined by the extraction with tributyl phosphate (TBP) and absorption spectroscopy in order to follow the rather rapid protolysis reaction of the complexes. The test solutions were prepared by dissolving the freshly obtained complexes into 0.50 - 0.001 M nitric acid solutions. The amounts of the undissociated complexes were determined at different elapses of time in the test solutions. The protolysis became significant when the concentration was below 0.15 M, and the dissociation rate suddenly increased at this concentration. At the concentrations above 0.2 M, the absorption peak of the complexes at 480 nm survived even after 144 hours. But below 0.15 M, the formation of dissociation products by protolysis was observed after the disappearance of the absorption peak. The amount of dissociation products rapidly increased after the preparation of the test solution as the concentration decreased below 0.15 M.

  20. Solution of Schroedinger Equation for Two-Dimensional Complex Quartic Potentials

    International Nuclear Information System (INIS)

    Singh, Ram Mehar; Chand, Fakir; Mishra, S. C.

    2009-01-01

    We investigate the quasi-exact solutions of the Schroedinger wave equation for two-dimensional non-hermitian complex Hamiltonian systems within the frame work of an extended complex phase space characterized by x = x 1 + ip 3 , y = x 2 + ip 4 , p x = p 1 + ix 3 , p y = p 2 + ix 4 . Explicit expressions of the energy eigenvalues and the eigenfunctions for ground and first excited states for a complex quartic potential are obtained. Eigenvalue spectra of some variants of the complex quartic potential, including PT-symmetric one, are also worked out. (general)

  1. Laser-induced flourescence studies of Cm3+ complexes in solution

    International Nuclear Information System (INIS)

    Beitz, J.V.

    1989-01-01

    Photophysical studies of complexed Cm 3 + in solution have been carried out using a laser-induced fluorescence method. The luminescence decay rate of the first excited J=7/2 state of Cm 3 + was measured using carbonate, nitrate, and two extractant aminocarboxylic acids as complexing ligands in aqueous solution. Cm(ClO 4 ) 3 dissolved in methyl sulfoxide also was studied. Solvent deuteration provided insight into the dominant nonradiative luminescence quenching mechanism which was found to be electronic-to- vibrational energy transfer. Emission spectra of Cm 3 + complexed by the various ligands studied are reported. Prior spectroscopic and photophysical studies of Cm 3 + in solution are reviewed. 24 refs. , 2 figs., 1 tab

  2. The inverse Fourier problem in the case of poor resolution in one given direction: the maximum-entropy solution

    International Nuclear Information System (INIS)

    Papoular, R.J.; Zheludev, A.; Ressouche, E.; Schweizer, J.

    1995-01-01

    When density distributions in crystals are reconstructed from 3D diffraction data, a problem sometimes occurs when the spatial resolution in one given direction is very small compared to that in perpendicular directions. In this case, a 2D projected density is usually reconstructed. For this task, the conventional Fourier inversion method only makes use of those structure factors measured in the projection plane. All the other structure factors contribute zero to the reconstruction of a projected density. On the contrary, the maximum-entropy method uses all the 3D data, to yield 3D-enhanced 2D projected density maps. It is even possible to reconstruct a projection in the extreme case when not one structure factor in the plane of projection is known. In the case of poor resolution along one given direction, a Fourier inversion reconstruction gives very low quality 3D densities 'smeared' in the third dimension. The application of the maximum-entropy procedure reduces the smearing significantly and reasonably well resolved projections along most directions can now be obtained from the MaxEnt 3D density. To illustrate these two ideas, particular examples based on real polarized neutron diffraction data sets are presented. (orig.)

  3. Solution structure of the Grb2 SH2 domain complexed with a high-affinity inhibitor

    International Nuclear Information System (INIS)

    Ogura, Kenji; Shiga, Takanori; Yokochi, Masashi; Yuzawa, Satoru; Burke, Terrence R.; Inagaki, Fuyuhiko

    2008-01-01

    The solution structure of the growth factor receptor-bound protein 2 (Grb2) SH2 domain complexed with a high-affinity inhibitor containing a non-phosphorus phosphate mimetic within a macrocyclic platform was determined by nuclear magnetic resonance (NMR) spectroscopy. Unambiguous assignments of the bound inhibitor and intermolecular NOEs between the Grb2 SH2 domain and the inhibitor was accomplished using perdeuterated Grb2 SH2 protein. The well-defined solution structure of the complex was obtained and compared to those by X-ray crystallography. Since the crystal structure of the Grb2 SH2 domain formed a domain-swapped dimer and several inhibitors were bound to a hinge region, there were appreciable differences between the solution and crystal structures. Based on the binding interactions between the inhibitor and the Grb2 SH2 domain in solution, we proposed a design of second-generation inhibitors that could be expected to have higher affinity

  4. Nuclear inelastic scattering of synchrotron radiation on solutions of 57Fe complexes

    International Nuclear Information System (INIS)

    Vanko, Gy.; Vertes, A.; Bottyan, L.; Nagy, D.L.; Szilagyi, E.

    2000-01-01

    Nuclear inelastic resonant scattering of synchrotron radiation was applied to the study solutions of 57 Fe complexes. In order to reveal different inelastic contributions solutions of two different 57 Fe complexes of different molecular dimensions with solvents of substantially different viscosities were studied. We argue that the only former experiment available in the literature overestimates the role of the diffusivity in affecting the spectrum. The first direct observation of an intramolecular vibrational transition assisting the nuclear resonance absorption in a liquid is reported. (author)

  5. Study of the formation of soluble complexes of sodium caseinate and xanthan in solution.

    Science.gov (United States)

    Bouhannache, Bouchra; HadjSadok, Abdelkader; Touabet, Abdelkrim

    2017-09-01

    The main objective of this work was to determinate the optimum conditions for the formation of soluble complexes between sodium caseinate and xanthan in solution at neutral pH, in the presence of the NaCl. The study of the influence of the concentrations of these three substances showed that salt was the most influent factor. It worsens the thermodynamic incompatibility of the two biopolymers in solution, when they are present at large amounts. However, it contributes to soluble complexes formation, when sodium caseinate concentration is below 5.5%. In this case, gels with enhanced rheological properties were obtained. Infrared spectroscopy confirmed that the complexes formation within these gels involves hydrophobic interactions. On the other hand, dynamic light scattering revealed that dilution cause their dissociation. These soluble complexes are promising ingredients to ensure new texturing properties.

  6. Higher derivative discontinuous solutions to linear ordinary differential equations: a new route to complexity?

    International Nuclear Information System (INIS)

    Datta, Dhurjati Prasad; Bose, Manoj Kumar

    2004-01-01

    We present a new one parameter family of second derivative discontinuous solutions to the simplest scale invariant linear ordinary differential equation. We also point out how the construction could be extended to generate families of higher derivative discontinuous solutions as well. The discontinuity can occur only for a subset of even order derivatives, viz., 2nd, 4th, 8th, 16th,.... The solutions are shown to break the discrete parity (reflection) symmetry of the underlying equation. These results are expected to gain significance in the contemporary search of a new dynamical principle for understanding complex phenomena in nature

  7. Complex Liver Resections for Colorectal Metastases: Are They Safe in the Low-Volume, Resource-Poor Caribbean Setting?

    Directory of Open Access Journals (Sweden)

    Shamir O. Cawich

    2015-01-01

    Full Text Available Introduction. Although many authorities suggest that major liver resections should only be carried out in high-volume specialized centres, many patients in the Caribbean do not have access to these health care systems. Presentation of a Case. A 50-year-old woman with a solitary colorectal metastasis invading the inferior vena cava underwent an extended left hepatectomy with caval resection and reconstruction. Several technical maneuvers were utilized that were suited to the resource-poor environment. Conclusion. We suggest that good outcomes can still be attained in the resource-poor, low-volume centres once dedicated and appropriately trained teams are available.

  8. Exact solutions of the one-dimensional generalized modified complex Ginzburg-Landau equation

    International Nuclear Information System (INIS)

    Yomba, Emmanuel; Kofane, Timoleon Crepin

    2003-01-01

    The one-dimensional (1D) generalized modified complex Ginzburg-Landau (MCGL) equation for the traveling wave systems is analytically studied. Exact solutions of this equation are obtained using a method which combines the Painleve test for integrability in the formalism of Weiss-Tabor-Carnevale and Hirota technique of bilinearization. We show that pulses, fronts, periodic unbounded waves, sources, sinks and solution as collision between two fronts are the important coherent structures that organize much of the dynamical properties of these traveling wave systems. The degeneracies of the 1D generalized MCGL equation are examined as well as several of their solutions. These degeneracies include two important equations: the 1D generalized modified Schroedinger equation and the 1D generalized real modified Ginzburg-Landau equation. We obtain that the one parameter family of traveling localized source solutions called 'Nozaki-Bekki holes' become a subfamily of the dark soliton solutions in the 1D generalized modified Schroedinger limit

  9. Treatment of plutonium-bearing solutions: A brief survey of the DOE complex

    International Nuclear Information System (INIS)

    Conner, C.; Chamberlain, D.B.; Chen, L.; Vandegrift, G.F.

    1995-03-01

    With the abrupt shutdown of some DOE facilities, a significant volume of in-process material was left in place and still requires treatment for interim storage. Because the systems containing these process streams have deteriorated since shutdown, a portable system for treating the solutions may be useful. A brief survey was made of the DOE complex on the need for a portable treatment system to treat plutonium-bearing solutions. A survey was completed to determine (1) the compositions and volumes of solutions and heels present, (2) the methods that have been used to treat these solutions and heels in the past, and (3) the potential problems that exist in removing and treating these solutions. Based on the surveys and on the Defense Nuclear Facilities Safety Board Recommendation 94-1, design criteria for a portable treatment system were generated

  10. Aspects of the structure and solution chemistry of some technetium-tripolyphosphate complexes

    International Nuclear Information System (INIS)

    Miller, G.G.

    1983-01-01

    Several distinctly different complexes of Tc(III) and Tc(IV) with the ligand tripolyphosphate were prepared and studied electrochemically. In acidic solution, a transient Tc(III) species was observed, the electrochemical behavior of which proves that it is not monomeric in Tc and strongly suggests that it is a dimer. This material is radically different in its polarographic behavior from the Tc(III) complex resulting from the controlled potential electrolysis of TcO 4 - at a mercury pool cathode in the same electrolyte. The latter, air sensitive, complex can be reversibly oxidized to a Tc(IV) complex which is stable towards further oxidation but which undergoes hydrolysis in both acidic and alkaline media. The rate law for the hydrolysis in basic solution is: rate = 582 I mol -1 min -1 [Tc(IV)][OH - ]. The hydrolytic reaction in acidic solution is accelerated by hydrogen ion, indicating that a mechanism different from that in basic media is involved. Tc(IV) tripolyphosphate complexes prepared by ligand exchange reactions of TcBr 6 2- were shown by polarography to be different from the complexes prepared electrochemically. The gel permeation chromatographic behavior of one ligand substitution product showed it to be polymeric with a limiting tripolyphosphate to technetium ratio of 1:1

  11. Formation and stabilization of anionic metal complexes in concentrated aqueous quaternary ammonium salt solutions

    International Nuclear Information System (INIS)

    Aronson, F.L.; Hwang, L.L.Y.; Ronca, N.; Solomon, N.A.; Steigman, J.

    1985-01-01

    Anionic complexes of transition metals were stabilized in aqueous solutions containing high concentrations of various short-chain quaternary ammonium salts. Compounds with longer paraffin chains were effective in much less concentrated solution. Complex ions were detected spectrophotometrically. FeCl 4 - , which is usually formed in concentrated HCl, was the predominant Fe(III) complex in 30 m choline chloride containing only 0.12 M HCl. A yellow transitory Tc(VII) chloro-addition intermediate, formed in the reduction of TcO 4 - by concentrated HCl, was stabilized when the solution also contained 25 m choline chloride. Its spectrum, as well as the isolation of an already known Tc(VII) bipyridyl complex, is reported. Concentrated organic electrolytes also stabilized Tc(V) oxide halides against disproportionation and Tc(IV) hexahalides against hydrolysis. Halochromates of Cr(VI) were formed and stabilized in dilute acid containing quaternary ammonium salts. Their UV spectra showed the well-resolved vibronic fine structure associated with the symmetric chromium-to-oxygen charge-transfer band. It is known that these progressions are resolved in aprotic solvents, but not in aqueous acidic solution alone, and that the loss of fine structure in aqueous media is due to hydrogen bonding. The stabilization of anionic metal complexes and the resolution of vibronic structure in halochromates are probably consequences of water-structure-enforced ion paring. The present work suggests that the water molecules in immediate contact with the complex anions are more strongly hydrogen bonded to each other than to the complex. 21 references, 4 figures

  12. [Influence of the earthworm Lumbricus terrestris on soil solution complexation capacity].

    Science.gov (United States)

    el Gharmali, A; Rada, A; el Meray, M; Nejmeddine, A

    2001-04-01

    Four soil samples highly contaminated with metals of urban and mine origin (SE1, SE2, SM1, SM2) and having different physico-chemical proprieties were selected to study copper complexation capacity (LT) of soil solution. The effect of Lumbricus terrestris on copper complexation capacity of soil solution was investigated on SE1 and SE2. The complexation capacity was estimated by amperometric titration of soil solution by copper. Free hydrated cation and labile complexes of copper were determined by DPASV. The results show that the copper complexation capacity variation depends on the physico-chemical characteristics of soils, particularly pH. Thus, the values of copper complexation capacity are 0; 0.6 x 10(-7); 1.8 x 10(-7) and 5.5 x 10(-7) mol l-1 respectively for SM2; SM1; SE1 and SE2 which are pH 5; 5.4; 6.5 and 7.4. Based on these results, the bioavailability levels of heavy metals show the following pool ranking: SM2 > SM1 > SE1 > SE2. The copper complexation capacity of soil solution increases with the soil disturbance by Lumbricus terrestris. This is more obvious when the time of disturbance by lumbrics is longer. Indeed, average values determined for 1 month and 3 months are 3.8 x 10(-7) and 7.8 x 10(-7) mol l-1 for SE1; 7.7 x 10(-7) and 15.2 x 10(-7) mol l-1 for SE2 respectively. It seems that the action of earthworm on soil can contribute to the decrease of bioavailability of heavy metals, particularly copper.

  13. Steric structure and thermodynamic aspects of Dy3+ complexes with aminobenzoic acids in aqueous solutions

    International Nuclear Information System (INIS)

    Kondrashina, Yu.G.; Mustafina, A.R.; Vul'fson, S.G.

    1994-01-01

    Stability and structure of dysprosium(3) aminobenzoate complexes with molar ratios Dy:L 1:1 and 1:2 (HL-aminobenzoic acid) in aqueous solutions are determined on the basis of pH-metric and paramagnetic birefringence data. The increase of conjugation effect in the series of benzoic, meta- ortho-, and para-aminobenzoic acid results in the increase of stability of 1:1 and 1:2 complexes. Features of the structure and coordination of ligands in dysprosium complexes with meta-, ortho-, and para-aminobenzoic acid are considered. 11 refs.; 4 figs.; 2 tabs

  14. General classical solutions of the complex Grassmannian and CP sub(N-1) sigma models

    International Nuclear Information System (INIS)

    Sasaki, Ryu.

    1983-05-01

    General classical solutions are constructed for the complex Grassmannian non-linear sigma models in two euclidean dimensions in terms of holomorphic functions. The Grassmannian sigma models are a simple generalization of the well known CP sup(N-1) model in two dimensions and they share various interesting properties; existence of (anti-) instantons, an infinite number of conserved quantities and complete integrability. (author)

  15. Electron spectra and mechanism of complexing of uranyl nitrate in water-acetone solutions

    International Nuclear Information System (INIS)

    Zazhogin, A.A.; Zazhogin, A.P.; Komyak, A.I.; Serafimovich, A.I.

    2003-01-01

    Based on the analysis of the luminescence and electronic absorption spectra, the processes of complexing in an aqueous solution of UO 2 (NO 3 ) 2 ·6H 2 O with small additions of acetone have been studied. In a pure aqueous solution, uranyl exists as the complex UO 2 ·5H 2 O. It is shown that the addition of acetone to the solution leads to the displacement of some water molecules out of the first coordination sphere of uranyl and the formation of the uranyl nitrate dihydrate complexes UO 2 (NO 3 ) 2 ·2H 2 O. It has been established that the stability of these complexes is determined by the decrease in the water activity and in the degree of hydration of uranyl and nitrate, which is the result of the local increase in the concentration of acetone molecules (due to their hydrophobicity) in the regions of the solution where uranyl and nitrate ions are found. The experimental facts supported the mechanism proposed are presented. (authors)

  16. Wormhole solutions with a complex ghost scalar field and their instability

    Science.gov (United States)

    Dzhunushaliev, Vladimir; Folomeev, Vladimir; Kleihaus, Burkhard; Kunz, Jutta

    2018-01-01

    We study compact configurations with a nontrivial wormholelike spacetime topology supported by a complex ghost scalar field with a quartic self-interaction. For this case, we obtain regular asymptotically flat equilibrium solutions possessing reflection symmetry. We then show their instability with respect to linear radial perturbations.

  17. ON ENTIRE SOLUTIONS OF TWO TYPES OF SYSTEMS OF COMPLEX DIFFERENTIAL-DIFFERENCE EQUATIONS

    Institute of Scientific and Technical Information of China (English)

    Lingyun GAO

    2017-01-01

    In this paper,we will mainly investigate entire solutions with finite order of two types of systems of differential-difference equations,and obtain some interesting results.It extends some results concerning complex differential (difference) equations to the systems of differential-difference equations.

  18. Spectrophotometric study of holmium complexation in KOH solutions at 25 Deg C

    International Nuclear Information System (INIS)

    Stepanchikova, S.A.; Bitejkina, R.P.

    2006-01-01

    Complexation of Ho 3+ in solutions of HoCl 3 and KOH at 25 Deg C is studied by indicator spectrophotometric method. Within the range of pH 9.25-10.10 and μ≤4 x 10 -4 stability constants of Ho 3+ hydroxocomplexes are measured and are extrapolated on zero ion strength [ru

  19. Computer analysis of potentiometric data of complexes formation in the solution

    Science.gov (United States)

    Jastrzab, Renata; Kaczmarek, Małgorzata T.; Tylkowski, Bartosz; Odani, Akira

    2018-02-01

    The determination of equilibrium constants is an important process for many branches of chemistry. In this review we provide the readers with a discussion on computer methods which have been applied for elaboration of potentiometric experimental data generated during complexes formation in solution. The review describes both: general basis of modeling tools and examples of the use of calculated stability constants.

  20. Orbiting the moons of Pluto complex solutions to the Einstein, Maxwell, Schroedinger and Dirac equations

    CERN Document Server

    Rauscher, Elizabeth A

    2011-01-01

    The Maxwell, Einstein, Schrödinger and Dirac equations are considered the most important equations in all of physics. This volume aims to provide new eight- and twelve-dimensional complex solutions to these equations for the first time in order to reveal

  1. Room temperature synthesis of protonated layered titanate sheets using peroxo titanium carbonate complex solution.

    Science.gov (United States)

    Sutradhar, Narottam; Sinhamahapatra, Apurba; Pahari, Sandip Kumar; Bajaj, Hari C; Panda, Asit Baran

    2011-07-21

    We report the synthesis of peroxo titanium carbonate complex solution as a novel water-soluble precursor for the direct synthesis of layered protonated titanate at room temperature. The synthesized titanates showed excellent removal capacity for Pb(2+) and methylene blue. Based on experimental observations, a probable mechanism for the formation of protonated layered dititanate sheets is also discussed.

  2. Using the Solution Space Diagram in Measuring the Effect of Sector Complexity During Merging Scenarios

    NARCIS (Netherlands)

    Abdul Rahman, S.M.B.; Van Paassen, M.M.; Mulder, M.

    2011-01-01

    When designing Air Traffic Control (ATC) sectors and procedures, traffic complexity and workload are important issues. For predicting ATC workload, metrics based on the Solution Space Diagram (SSD) have been proposed. This paper studies the effect of sector design on workload and SSD metrics. When

  3. Complexation of Polyelectrolytes with Hydrophobic Drug Molecules in Salt-Free Solution: Theory and Simulations.

    Science.gov (United States)

    Lei, Qun-Li; Hadinoto, Kunn; Ni, Ran

    2017-04-18

    The delivery and dissolution of poorly soluble drugs is challenging in the pharmaceutical industry. One way to significantly improve the delivery efficiency is to incorporate these hydrophobic small molecules into a colloidal polyelectrolyes(PE)-drug complex in their ionized states. Despite its huge application value, the general mechanism of PE collapse and complex formation in this system has not been well understood. In this work, by combining a mean-field theory with extensive molecular simulations, we unveil the phase behaviors of the system under dilute and salt-free conditions. We find that the complexation is a first-order-like phase transition triggered by the hydrophobic attraction between the drug molecules. Importantly, the valence ratio between the drug molecule and PE monomer plays a crucial role in determining the stability and morphology of the complex. Moreover, the sign of the zeta potential and the net charge of the complex are found to be inverted as the hydrophobicity of the drug molecules increases. Both theory and simulation indicate that the complexation point and complex morphology and the electrostatic properties of the complex have a weak dependence on chain length. Finally, the dynamics aspect of PE-drug complexation is also explored, and it is found that the complex can be trapped into a nonequilibrium glasslike state when the hydropobicity of the drug molecule is too strong. Our work gives a clear physical picture behind the PE-drug complexation phenomenon and provides guidelines to fabricate the colloidal PE-drug complex with the desired physical characteristics.

  4. Ammonia complexes of metals in aqueous solutions with high concentrations of ammonia

    International Nuclear Information System (INIS)

    Padar, T.G.; Novikov, L.K.; Stupko, T.V.; Isaev, I.D.; Pashkov, G.L.; Mironov, V.E.

    1991-01-01

    Potentiometric method, glass electrodes and Bierrum function were used to study the formation of ammonia complexes of magnesium, calcium, cadmium, zinc, copper(2) and silver in 2.0 mol/dm 3 aqueous solutions of ammonia nitrate with 0-18 mol/dm 3 ammonia concentrations at 25.0 deg C. Step constants of stability of studied complexes were calculated and their compositions were determined with account of nonideal character of aqueous-salt solutions with ammonia concentrations above 1.0 mol/dm 3 . Values of correction effects on salting out ammonia action for Bierrum function in solutions with 1.0-18 mol/dm 3 ammonia concentrations were found

  5. EXAFS Phase Retrieval Solution Tracking for Complex Multi-Component System: Synthesized Topological Inverse Computation

    International Nuclear Information System (INIS)

    Lee, Jay Min; Yang, Dong-Seok; Bunker, Grant B

    2013-01-01

    Using the FEFF kernel A(k,r), we describe the inverse computation from χ(k)-data to g(r)-solution in terms of a singularity regularization method based on complete Bayesian statistics process. In this work, we topologically decompose the system-matched invariant projection operators into two distinct types, (A + AA + A) and (AA + AA + ), and achieved Synthesized Topological Inversion Computation (STIC), by employing a 12-operator-closed-loop emulator of the symplectic transformation. This leads to a numerically self-consistent solution as the optimal near-singular regularization parameters are sought, dramatically suppressing instability problems connected with finite precision arithmetic in ill-posed systems. By statistically correlating a pair of measured data, it was feasible to compute an optimal EXAFS phase retrieval solution expressed in terms of the complex-valued χ(k), and this approach was successfully used to determine the optimal g(r) for a complex multi-component system.

  6. Electrochemical studies of plutonium(IV) complexes in aqueous nitrate solutions

    International Nuclear Information System (INIS)

    Kim, Seong-Yun; Asakura, Toshihide; Morita, Yasuji

    2005-01-01

    Electrochemistry has been used to investigate the behavior of plutonium (IV) in 1-7 M HNO 3 solutions. These Pu(IV) complexes were found to be reduced quasi-reversibly to Pu(III) species. The formal redox potentials (E 0 ) for Pu(IV)/Pu(III) couples were determined to be +0.721, +0.712, +0.706, +0.705, +0.704, 0.694, and +0.696 V (vs. Ag/AgCl(SSE)) for Pu(IV) complexes in 1, 2, 3, 4, 5, 6, 7 M HNO 3 solutions, respectively. These results indicate that the reduction product of Pu(IV) is Pu(III), which is considerably stable in HNO 3 solution. (author)

  7. Labile synthetic cadmium complexes are not bioavailable to Pseudokirchneriella subcapitata in resin buffered solutions

    Energy Technology Data Exchange (ETDEWEB)

    Verheyen, L., E-mail: Liesbeth.Verheyen@ees.kuleuven.be [Division of Soil and Water Management, K.U. Leuven, Kasteelpark Arenberg 20, Box 2459, 3001 Heverlee (Belgium); Merckx, R. [Division of Soil and Water Management, K.U.Leuven, Kasteelpark Arenberg 20, Box 2459, 3001 Heverlee (Belgium); Smolders, E., E-mail: Erik.Smolders@ees.kuleuven.be [Division of Soil and Water Management, K.U. Leuven, Kasteelpark Arenberg 20, Box 2459, 3001 Heverlee (Belgium)

    2012-11-15

    The Free Ion Activity Model (FIAM) predicts that cadmium (Cd) uptake by organisms is identical for solutions with the same free Cd{sup 2+} concentration and inorganic composition. Clear exceptions to the FIAM have been shown for Cd uptake by plant roots, periphyton and human cells where labile Cd complexes increase bioavailability and which has been attributed to their role in enhancing Cd diffusion towards the uptake cells. Here, we assessed the role of labile Cd complexes on Cd uptake by algae, for which diffusion limitations should be less pronounced due to their smaller size. Long-term (3 days) Cd uptake by the green algae Pseudokirchneriella subcapitata was measured in resin buffered solutions with or without synthetic ligands and at three Cd{sup 2+} ion activities (pCd 8.2-5.7). The free Cd{sup 2+} activity was maintained during the test using a metal-selective resin located in the algal bottles. Total dissolved Cd increased up to 35-fold by adding the synthetic ligands at constant Cd{sup 2+} activity. In contrast, Cd uptake by algae increased maximally 2.8 fold with increasing concentration of the synthetic ligands and the availability of the complexes were maximally 5.2% relative to Cd{sup 2+} for NTA and CDTA complexes. It is concluded that labile Cd complexes do not greatly enhance Cd bioavailability to the unicellular algae and calculations suggest that Cd transport from solution to these small cells is not rate limiting.

  8. Labile synthetic cadmium complexes are not bioavailable to Pseudokirchneriella subcapitata in resin buffered solutions

    International Nuclear Information System (INIS)

    Verheyen, L.; Merckx, R.; Smolders, E.

    2012-01-01

    The Free Ion Activity Model (FIAM) predicts that cadmium (Cd) uptake by organisms is identical for solutions with the same free Cd 2+ concentration and inorganic composition. Clear exceptions to the FIAM have been shown for Cd uptake by plant roots, periphyton and human cells where labile Cd complexes increase bioavailability and which has been attributed to their role in enhancing Cd diffusion towards the uptake cells. Here, we assessed the role of labile Cd complexes on Cd uptake by algae, for which diffusion limitations should be less pronounced due to their smaller size. Long-term (3 days) Cd uptake by the green algae Pseudokirchneriella subcapitata was measured in resin buffered solutions with or without synthetic ligands and at three Cd 2+ ion activities (pCd 8.2–5.7). The free Cd 2+ activity was maintained during the test using a metal-selective resin located in the algal bottles. Total dissolved Cd increased up to 35-fold by adding the synthetic ligands at constant Cd 2+ activity. In contrast, Cd uptake by algae increased maximally 2.8 fold with increasing concentration of the synthetic ligands and the availability of the complexes were maximally 5.2% relative to Cd 2+ for NTA and CDTA complexes. It is concluded that labile Cd complexes do not greatly enhance Cd bioavailability to the unicellular algae and calculations suggest that Cd transport from solution to these small cells is not rate limiting.

  9. Structure solution of DNA-binding proteins and complexes with ARCIMBOLDO libraries

    Energy Technology Data Exchange (ETDEWEB)

    Pröpper, Kevin [University of Göttingen, (Germany); Instituto de Biologia Molecular de Barcelona (IBMB-CSIC), (Spain); Meindl, Kathrin; Sammito, Massimo [Instituto de Biologia Molecular de Barcelona (IBMB-CSIC), (Spain); Dittrich, Birger; Sheldrick, George M. [University of Göttingen, (Germany); Pohl, Ehmke, E-mail: ehmke.pohl@durham.ac.uk [Durham University, (United Kingdom); Usón, Isabel, E-mail: ehmke.pohl@durham.ac.uk [Instituto de Biologia Molecular de Barcelona (IBMB-CSIC), (Spain); Institucio Catalana de Recerca i Estudis Avancats (ICREA), (Spain); University of Göttingen, (Germany)

    2014-06-01

    The structure solution of DNA-binding protein structures and complexes based on the combination of location of DNA-binding protein motif fragments with density modification in a multi-solution frame is described. Protein–DNA interactions play a major role in all aspects of genetic activity within an organism, such as transcription, packaging, rearrangement, replication and repair. The molecular detail of protein–DNA interactions can be best visualized through crystallography, and structures emphasizing insight into the principles of binding and base-sequence recognition are essential to understanding the subtleties of the underlying mechanisms. An increasing number of high-quality DNA-binding protein structure determinations have been witnessed despite the fact that the crystallographic particularities of nucleic acids tend to pose specific challenges to methods primarily developed for proteins. Crystallographic structure solution of protein–DNA complexes therefore remains a challenging area that is in need of optimized experimental and computational methods. The potential of the structure-solution program ARCIMBOLDO for the solution of protein–DNA complexes has therefore been assessed. The method is based on the combination of locating small, very accurate fragments using the program Phaser and density modification with the program SHELXE. Whereas for typical proteins main-chain α-helices provide the ideal, almost ubiquitous, small fragments to start searches, in the case of DNA complexes the binding motifs and DNA double helix constitute suitable search fragments. The aim of this work is to provide an effective library of search fragments as well as to determine the optimal ARCIMBOLDO strategy for the solution of this class of structures.

  10. Iodine K-edge EXAFS analysis of iodide ion-cyclodextrin inclusion complexes in aqueous solution

    International Nuclear Information System (INIS)

    Kaneko, T; Ueda, M; Nagamatsu, S; Konishi, T; Fujikawa, T; Mizumaki, M

    2009-01-01

    We study the structure of inclusion complexes of α-, β-, γ-cyclodextrin with mono-iodide ion in aqueous solution by means of iodine K-edge EXAFS spectroscopy. The analysis is based on the assumption that two kinds of iodide ions exist in KI-cyclodextrin aqueous solution i.e. hydrated mono-iodide ions and one-one mono-iodide-cyclodextrin inclusion complexes. In KI-α-cyclodextrin system, iodine K-edge EXAFS analyse show that the average coordination number of the oxygen atoms in water molecules in the first hydration shell decreases as the fraction of included ions increases. This result suggests that dehydration process accompanies the formation of the inclusion complex. This is not found in the case of β-cyclodextrin, indicating that in this case the iodide ions are included together with the whole first hydration shell.

  11. Separation of glycols from dilute aqueous solutions via complexation with boronic acids

    Energy Technology Data Exchange (ETDEWEB)

    Randel, L.A.; King, C.J.

    1991-07-01

    This work examines methods of separating low molecular weight glycols from dilute aqueous solution. Extraction into conventional solvents is generally not economical, since, in the literature reviewed, distribution ratios for the two- to four-carbon glycols are all less than one. Distribution ratios can be increased, however, by incorporating into the organic phase an extracting agent that will complex with the solute of interest. The extracting agent investigated in this work is 3-nitrophenylboronic acid (NPBA). NPBA, a boric acid derivative, reversibly complexes with many glycols. The literature on complexation of borate and related compounds with glycols, including mechanistic data, measurement techniques, and applications to separation processes, provides information valuable for designing experiments with NPBA and is reviewed herein. 88 refs., 15 figs., 24 tabs.

  12. A new sub-equation method applied to obtain exact travelling wave solutions of some complex nonlinear equations

    International Nuclear Information System (INIS)

    Zhang Huiqun

    2009-01-01

    By using a new coupled Riccati equations, a direct algebraic method, which was applied to obtain exact travelling wave solutions of some complex nonlinear equations, is improved. And the exact travelling wave solutions of the complex KdV equation, Boussinesq equation and Klein-Gordon equation are investigated using the improved method. The method presented in this paper can also be applied to construct exact travelling wave solutions for other nonlinear complex equations.

  13. A relativistic density functional study of uranyl hydrolysis and complexation by carboxylic acids in aqueous solution

    Energy Technology Data Exchange (ETDEWEB)

    Ray, Rupashree Shyama

    2009-02-10

    In this work, the complexation of uranium in its most stable oxidation state VI in aqueous solution was studied computationally, within the framework of density functional (DF) theory. The thesis is divided into the following parts: Chapter 2 briefly summarizes the relevant general aspects of actinide chemistry and then focuses on actinide environmental chemistry. Experimental results on hydrolysis, actinide complexation by carboxylic acids, and humic substances are presented to establish a background for the subsequent discussion. Chapter 3 describes the computational method used in this work and the relevant features of the parallel quantum chemistry code PARAGAUSS employed. First, the most relevant basics of the applied density functional approach are presented focusing on relativistic effects. Then, the treatment of solvent effects, essential for an adequate modeling of actinide species in aqueous solution, will be introduced. At the end of this chapter, computational parameters and procedures will be summarized. Chapter 4 presents the computational results including a comparison to available experimental data. In the beginning, the mononuclear hydrolysis product of UO{sub 2}{sup 2+}, [UO{sub 2}OH]{sup +}, will be discussed. The second part deals with actinide complexation by carboxylate ligands. First of all the coordination number for uranylacetate will be discussed with respect to implications for the complexation of actinides by humic substances followed by the uranyl complexation of aromatic carboxylic acids in comparison to earlier results for aliphatic ones. In the end, the ternary uranyl-hydroxo-acetate are discussed, as models of uranyl humate complexation at ambient condition.

  14. A relativistic density functional study of uranyl hydrolysis and complexation by carboxylic acids in aqueous solution

    International Nuclear Information System (INIS)

    Ray, Rupashree Shyama

    2009-01-01

    In this work, the complexation of uranium in its most stable oxidation state VI in aqueous solution was studied computationally, within the framework of density functional (DF) theory. The thesis is divided into the following parts: Chapter 2 briefly summarizes the relevant general aspects of actinide chemistry and then focuses on actinide environmental chemistry. Experimental results on hydrolysis, actinide complexation by carboxylic acids, and humic substances are presented to establish a background for the subsequent discussion. Chapter 3 describes the computational method used in this work and the relevant features of the parallel quantum chemistry code PARAGAUSS employed. First, the most relevant basics of the applied density functional approach are presented focusing on relativistic effects. Then, the treatment of solvent effects, essential for an adequate modeling of actinide species in aqueous solution, will be introduced. At the end of this chapter, computational parameters and procedures will be summarized. Chapter 4 presents the computational results including a comparison to available experimental data. In the beginning, the mononuclear hydrolysis product of UO_2"2"+, [UO_2OH]"+, will be discussed. The second part deals with actinide complexation by carboxylate ligands. First of all the coordination number for uranylacetate will be discussed with respect to implications for the complexation of actinides by humic substances followed by the uranyl complexation of aromatic carboxylic acids in comparison to earlier results for aliphatic ones. In the end, the ternary uranyl-hydroxo-acetate are discussed, as models of uranyl humate complexation at ambient condition.

  15. Approximate solutions for the two-dimensional integral transport equation. Solution of complex two-dimensional transport problems

    International Nuclear Information System (INIS)

    Sanchez, Richard.

    1980-11-01

    This work is divided into two parts: the first part deals with the solution of complex two-dimensional transport problems, the second one (note CEA-N-2166) treats the critically mixed methods of resolution. A set of approximate solutions for the isotropic two-dimensional neutron transport problem has been developed using the interface current formalism. The method has been applied to regular lattices of rectangular cells containing a fuel pin, cladding, and water, or homogenized structural material. The cells are divided into zones that are homogeneous. A zone-wise flux expansion is used to formulate a direct collision probability problem within a cell. The coupling of the cells is effected by making extra assumptions on the currents entering and leaving the interfaces. Two codes have been written: CALLIOPE uses a cylindrical cell model and one or three terms for the flux expansion, and NAUSICAA uses a two-dimensional flux representation and does a truly two-dimensional calculation inside each cell. In both codes, one or three terms can be used to make a space-independent expansion of the angular fluxes entering and leaving each side of the cell. The accuracies and computing times achieved with the different approximations are illustrated by numerical studies on two benchmark problems and by calculations performed in the APOLLO multigroup code [fr

  16. Comparative study of uranyl(VI) and -(V) carbonato complexes in an aqueous solution.

    Science.gov (United States)

    Ikeda, Atsushi; Hennig, Christoph; Tsushima, Satoru; Takao, Koichiro; Ikeda, Yasuhisa; Scheinost, Andreas C; Bernhard, Gert

    2007-05-14

    Electrochemical, complexation, and electronic properties of uranyl(VI) and -(V) carbonato complexes in an aqueous Na2CO3 solution have been investigated to define the appropriate conditions for preparing pure uranyl(V) samples and to understand the difference in coordination character between UO22+ and UO2+. Cyclic voltammetry using three different working electrodes of platinum, gold, and glassy carbon has suggested that the electrochemical reaction of uranyl(VI) carbonate species proceeds quasi-reversibly. Electrolysis of UO22+ has been performed in Na2CO3 solutions of more than 0.8 M with a limited pH range of 11.7 < pH < 12.0 using a platinum mesh electrode. It produces a high purity of the uranyl(V) carbonate solution, which has been confirmed to be stable for at least 2 weeks in a sealed glass cuvette. Extended X-ray absorption fine structure (EXAFS) measurements revealed the structural arrangement of uranyl(VI) and -(V) tricarbonato complexes, [UO2(CO3)3]n- [n = 4 for uranyl(VI), 5 for uranyl(V)]. The bond distances of U-Oax, U-Oeq, U-C, and U-Odist are determined to be 1.81, 2.44, 2.92, and 4.17 A for the uranyl(VI) complex and 1.91, 2.50, 2.93, and 4.23 A for the uranyl(V) complex, respectively. The validity of the structural parameters obtained from EXAFS has been supported by quantum chemical calculations for the uranyl(VI) complex. The uranium LI- and LIII-edge X-ray absorption near-edge structure spectra have been interpreted in terms of electron transitions and multiple-scattering features.

  17. The problem of complex eigensystems in the semianalytical solution for advancement of time in solute transport simulations: a new method using real arithmetic

    Science.gov (United States)

    Umari, Amjad M.J.; Gorelick, Steven M.

    1986-01-01

    In the numerical modeling of groundwater solute transport, explicit solutions may be obtained for the concentration field at any future time without computing concentrations at intermediate times. The spatial variables are discretized and time is left continuous in the governing differential equation. These semianalytical solutions have been presented in the literature and involve the eigensystem of a coefficient matrix. This eigensystem may be complex (i.e., have imaginary components) due to the asymmetry created by the advection term in the governing advection-dispersion equation. Previous investigators have either used complex arithmetic to represent a complex eigensystem or chosen large dispersivity values for which the imaginary components of the complex eigenvalues may be ignored without significant error. It is shown here that the error due to ignoring the imaginary components of complex eigenvalues is large for small dispersivity values. A new algorithm that represents the complex eigensystem by converting it to a real eigensystem is presented. The method requires only real arithmetic.

  18. Self-Assembly of Discrete Metal Complexes in Aqueous Solution via Block Copolypeptide Amphiphiles

    Directory of Open Access Journals (Sweden)

    Timothy J. Deming

    2013-01-01

    Full Text Available The integration of discrete metal complexes has been attracting significant interest due to the potential of these materials for soft metal-metal interactions and supramolecular assembly. Additionally, block copolypeptide amphiphiles have been investigated concerning their capacity for self-assembly into structures such as nanoparticles, nanosheets and nanofibers. In this study, we combined these two concepts by investigating the self-assembly of discrete metal complexes in aqueous solution using block copolypeptides. Normally, discrete metal complexes such as [Au(CN2]−, when molecularly dispersed in water, cannot interact with one another. Our results demonstrated, however, that the addition of block copolypeptide amphiphiles such as K183L19 to [Au(CN2]− solutions induced one-dimensional integration of the discrete metal complex, resulting in photoluminescence originating from multinuclear complexes with metal-metal interactions. Transmission electron microscopy (TEM showed a fibrous nanostructure with lengths and widths of approximately 100 and 20 nm, respectively, which grew to form advanced nanoarchitectures, including those resembling the weave patterns of Waraji (traditional Japanese straw sandals. This concept of combining block copolypeptide amphiphiles with discrete coordination compounds allows the design of flexible and functional supramolecular coordination systems in water.

  19. Highly photoluminescent europium tetraphenylimidodiphosphinate ternary complexes with heteroaromatic co-ligands. Solution and solid state studies

    Energy Technology Data Exchange (ETDEWEB)

    Pietraszkiewicz, Marek, E-mail: mpietraszkiewicz@ichf.edu.pl [Institute of Physical Chemistry, Polish Academy of Sciences, Kasprzaka 44/52, 01-224 Warsaw (Poland); Pietraszkiewicz, Oksana; Karpiuk, Jerzy; Majka, Alina [Institute of Physical Chemistry, Polish Academy of Sciences, Kasprzaka 44/52, 01-224 Warsaw (Poland); Dutkiewicz, Grzegorz; Borowiak, Teresa [Adam Mickiewicz University, Faculty of Chemistry, Department of Crystallography, Grunwaldzka 6, 60-780 Poznań (Poland); Kaczmarek, Anna M. [L3–Luminescent Lanthanide Lab, f-element coordination chemistry, Ghent University, Department of Inorganic and Physical Chemistry, Krijgslaan 281, Building S3, 9000 Gent (Belgium); Van Deun, Rik, E-mail: rik.vandeun@ugent.be [L3–Luminescent Lanthanide Lab, f-element coordination chemistry, Ghent University, Department of Inorganic and Physical Chemistry, Krijgslaan 281, Building S3, 9000 Gent (Belgium)

    2016-02-15

    Tetraphenylimidodiphosphinate (tpip) forms neutral 3:1 complexes with lanthanide ions. These complexes can accommodate one ancillary planar heterocyclic ligand to complement their coordination sphere of Eu{sup 3+} to coordination number 8. Several co-ligands were tested to form new complexes: 1,10-phenanthroline, bathophenanthroline, 2,4,6-tris(2-pyridyl)-1,3,5-triazine, dipyrido[3,2-f:2′,3′-h]quinoxaline and 2,2′:6′,2′′-terpyridine. The addition of heterocyclic N,N-bidentate co-ligands to the coordination sphere results in a dramatic (by a factor of 45–50) luminescence enhancement of the parent Eu(tpip){sub 3}. The solid-state measurements confirmed that the ancillary ligands strongly increased the photoluminescence quantum yield (PLQY) of the investigated complexes. - Highlights: • We have disovered highly photoluminescent ternary Eu(III) complexes. • They consist of Eu(III) tetraphenylimidodiphosphinate, and planar heterocyclic ligands. • The increase in photoluminescence quantum yields in solution is enhanced up to 50 times in solution. • The solid-state photoluminescence exceeds 80% at room temperature.

  20. Highly photoluminescent europium tetraphenylimidodiphosphinate ternary complexes with heteroaromatic co-ligands. Solution and solid state studies

    International Nuclear Information System (INIS)

    Pietraszkiewicz, Marek; Pietraszkiewicz, Oksana; Karpiuk, Jerzy; Majka, Alina; Dutkiewicz, Grzegorz; Borowiak, Teresa; Kaczmarek, Anna M.; Van Deun, Rik

    2016-01-01

    Tetraphenylimidodiphosphinate (tpip) forms neutral 3:1 complexes with lanthanide ions. These complexes can accommodate one ancillary planar heterocyclic ligand to complement their coordination sphere of Eu 3+ to coordination number 8. Several co-ligands were tested to form new complexes: 1,10-phenanthroline, bathophenanthroline, 2,4,6-tris(2-pyridyl)-1,3,5-triazine, dipyrido[3,2-f:2′,3′-h]quinoxaline and 2,2′:6′,2′′-terpyridine. The addition of heterocyclic N,N-bidentate co-ligands to the coordination sphere results in a dramatic (by a factor of 45–50) luminescence enhancement of the parent Eu(tpip) 3 . The solid-state measurements confirmed that the ancillary ligands strongly increased the photoluminescence quantum yield (PLQY) of the investigated complexes. - Highlights: • We have disovered highly photoluminescent ternary Eu(III) complexes. • They consist of Eu(III) tetraphenylimidodiphosphinate, and planar heterocyclic ligands. • The increase in photoluminescence quantum yields in solution is enhanced up to 50 times in solution. • The solid-state photoluminescence exceeds 80% at room temperature.

  1. Functions of chalcogenide electrodes in solutions of complexing reagents and interfering ions

    International Nuclear Information System (INIS)

    Kiyanskij, V.V.

    1990-01-01

    The possibility to modify chalcogenide electrodes and their behaviour in solutions of complexing reagents for the development of new methods of potentiometric titration has been studied. It is shown that complexing reagents (EDTA, cupferron, 8-hydroxyquinoline, sodium dithiocarbaminate) and Cu(2), Hg(2) produce a strong effect on the functions of Ag, Cu, Cd, Pb - selective electrodes, which is used for titration of potential-determining and non-potential-determining ions ions (Sr 2+ , La 3+ etc.) and also for modification of sulfide-selecting electrode. A method of potentiometric titration of sulfates and chlorides with modified Cd- and Ag-selective electrodes is suggested

  2. Solution XAS Analysis for Exploring the Active Species in Homogeneous Vanadium Complex Catalysis

    Science.gov (United States)

    Nomura, Kotohiro; Mitsudome, Takato; Tsutsumi, Ken; Yamazoe, Seiji

    2018-06-01

    Selected examples in V K-edge X-ray Absorption Near Edge Structure (XANES) analysis of a series of vanadium complexes containing imido ligands (possessing metal-nitrogen double bond) in toluene solution have been introduced, and their pre-edge and the edge were affected by their structures and nature of ligands. Selected results in exploring the oxidation states of the active species in ethylene dimerization/polymerization using homogeneous vanadium catalysts [consisting of (imido)vanadium(V) complexes and Al cocatalysts] by X-ray absorption spectroscopy (XAS) analyses have been introduced. It has been demonstrated that the method should provide more clear information concerning the active species in situ, especially by combination with the other methods (NMR and ESR spectra, X-ray crystallographic analysis, and reaction chemistry), and should be powerful tool for study of catalysis mechanism as well as for the structural analysis in solution.

  3. Geometry and quadratic nonlinearity of charge transfer complexes in solution: A theoretical study

    International Nuclear Information System (INIS)

    Mukhopadhyay, S.; Ramasesha, S.; Pandey, Ravindra; Das, Puspendu K.

    2011-01-01

    In this paper, we have computed the quadratic nonlinear optical (NLO) properties of a class of weak charge transfer (CT) complexes. These weak complexes are formed when the methyl substituted benzenes (donors) are added to strong acceptors like chloranil (CHL) or di-chloro-di-cyano benzoquinone (DDQ) in chloroform or in dichloromethane. The formation of such complexes is manifested by the presence of a broad absorption maximum in the visible range of the spectrum where neither the donor nor the acceptor absorbs. The appearance of this visible band is due to CT interactions, which result in strong NLO responses. We have employed the semiempirical intermediate neglect of differential overlap (INDO/S) Hamiltonian to calculate the energy levels of these CT complexes using single and double configuration interaction (SDCI). The solvent effects are taken into account by using the self-consistent reaction field (SCRF) scheme. The geometry of the complex is obtained by exploring different relative molecular geometries by rotating the acceptor with respect to the fixed donor about three different axes. The theoretical geometry that best fits the experimental energy gaps, β HRS and macroscopic depolarization ratios is taken to be the most probable geometry of the complex. Our studies show that the most probable geometry of these complexes in solution is the parallel displaced structure with a significant twist in some cases.

  4. EPR study of complex formation between copper (II) ions and sympathomimetic amines in aqueous solution

    Energy Technology Data Exchange (ETDEWEB)

    Preoteasa, E.A. [Inst. of Atomic Physics, IFIN, Bucharest (Romania); Duliu, O.G.; Grecu, V.V. [Bucharest, Univ. (Romania). Dept. of Atomic and Nuclear Physics

    1997-07-01

    The complex formation between sympathomimetic amines (SA): adrenaline (AD), noradrenaline (NA), dopamine (DA), ephedrine (ED) and p-tyramine (pTA), and Cu(II) ion in aqueous solution has been studied by X-band EPR at room temperature. Excepting pTA, all investigated SA yielded two types of complexes in different pH domains. All complexes consistent with a ligand fields having a distorted octahedral symmetry, i.e., hexacoordination of Cu(II). The covalence coefficient calculated from the isotropic g and A values has shown strong ionic sigma-type ligand bonds. A structural model with the Cu(II) ion bound by four catecholic O(hydroxy) atoms for the low pH complexes of AD, NA and DA is proposed. For the high pH complexes of the former compounds as well as for both Ed complexes, the authors suppose Cu(II) bound by two N (amino) and two O (hydroxy) atoms. The spectra are consistent to water binding on the longitudinal octahedron axis in all compounds excepting the high pH complex of Ed, where OH2- ions are bound. Possible implications for the SA-cell receptors interactions are discussed.

  5. Borate-polyol complexes in aqueous solution: determination of enthalpies by thermometric titrimetry.

    Science.gov (United States)

    Aruga, R

    1985-06-01

    Enthalpies for the reaction of borate with 1,2-ethanediol, 1,2-propanediol, 1,2,3-propanetriol and d-mannitol have been determined by thermometric titrimetry. From these enthalpies and equilibrium constants taken from the literature, corresponding entropies have been calculated. The data refer to aqueous solutions at 25 degrees and I = 1.0M (NaNO(3)). The results indicate reasons for the differences in the stabilities of the complexes.

  6. A model based bayesian solution for characterization of complex damage scenarios in aerospace composite structures.

    Science.gov (United States)

    Reed, H; Leckey, Cara A C; Dick, A; Harvey, G; Dobson, J

    2018-01-01

    Ultrasonic damage detection and characterization is commonly used in nondestructive evaluation (NDE) of aerospace composite components. In recent years there has been an increased development of guided wave based methods. In real materials and structures, these dispersive waves result in complicated behavior in the presence of complex damage scenarios. Model-based characterization methods utilize accurate three dimensional finite element models (FEMs) of guided wave interaction with realistic damage scenarios to aid in defect identification and classification. This work describes an inverse solution for realistic composite damage characterization by comparing the wavenumber-frequency spectra of experimental and simulated ultrasonic inspections. The composite laminate material properties are first verified through a Bayesian solution (Markov chain Monte Carlo), enabling uncertainty quantification surrounding the characterization. A study is undertaken to assess the efficacy of the proposed damage model and comparative metrics between the experimental and simulated output. The FEM is then parameterized with a damage model capable of describing the typical complex damage created by impact events in composites. The damage is characterized through a transdimensional Markov chain Monte Carlo solution, enabling a flexible damage model capable of adapting to the complex damage geometry investigated here. The posterior probability distributions of the individual delamination petals as well as the overall envelope of the damage site are determined. Copyright © 2017 Elsevier B.V. All rights reserved.

  7. Mass spectrometric studies of the complexing behaviour of actinide ions in solution

    International Nuclear Information System (INIS)

    Steppert, Michael

    2012-01-01

    As the long-term radiotoxicity of spent nuclear fuel is governed by Plutonium and the Minor Actinides, these elements are focussed on for investigations in the framework of safety assessment for nuclear waste repositories. To shed more light on the selectivity of the partitioning ligands BTP and BTBP towards the extraction of trivalent actinides, the complexes these ligands form with lanthanides in octanolic solution were characterized. The differences in the extraction efficiencies among the different lanthanides were traced back to the varying preferential formation of Ln(BTP)3 complexes, depending on the ionic radius of the lanthanides. Additionally it was shown that depending on the sterical demand of BTBP ligands nitrate anions coordinate in the first coordination shell of Eu(BTBP)2-complexes. As the behavior of Plutonium under geochemical conditions is of particular interest for the safety assessment of potential nuclear waste repositories, the second part of the thesis focuses on the hydrolysis and colloid formation behavior of aqueous Plutonium solutions. The solution species of Zirconium(IV) as analogue for Plutonium(IV) as well as of Uranium(VI) and Plutonium(VI) were characterized and quantified by means of electrospray ionization mass spectrometry. Moreover the colloid-induced reduction of Pu(V) to Pu(IV) and the subsequent formation of colloidal species was investigated. [de

  8. Neptunium carbonato complexes in aqueous solution: an electrochemical, spectroscopic, and quantum chemical study.

    Science.gov (United States)

    Ikeda-Ohno, Atsushi; Tsushima, Satoru; Takao, Koichiro; Rossberg, André; Funke, Harald; Scheinost, Andreas C; Bernhard, Gert; Yaita, Tsuyoshi; Hennig, Christoph

    2009-12-21

    The electrochemical behavior and complex structure of Np carbonato complexes, which are of major concern for the geological disposal of radioactive wastes, have been investigated in aqueous Na(2)CO(3) and Na(2)CO(3)/NaOH solutions at different oxidation states by using cyclic voltammetry, X-ray absorption spectroscopy, and density functional theory calculations. The end-member complexes of penta- and hexavalent Np in 1.5 M Na(2)CO(3) with pH = 11.7 have been determined as a transdioxo neptunyl tricarbonato complex, [NpO(2)(CO(3))(3)](n-) (n = 5 for Np(V), and 4 for Np(VI)). Hence, the electrochemical reaction of the Np(V/VI) redox couple merely results in the shortening/lengthening of bond distances mainly because of the change of the cationic charge of Np, without any structural rearrangement. This explains the observed reversible-like feature on their cyclic voltammograms. In contrast, the electrochemical oxidation of Np(V) in a highly basic carbonate solution of 2.0 M Na(2)CO(3)/1.0 M NaOH (pH > 13) yielded a stable heptavalent Np complex of [Np(VII)O(4)(OH)(2)](3-), indicating that the oxidation reaction from Np(V) to Np(VII) in the carbonate solution involves a drastic structural rearrangement from the transdioxo configuration to a square-planar-tetraoxo configuration, as well as exchanging the coordinating anions from carbonate ions (CO(3)(2-)) to hydroxide ions (OH(-)).

  9. Small vessel disease, neurovascular regulation and cognitive impairment: post-mortem studies reveal a complex relationship, still poorly understood.

    Science.gov (United States)

    Love, Seth; Miners, J Scott

    2017-07-15

    The contribution of vascular disease to cognitive impairment is under-recognized and the pathogenesis is poorly understood. This information gap has multiple causes, including a lack of post-mortem validation of clinical diagnoses of vascular cognitive impairment (VCI) or vascular dementia (VaD), the exclusion of cases with concomitant neurodegenerative disease when diagnosing VCI/VaD, and a lack of standardization of neuropathological assessment protocols for vascular disease. Other contributors include a focus on end-stage destructive lesions to the exclusion of more subtle types of diffuse brain injury, on structural abnormalities of arteries and arterioles to the exclusion of non-structural abnormalities and capillary damage, and the use of post-mortem sampling strategies that are biased towards the identification of neurodegenerative pathologies. Recent studies have demonstrated the value of detailed neuropathology in characterizing vascular contributions to cognitive impairment (e.g. in diabetes), and highlight the importance of diffuse white matter changes, capillary damage and vasoregulatory abnormalities in VCI/VaD. The use of standardized, evidence-based post-mortem assessment protocols and the inclusion of biochemical as well as morphological methods in neuropathological studies should improve the accuracy of determination of the contribution of vascular disease to cognitive impairment and clarify the relative contribution of different pathogenic processes to the tissue damage. © 2017 The Author(s). published by Portland Press Limited on behalf of the Biochemical Society.

  10. Solution or suspension - Does it matter for lipid based systems? In vivo studies of chase dosing lipid vehicles with aqueous suspensions of a poorly soluble drug.

    Science.gov (United States)

    Larsen, A T; Holm, R; Müllertz, A

    2017-08-01

    In this study, the potential of co-administering an aqueous suspension with a placebo lipid vehicle, i.e. chase dosing, was investigated in rats relative to the aqueous suspension alone or a solution of the drug in the lipid vehicle. The lipid investigated in the present study was Labrafil M2125CS and three evaluated poorly soluble model compounds, danazol, cinnarizine and halofantrine. For cinnarizine and danazol the oral bioavailability in rats after chase dosing or dosing the compound dissolved in Labrafil M21515CS was similar and significantly higher than for the aqueous suspension. For halofantrine the chase dosed group had a tendency towards a low bioavailability relative to the Labrafil M2125CS solution, but still a significant higher bioavailability relative to the aqueous suspension. This could be due to factors such as a slower dissolution rate in the intestinal phase of halofantrine or a lower solubility in the colloidal structures formed during digestion, but other mechanisms may also be involved. The study thereby supported the potential of chase dosing as a potential dosing regimen in situations where it is beneficial to have a drug in the solid state, e.g. due to chemical stability issues in the lipid vehicle. Copyright © 2017 Elsevier B.V. All rights reserved.

  11. Soil solution and sugar maple response to NH(4)NO (3) additions in a base-poor northern hardwood forest of Québec, Canada.

    Science.gov (United States)

    Moore, Jean-David; Houle, Daniel

    2009-08-01

    Nitrogen additions (NH4NO3) at rates of three- and ten-fold ambient atmospheric deposition (8.5 kg ha(-1) year(-1)) were realised in an acid- and base-poor northern hardwood forest of Québec, Canada. Soil solution chemistry, foliar chemistry, crown dieback and basal area growth of sugar maple (Acer saccharum Marsh.) were measured. Except for a transitory increase of NO3 and NH4 concentrations, there was no persistent increase in their level in soil solution 3 years after N treatments, with the exception of one plot out of three, that received the highest N addition, beginning to show persistent and high NO3 concentrations after 2 years of N additions. Three years of N additions have significantly increased the N DRIS index of sugar maple but not N foliar concentration. Potassium, Ca and Mn foliar concentrations, as well as P and Ca DRIS indices, decreased in treated plots after 3 years. No treatment effect was observed for basal area growth and dieback rate. One unexpected result was the significant decrease in foliar Ca even in the treated plots that received low N rates, despite the absence of significant NO3-induced leaching of Ca. The mechanism responsible for the decrease in foliar Ca is not known. Our results, however, clearly demonstrate that increased N deposition at sites with low base saturation may affect Ca nutrition even when clear signs of N saturation are not observed.

  12. The solution of a chiral random matrix model with complex eigenvalues

    International Nuclear Information System (INIS)

    Akemann, G

    2003-01-01

    We describe in detail the solution of the extension of the chiral Gaussian unitary ensemble (chGUE) into the complex plane. The correlation functions of the model are first calculated for a finite number of N complex eigenvalues, where we exploit the existence of orthogonal Laguerre polynomials in the complex plane. When taking the large-N limit we derive new correlation functions in the case of weak and strong non-Hermiticity, thus describing the transition from the chGUE to a generalized Ginibre ensemble. We briefly discuss applications to the Dirac operator eigenvalue spectrum in quantum chromodynamics with non-vanishing chemical potential. This is an extended version of hep-th/0204068

  13. Selection of rational technical solutions in designing a robotized assembly complex

    International Nuclear Information System (INIS)

    Petrov, B.M.; Rasulbekov, R.I.

    1984-01-01

    One of the methods permitting a more objective approach to decision making in design is the method of ordered search which, in combination with the methods of expert estimate was used in designing the robotized assembly-finishing complex for automobile tires. The assembly-finishing complex consists of a number of functionally independent parts, i.e., modules provided with manipulators and mutually connected by a transport system with intermediate storage. The modified method of ordered search, examined in the present work, was therefore used for each module separately, and not for the complex as a whole. We will examine the main principles of our approach to the selection of design solutions for the example of a module for laying on the bottom-cushion cords

  14. Nitrate adsorption from aqueous solution using granular chitosan-Fe{sup 3+} complex

    Energy Technology Data Exchange (ETDEWEB)

    Hu, Qili [School of Water Resources and Environment, China University of Geosciences (Beijing), Beijing, 100083 (China); Key Laboratory of Groundwater Cycle and Environment Evolution,China University of Geosciences (Beijing), Ministry of Education, Beijing, 100083 (China); Chen, Nan, E-mail: chennan@cugb.edu.cn [School of Water Resources and Environment, China University of Geosciences (Beijing), Beijing, 100083 (China); Key Laboratory of Groundwater Cycle and Environment Evolution, China University of Geosciences (Beijing), Ministry of Education, Beijing, 100083 (China); Feng, Chuanping [School of Water Resources and Environment, China University of Geosciences (Beijing), Beijing, 100083 (China); Key Laboratory of Groundwater Cycle and Environment Evolution, China University of Geosciences (Beijing), Ministry of Education, Beijing, 100083 (China); Hu, WeiWu [The Journal Center, China University of Geosciences (Beijing), Beijing, 100083 (China)

    2015-08-30

    Highlights: • Granular chitosan-Fe{sup 3+} complex had high performance for nitrate adsorption. • Granular chitosan-Fe{sup 3+} complex had shorter equilibrium time (1.5 h). • Nitrate adsorption was ascribed to ion exchange and electrostatic attraction. • Granular chitosan-Fe{sup 3+} complex could be regenerated using NaCl solution. - Abstract: In the present study, In order to efficiently remove nitrate, granular chitosan-Fe{sup 3+} complex with high chemical stability and good environmental adaptation was synthesized through precipitation method and characterized using SEM, XRD, BET and FTIR. The nitrate adsorption performance was evaluated by batch experiments. The results indicated that granular chitosan-Fe{sup 3+} complex was an amorphous and mesoporous material. The BET specific surface area and average pore size were 8.98 m{sup 2} g{sup −1} and 56.94 Å, respectively. The point of zero charge was obtained at pH 5. The maximum adsorption capacity reached 8.35 mg NO{sub 3}{sup −}-N g{sup −1} based on Langmuir–Freundlich model. Moreover, no significant change in the nitrate removal efficiency was observed in the pH range of 3.0–10.0. The adverse influence of sulphate on nitrate removal was the most significant, followed by bicarbonate and fluoride, whereas chloride had slightly adverse effect. Adsorption process followed the pseudo-second-order kinetic model, and the experimental equilibrium data were fitted well with the Langmuir–Freundlich and D–R isotherm models. Thermodynamic parameters revealed that nitrate adsorption was a spontaneous and exothermic process. Granular chitosan-Fe{sup 3+} complex could be effectively regenerated by NaCl solution.

  15. EPR spectra of vanadyl(2) intra-complexes with amino acids in solutions

    International Nuclear Information System (INIS)

    Shodiev, U.M.; Musaev, Z.M.; Khodzhaev, O.F.; Usmankhodzhaeva, Ya.S.; Parpiev, N.A.

    1987-01-01

    EPR spectra of vanadyl (2) intracomplexes with glycine, α- and β-alanines, benzoylglycine, lencine, glutamine and the aspartic acid of VOL 2 xH 2 O composition as well as with cystine of VOLxH 2 O composition (where L-monodeprotonated, in case of cystine and the aspartic acid - dideprotonated form of the amino acid) in aqueous, methanol, dimethylsulfoxide and pyridine solutions are studied. It is established that the structure determined in the solid state is retained in the dimethylsulfoxide solution and partially - in methanol. In aqueous, pyridine and partially in methanol solutions complexes are distorted and two molecules of the amino acid are coordinated monodentately through oxygen atoms of the carboxyl group, and ''vacant'' coordination places in the equatorial plane take two molecules of the solvent. From the data obtained it follows that the metal - nitrogen bond in the vanadyl (2) complexes studied with amino acids is not so strong than the metal - oxygen bond of the carboxyl ligand group

  16. Thermodynamics of mixed-ligand complex formation of mercury (II) ethylenediaminetetraacetate with amino acids in solution

    Energy Technology Data Exchange (ETDEWEB)

    Pyreu, Dmitrii, E-mail: pyreu@mail.ru [Department of Inorganic and Analytic Chemistry, Ivanovo State University, Ermak 39, Ivanovo 153025 (Russian Federation); Kozlovskii, Eugenii [Department of Inorganic and Analytic Chemistry, Ivanovo State University, Ermak 39, Ivanovo 153025 (Russian Federation); Gruzdev, Matvei; Kumeev, Roman [Institute of Solution Chemistry, Ivanovo (Russian Federation)

    2012-11-20

    Highlights: Black-Right-Pointing-Pointer Stable mixed ligand complexes of HgEdta with amino acids at physiological pH value. Black-Right-Pointing-Pointer The thermodynamic and NMR data evident the ambidentate coordination mode of arginine. Black-Right-Pointing-Pointer Participation of the guanidinic group of Arg in coordination process. Black-Right-Pointing-Pointer Binuclear complexes (HgEdta){sub 2}L with the bridging function of amino acid. - Abstract: The mixed-ligand complex formation in the systems Hg{sup 2+} - Edta{sup 4-} - L{sup -}(L = Arg, Orn, Ser) has been studied by means of calorimetry, pH-potentiometry and NMR spectroscopy in aqueous solution at 298.15 K and the ionic strength of I = 0.5 (KNO{sub 3}). The thermodynamic parameters of formation of the HgEdtaL, HgEdtaHL and (HgEdta){sub 2}L complexes have been determined. The most probable coordination mode for the complexone and the amino acid in the mixed-ligand complexes was discussed.

  17. Complex formation between neptunium(V) and various thiosemicarbazide derivatives in aqueous solution

    International Nuclear Information System (INIS)

    Chuguryan, D.G.; Dzyubenko, V.I.; Gerbeleu, N.V.

    1987-01-01

    Complex formation between neptunium(V) and various thiosemicarbazide derivatives in solution has been studied spectrophotometrically in the pH range 4-10. Stepwise formation of three types of complexes, with composition NpO 2 HA, NpO 2 A - , and NpOHA 2- , has been demonstrated with salicylaldehyde thiosemicarbazone (H 2 L) and salicylaldehyde S-methyl-isothiosemicarbazone (H 2 Q) at t = 25 +/- 1 0 C and μ = 0.05. The logarithmic stability constants of the first two complexes are 5.14 +/- 0.06, 11.85 +/- 0.04 and 8.42 +/- 0.09, 13.33 +/- 0.015 for H 2 L and H 2 Q, respectively; equilibrium constants for the formation of hydroxo complexes of the form NpO 2 OHL 2- and NpO 2 OHQ 2- were also determined, and found to be equal to (2.23 +/-0.37) x 10 -5 and (5.02 +/- 0.9) x 10 -5 , respectively. In the case of S-methyl-N 1 ,N 4 -bis(salicylidene)isothiosemicarbazide (H 2 Z), only one type of complex is formed under these experimental conditions, namely, NpO 2 Z - , with a logarithmic stability constant of 4.78 +/- 0.03. Dissociation constants for H 2 Q and H 2 Z were also determined

  18. Self-assembly of a helical zinc-europium complex: speciation in aqueous solution and luminescence

    Directory of Open Access Journals (Sweden)

    Emmanuel eDeiters

    2013-09-01

    Full Text Available Two new tridentate(NNO-bidentate(NN compartmental ligands, HL5 and HL6, are synthesized from pyridine and benzimidazole synthons. They react in aqueous solution under physiological conditions with ZnII, LnIII, or a mixture thereof, to yield complexes of different stoichiometries, 1:3, 2:2, 2:3, 1:1:3, the speciation of which is established by UV-visible titrations and ESI mass spectrometry. Photophysical studies of the EuIII-containing solutions in Tris-HCl 0.1 M (pH = 7.4 show that lanthanide luminescence arises from a unique N6O3 coordination site with pseudo D3 symmetry. Relevant parameters such as crystal field splitting, lifetime, radiative lifetime and intrinsic quantum yield perfectly match those reported for dinuclear 4f-4f helicates in which the EuIII ion has the same coordination environment.

  19. Removal of Lead Hydroxides Complexes from Solutions Formed in Silver/Gold: Cyanidation Process

    Science.gov (United States)

    Parga, José R.; Martinez, Raul Flores; Moreno, Hector; Gomes, Andrew Jewel; Cocke, David L.

    2014-04-01

    The presence of lead hydroxides in "pregnant cyanide solution" decreases the quality of the Dore obtained in the recovery processes of gold and silver, so it is convenient to remove them. The adsorbent capacity of the low cost cow bone powder was investigated for the removal of lead ions from a solution of lead hydroxide complexes at different initial metal ion concentrations (10 to 50 mg/L), and reaction time. Experiments were carried out in batches. The maximum sorption capacity of lead determined by the Langmuir model was found to be 126.58 mg/g, and the separation factor R L was between 0 and 1, indicating a significant affinity of bone for lead. Experimental data follow pseudo-second order kinetics suggesting chemisorption. It is concluded that cow bone powder can be successfully used for the removal of lead ions, and improves the quality of the silver-gold cyanides precipitate.

  20. Formation of ammonia complexes of alkaline earth elements in aqueous solutions

    International Nuclear Information System (INIS)

    Padar, T.G.; Stupko, T.V.; Isaev, I.D.; Pashkov, G.L.; Mironov, V.E.

    1990-01-01

    Coefficients of ammonia distribution between aqueous solutions of calcium, strontium, barium and ammonium perchlorate mixtures at ionic strength - 0.50; 1.0 and 1.5 at 298.2 K and ammonia concentrations 0.2-10 mol/dm 3 are measured. Formation of ammonia complexes of M(NH 3 ) n 2+ composition is shown. Logarithms of stepped stability constants for solutions with zero ionic strength for Ca 2+ are: -0.13; -0.25; -0.52 and -0.77, where n=1-4; for Sr 2+ : -0.04; -0.42 and -0.70, where n=1-3 and for Ba 2+ : -0.11; -0.50 and 0.76, where n=1-3

  1. Characterization of amorphous yttria layers deposited by aqueous solutions of Y-chelate alkoxides complex

    Science.gov (United States)

    Kim, Young-Soon; Lee, Yu-Ri; Kim, Byeong-Joo; Lee, Jae-Hun; Moon, Seung-Hyun; Lee, Hunju

    2015-01-01

    Crack-free amorphous yttria layers were deposited by dip coating in solutions of different Y-chelate alkoxides complex. Three Y-chelate solutions of different concentrations were prepared using yttrium acetate tetrahydrate, yttrium stearic acid as Y source materials. PEG, diethanolamine were used as chelating agents, while ethanol, methanol and tetradecane were used as solvent. Three different combinations of chelating and solvents were used to prepare solutions for Y2O3 dip coating on SUS, electropolished and non-electropolished Hastelloy C-276 substrates. The thickness of the films was varied by changing the number of dipping cycles. At an optimized condition, the substrate surface roughness (rms) value was reduced from ∼50 nm to ∼1 nm over a 10 × 10 μm2 area. After Y2O3 deposition, MgO was deposited using ion-beam assisted deposition (IBAD), then LaMnO3 (LMO) was deposited using sputtering and GdBCO was deposited using reactive co-evaporation by deposition and reaction (RCE-DR). Detailed X-ray study indicates that LMO/MgO/Y2O3 and GdBCO/LMO/MgO/Y2O3 stack films have good out-of-plane and in-plane textures with strong c-axis alignment. The critical current (Ic) of GdBCO/LMO/MgO/Y2O3 multilayer structure varied from 190 to 420 A/cm with different solutions, when measured at 77 K. These results demonstrated that amorphous yttria can be easily deposited by dip coating using Y-chelates complex as a diffusion barrier and nucleation layer.

  2. γ-radiolysis of aqueous and aqueous-ethanol solutions of cobalt(3) cyanide complexes

    International Nuclear Information System (INIS)

    Kutsaev, V.G.; Potapov, I.A.; Rozenkevich, M.B.; Sakharovskij, Yu.A.; Bulgakova, G.P.; Zagorets, P.A.

    1984-01-01

    The method of stationary γ-radiolysis has been used to investigate Na 3 [Co 3 (CN) 6 ] and K 2 [Co 3 (CN) 5 H 2 O] reduction in aqueous solutions in the presence of NaCN, KCN, KCl and C 2 H 5 OH additions. [Co 2 (CN) 5 ] 3- ion is shown to be the product of reduction. Radiation-chemical yield increases in the presence of alkali metal cyanides and large quantities (10-20 vol.%) of C 2 H 5 OH. Energy consumption for radiation-chemical reduction of Co 3 cyanide complexes is 50 times lower than for photochemical one

  3. Low-complexity computation of plate eigenmodes with Vekua approximations and the method of particular solutions

    Science.gov (United States)

    Chardon, Gilles; Daudet, Laurent

    2013-11-01

    This paper extends the method of particular solutions (MPS) to the computation of eigenfrequencies and eigenmodes of thin plates, in the framework of the Kirchhoff-Love plate theory. Specific approximation schemes are developed, with plane waves (MPS-PW) or Fourier-Bessel functions (MPS-FB). This framework also requires a suitable formulation of the boundary conditions. Numerical tests, on two plates with various boundary conditions, demonstrate that the proposed approach provides competitive results with standard numerical schemes such as the finite element method, at reduced complexity, and with large flexibility in the implementation choices.

  4. Approximate analytical solutions in the analysis of elastic structures of complex geometry

    Science.gov (United States)

    Goloskokov, Dmitriy P.; Matrosov, Alexander V.

    2018-05-01

    A method of analytical decomposition for analysis plane structures of a complex configuration is presented. For each part of the structure in the form of a rectangle all the components of the stress-strain state are constructed by the superposition method. The method is based on two solutions derived in the form of trigonometric series with unknown coefficients using the method of initial functions. The coefficients are determined from the system of linear algebraic equations obtained while satisfying the boundary conditions and the conditions for joining the structure parts. The components of the stress-strain state of a bent plate with holes are calculated using the analytical decomposition method.

  5. Intelligent monitoring and fault diagnosis for ATLAS TDAQ: a complex event processing solution

    CERN Document Server

    Magnoni, Luca; Luppi, Eleonora

    Effective monitoring and analysis tools are fundamental in modern IT infrastructures to get insights on the overall system behavior and to deal promptly and effectively with failures. In recent years, Complex Event Processing (CEP) technologies have emerged as effective solutions for information processing from the most disparate fields: from wireless sensor networks to financial analysis. This thesis proposes an innovative approach to monitor and operate complex and distributed computing systems, in particular referring to the ATLAS Trigger and Data Acquisition (TDAQ) system currently in use at the European Organization for Nuclear Research (CERN). The result of this research, the AAL project, is currently used to provide ATLAS data acquisition operators with automated error detection and intelligent system analysis. The thesis begins by describing the TDAQ system and the controlling architecture, with a focus on the monitoring infrastructure and the expert system used for error detection and automated reco...

  6. A Solution Study of Complex Formation of Some Diamines with Lanthanones

    Directory of Open Access Journals (Sweden)

    J. J. Vora

    2009-01-01

    Full Text Available To study the metal ligand equilibrium in aqueous solution, the well known Irving-Rossotti titration method was used. The temperature selected is 30±0.10C at ionic strength 0.2 M (NaClO4 which was maintained constant through out the work. The binary metal complex (ML2 formation was studied. The metals selected are Sm3+, Gd3+, Dy3+ and Yb3+. The diamine ligands taken are ethylenediamine, 1,2 diamino propane, 1,3 diamino propane, N-N diethyl ethylenediamine and N-N -dimethyl ethylenediamine. Factors that affected the stability of the complexes are size and ionic potential of lanthanone ions, basicity of ligands, ring size and steric effect of ligands.

  7. Comment on "Defocusing complex short-pulse equation and its multi-dark-soliton solution"

    Science.gov (United States)

    Youssoufa, Saliou; Kuetche, Victor K.; Kofane, Timoleon C.

    2017-08-01

    In their recent paper, Feng et al. [Phys. Rev. E 93, 052227 (2016), 10.1103/PhysRevE.93.052227] proposed a complex short-pulse equation of both focusing and defocusing types. They studied in detail the defocusing case and derived its multi-dark-soliton solutions. Nonetheless, from a physical viewpoint in order to better and deeply understand their genuine implications, we find it useful to provide a real and proper background for the derivation of the previous evolution system while showing that the expression of the nonlinear electric polarization the above authors used in their scheme is not suitable for getting the defocusing complex short-pulse equation.

  8. Synthesis, solid and solution studies of paraquat dichloride calixarene complexes. Molecular modelling

    International Nuclear Information System (INIS)

    Garcia S, I.; Ramirez, F. M.

    2010-01-01

    The interaction of the herbicide paraquat dichloride (P Q, substrate) with p-tert-butylcalix arenas (L, receptor) was investigated in both the solution and solid states. The isolated paraquat calixarene complexes were characterised by UV-visible, 1 H NMR, ESI-Ms, Luminescence and IR spectroscopies and elemental analysis. The stoichiometry of complexes 1 and 2 was 1:1 (1 herbicide: 1 calixarene) and both revealed a biexponential luminescence decay with lifetimes depending on the size and the conformational particularity of the calixarenes. Molecular modelling suggested that both calixarenes interact with the herbicide through cation-π interaction. P Q in included in the p-tert butylcalix a rene cavity, a situation favoured by its pinched conformation in polar solvent while it is partially included in the p-tert butylcalix a rene cavity because of its in-out cone conformation. The theoretical results, in particular using Mopac procedures, were in agreement with the experimental findings. (Author)

  9. Synthesis, solid and solution studies of paraquat dichloride calixarene complexes. Molecular modelling

    Energy Technology Data Exchange (ETDEWEB)

    Garcia S, I.; Ramirez, F. M., E-mail: flor.ramirez@inin.gob.m [ININ, Departamento de Quimica, Carretera Mexico-Toluca s/n, 52750 Ocoyoacac, Estado de Mexico (Mexico)

    2010-07-01

    The interaction of the herbicide paraquat dichloride (P Q, substrate) with p-tert-butylcalix arenas (L, receptor) was investigated in both the solution and solid states. The isolated paraquat calixarene complexes were characterised by UV-visible, {sup 1}H NMR, ESI-Ms, Luminescence and IR spectroscopies and elemental analysis. The stoichiometry of complexes 1 and 2 was 1:1 (1 herbicide: 1 calixarene) and both revealed a biexponential luminescence decay with lifetimes depending on the size and the conformational particularity of the calixarenes. Molecular modelling suggested that both calixarenes interact with the herbicide through cation-{pi} interaction. P Q in included in the p-tert butylcalix a rene cavity, a situation favoured by its pinched conformation in polar solvent while it is partially included in the p-tert butylcalix a rene cavity because of its in-out cone conformation. The theoretical results, in particular using Mopac procedures, were in agreement with the experimental findings. (Author)

  10. Plutonium (IV) complexation by nitrate in acid solutions of ionic strengths from 2 to 19 molal

    International Nuclear Information System (INIS)

    Berg, J.M.; Veirs, D.K.; Vaughn, R.B.; Cisneros, M.A.; Smith, C.A.

    1997-01-01

    Titrations of Pu(IV) with HNO 3 in a series of aqueous HClO 4 solutions ranging in ionic strength from 2 to 19 molal were followed using absorption spectrophotometry. The Pu 5f-5f spectra in the visible and near IR range change with complex formation. At each ionic strength, a series of spectra were obtained by varying nitrate concentration. Each series was deconvoluted into spectra f Pu 4+ (aq), Pu(NO 3 ) 3+ and Pu(NO 3 ) 2 2+ complexes, and simultaneously their formation constants were determined. When corrected for the incomplete dissociation of nitric acid, the ionic strength dependence of each formation constant can be described by two parameters, β 0 and Δ var-epsilon using the formulae of specific ion interaction theory. The difficulties with extending this analysis to higher nitrate coordination numbers are discussed

  11. Effect of Concentration on the Electrochemistry and Speciation of the Magnesium Aluminum Chloride Complex Electrolyte Solution.

    Science.gov (United States)

    See, Kimberly A; Liu, Yao-Min; Ha, Yeyoung; Barile, Christopher J; Gewirth, Andrew A

    2017-10-18

    Magnesium batteries offer an opportunity to use naturally abundant Mg and achieve large volumetric capacities reaching over four times that of conventional Li-based intercalation anodes. High volumetric capacity is enabled by the use of a Mg metal anode in which charge is stored via electrodeposition and stripping processes, however, electrolytes that support efficient Mg electrodeposition and stripping are few and are often prepared from highly reactive compounds. One interesting electrolyte solution that supports Mg deposition and stripping without the use of highly reactive reagents is the magnesium aluminum chloride complex (MACC) electrolyte. The MACC exhibits high Coulombic efficiencies and low deposition overpotentials following an electrolytic conditioning protocol that stabilizes species necessary for such behavior. Here, we discuss the effect of the MgCl 2 and AlCl 3 concentrations on the deposition overpotential, current density, and the conditioning process. Higher concentrations of MACC exhibit enhanced Mg electrodeposition current density and much faster conditioning. An increase in the salt concentrations causes a shift in the complex equilibria involving both cations. The conditioning process is strongly dependent on the concentration suggesting that the electrolyte is activated through a change in speciation of electrolyte complexes and is not simply due to the annihilation of electrolyte impurities. Additionally, the presence of the [Mg 2 (μ-Cl) 3 ·6THF] + in the electrolyte solution is again confirmed through careful analysis of experimental Raman spectra coupled with simulation and direct observation of the complex in sonic spray ionization mass spectrometry. Importantly, we suggest that the ∼210 cm -1 mode commonly observed in the Raman spectra of many Mg electrolytes is indicative of the C 3v symmetric [Mg 2 (μ-Cl) 3 ·6THF] + . The 210 cm -1 mode is present in many electrolytes containing MgCl 2 , so its assignment is of broad interest

  12. Exact solutions for oscillatory shear sweep behaviors of complex fluids from the Oldroyd 8-constant framework

    Science.gov (United States)

    Saengow, Chaimongkol; Giacomin, A. Jeffrey

    2018-03-01

    In this paper, we provide a new exact framework for analyzing the most commonly measured behaviors in large-amplitude oscillatory shear flow (LAOS), a popular flow for studying the nonlinear physics of complex fluids. Specifically, the strain rate sweep (also called the strain sweep) is used routinely to identify the onset of nonlinearity. By the strain rate sweep, we mean a sequence of LAOS experiments conducted at the same frequency, performed one after another, with increasing shear rate amplitude. In this paper, we give exact expressions for the nonlinear complex viscosity and the corresponding nonlinear complex normal stress coefficients, for the Oldroyd 8-constant framework for oscillatory shear sweeps. We choose the Oldroyd 8-constant framework for its rich diversity of popular special cases (we list 18 of these). We evaluate the Fourier integrals of our previous exact solution to get exact expressions for the real and imaginary parts of the complex viscosity, and for the complex normal stress coefficients, as functions of both test frequency and shear rate amplitude. We explore the role of infinite shear rate viscosity on strain rate sweep responses for the special case of the corotational Jeffreys fluid. We find that raising η∞ raises the real part of the complex viscosity and lowers the imaginary. In our worked examples, we thus first use the corotational Jeffreys fluid, and then, for greater accuracy, we use the Johnson-Segalman fluid, to describe the strain rate sweep response of molten atactic polystyrene. For our comparisons with data, we use the Spriggs relations to generalize the Oldroyd 8-constant framework to multimode. Our generalization yields unequivocally, a longest fluid relaxation time, used to assign Weissenberg and Deborah numbers to each oscillatory shear flow experiment. We then locate each experiment in the Pipkin space.

  13. Solution of the scattering T matrix equation in discrete complex momentum space

    International Nuclear Information System (INIS)

    Rawitscher, G.H.; Delic, G.

    1984-01-01

    The scattering solution to the Lippmann-Schwinger equation is expanded into a set of spherical Bessel functions of complex wave numbers, K/sub j/, with j = 1,2 , . . . , M. The value of each K/sub j/ is determined from the condition that the spherical Bessel function smoothly matches onto an asymptotically outgoing spherical Hankel (or Coulomb) function of the correct physical wave number at a matching point R. The spherical Bessel functions thus determined are Sturmian functions, and they form a complete set in the interval 0 to R. The coefficients of the expansion of the scattering function are determined by matrix inversion of a linear set of algebraic equations, which are equivalent to the solution of the T-matrix equation in complex momentum space. In view of the presence of a matching radius, no singularities are encountered for the Green's functions, and the inclusion of Coulomb potentials offers no computational difficulties. Three numerical examples are performed in order to illustrate the convergence of the elastic scattering matrix S with M. One of these consists of a set of coupled equations which describe the breakup of a deuteron as it scatters from the nucleus on 58 Ni. A value of M of 15 or less is found sufficient to reproduce the exact S matrix element to an accuracy of four figures after the decimal point

  14. Effects of solution pH and complexing reagents on uranium and thorium desorption under saturated equilibrium conditions

    International Nuclear Information System (INIS)

    Wang, Yug-Yea; Yu, C.

    1992-01-01

    Three contaminated bulk surface soils were used for investigating the effect of solution pH and complexing reagents on uranium and thorium desorption. At a low solution pH, the major chemical species of uranium and thorium, uranyl UO 2 +2 , thorium dihydroxide Th(OH) 2 +2 , and thorium hydroxide Th(OH) +3 , tend to form complexes with acetates in the solution phase, which increases the fractions of uranium and thorium desorbed into this phase. At a high solution pH, important uranium and thorium species such as uranyl tricarbonate complex UO 2 (CO) 33 -4 and thorium tetrahydroxide complex Th(OH) 4 tend to resist complexation with acetates. The presence of complexing reagents in solution can release radionuclides such as uranium and/or thorium from the soil to the solution by forming soluble complexes. Sodium bicarbonate (NaHCO 3 ) and diethylenetriaminepentaacetic acid (DTPA) are strong complex formers that released 38% to 62% of total uranium activity and 78% to 86% of total thorium activity, respectively, from the soil samples investigated. Solutions of 0.1 molar sodium nitrate (NaNO 3 ) and 0.1 molar sodium sulfate (Na 2 SO 4 ) were not effective complex formers with uranium and thorium under the experimental conditions. Fractions of uranium and thorium desorbed by 0.15g/200ml humic acid ranged from 4.62% to 6.17% and 1.59% to 7.09%, respectively. This work demonstrates the importance of a knowledge of solution chemistry in investigating the desorption of radionuclides

  15. Building University Capacity to Visualize Solutions to Complex Problems in the Arctic

    Science.gov (United States)

    Broderson, D.; Veazey, P.; Raymond, V. L.; Kowalski, K.; Prakash, A.; Signor, B.

    2016-12-01

    Rapidly changing environments are creating complex problems across the globe, which are particular magnified in the Arctic. These worldwide challenges can best be addressed through diverse and interdisciplinary research teams. It is incumbent on such teams to promote co-production of knowledge and data-driven decision-making by identifying effective methods to communicate their findings and to engage with the public. Decision Theater North (DTN) is a new semi-immersive visualization system that provides a space for teams to collaborate and develop solutions to complex problems, relying on diverse sets of skills and knowledge. It provides a venue to synthesize the talents of scientists, who gather information (data); modelers, who create models of complex systems; artists, who develop visualizations; communicators, who connect and bridge populations; and policymakers, who can use the visualizations to develop sustainable solutions to pressing problems. The mission of Decision Theater North is to provide a cutting-edge visual environment to facilitate dialogue and decision-making by stakeholders including government, industry, communities and academia. We achieve this mission by adopting a multi-faceted approach reflected in the theater's design, technology, networking capabilities, user support, community relationship building, and strategic partnerships. DTN is a joint project of Alaska's National Science Foundation Experimental Program to Stimulate Competitive Research (NSF EPSCoR) and the University of Alaska Fairbanks (UAF), who have brought the facility up to full operational status and are now expanding its development space to support larger team science efforts. Based in Fairbanks, Alaska, DTN is uniquely poised to address changes taking place in the Arctic and subarctic, and is connected with a larger network of decision theaters that include the Arizona State University Decision Theater Network and the McCain Institute in Washington, DC.

  16. Value distribution of meromorphic solutions of homogeneous and non-homogeneous complex linear differential-difference equations

    Directory of Open Access Journals (Sweden)

    Luo Li-Qin

    2016-01-01

    Full Text Available In this paper, we investigate the value distribution of meromorphic solutions of homogeneous and non-homogeneous complex linear differential-difference equations, and obtain the results on the relations between the order of the solutions and the convergence exponents of the zeros, poles, a-points and small function value points of the solutions, which show the relations in the case of non-homogeneous equations are sharper than the ones in the case of homogeneous equations.

  17. Characterization of amorphous yttria layers deposited by aqueous solutions of Y-chelate alkoxides complex

    Energy Technology Data Exchange (ETDEWEB)

    Kim, Young-Soon, E-mail: kyscjb@i-sunam.com; Lee, Yu-Ri; Kim, Byeong-Joo; Lee, Jae-Hun; Moon, Seung-Hyun; Lee, Hunju

    2015-01-15

    Highlights: • Economical method for crack-free amorphous yttria layer deposition by dip coating. • Simpler process for planar yttria film as a diffusion barrier and nucleation layer. • Easy control over the film properties with better characteristics. • Easy control over the thickness of the deposited films. • A feasible process that can be easily adopted by HTSCC industries. - Abstract: Crack-free amorphous yttria layers were deposited by dip coating in solutions of different Y-chelate alkoxides complex. Three Y-chelate solutions of different concentrations were prepared using yttrium acetate tetrahydrate, yttrium stearic acid as Y source materials. PEG, diethanolamine were used as chelating agents, while ethanol, methanol and tetradecane were used as solvent. Three different combinations of chelating and solvents were used to prepare solutions for Y{sub 2}O{sub 3} dip coating on SUS, electropolished and non-electropolished Hastelloy C-276 substrates. The thickness of the films was varied by changing the number of dipping cycles. At an optimized condition, the substrate surface roughness (rms) value was reduced from ∼50 nm to ∼1 nm over a 10 × 10 μm{sup 2} area. After Y{sub 2}O{sub 3} deposition, MgO was deposited using ion-beam assisted deposition (IBAD), then LaMnO{sub 3} (LMO) was deposited using sputtering and GdBCO was deposited using reactive co-evaporation by deposition and reaction (RCE-DR). Detailed X-ray study indicates that LMO/MgO/Y{sub 2}O{sub 3} and GdBCO/LMO/MgO/Y{sub 2}O{sub 3} stack films have good out-of-plane and in-plane textures with strong c-axis alignment. The critical current (Ic) of GdBCO/LMO/MgO/Y{sub 2}O{sub 3} multilayer structure varied from 190 to 420 A/cm with different solutions, when measured at 77 K. These results demonstrated that amorphous yttria can be easily deposited by dip coating using Y-chelates complex as a diffusion barrier and nucleation layer.

  18. Photochemical redox reactions of copper(II)-alanine complexes in aqueous solutions.

    Science.gov (United States)

    Lin, Chen-Jui; Hsu, Chao-Sheng; Wang, Po-Yen; Lin, Yi-Liang; Lo, Yu-Shiu; Wu, Chien-Hou

    2014-05-19

    The photochemical redox reactions of Cu(II)/alanine complexes have been studied in deaerated solutions over an extensive range of pH, Cu(II) concentration, and alanine concentration. Under irradiation, the ligand-to-metal charge transfer results in the reduction of Cu(II) to Cu(I) and the concomitant oxidation of alanine, which produces ammonia and acetaldehyde. Molar absorptivities and quantum yields of photoproducts for Cu(II)/alanine complexes at 313 nm are characterized mainly with the equilibrium Cu(II) speciation where the presence of simultaneously existing Cu(II) species is taken into account. By applying regression analysis, individual Cu(I) quantum yields are determined to be 0.094 ± 0.014 for the 1:1 complex (CuL) and 0.064 ± 0.012 for the 1:2 complex (CuL2). Individual quantum yields of ammonia are 0.055 ± 0.007 for CuL and 0.036 ± 0.005 for CuL2. Individual quantum yields of acetaldehyde are 0.030 ± 0.007 for CuL and 0.024 ± 0.007 for CuL2. CuL always has larger quantum yields than CuL2, which can be attributed to the Cu(II) stabilizing effect of the second ligand. For both CuL and CuL2, the individual quantum yields of Cu(I), ammonia, and acetaldehyde are in the ratio of 1.8:1:0.7. A reaction mechanism for the formation of the observed photoproducts is proposed.

  19. A New Efficient Analytical Method for Picolinate Ion Measurements in Complex Aqueous Solutions

    Energy Technology Data Exchange (ETDEWEB)

    Parazols, M.; Dodi, A. [CEA Cadarache, Lab Anal Radiochim and Chim, DEN, F-13108 St Paul Les Durance (France)

    2010-07-01

    This study focuses on the development of a new simple but sensitive, fast and quantitative liquid chromatography method for picolinate ion measurement in high ionic strength aqueous solutions. It involves cation separation over a chromatographic CS16 column using methane sulfonic acid as a mobile phase and detection by UV absorbance (254 nm). The CS16 column is a high-capacity stationary phase exhibiting both cation exchange and RP properties. It allows interaction with picolinate ions which are in their zwitterionic form at the pH of the mobile phase (1.3-1.7). Analysis is performed in 30 min with a detection limit of about 0.05 {mu}M and a quantification limit of about 0.15 {mu}M. Moreover, this analytical technique has been tested efficiently on complex aqueous samples from an effluent treatment facility. (authors)

  20. Positron annihilation in liquids and in solutions containing electron acceptors and charge-transfer complexes

    International Nuclear Information System (INIS)

    Jansen, P.

    1976-05-01

    Positron lifetime measurements and angular correlation measurements were performed in several organic liquids. The results strongly indicate that positronium is contained in a 'bubble' in the liquids. The radius of the bubble can be estimated by using broadness of the narrow component in the angular correlation distribution, and by using the surface tension of the liquids. Both methods give bubble radii from 4-7 A in the solvents investigated. The bubble influences the reaction mechanism between Ps and weak electron acceptors in such a way that the presence of the bubble decreases the reactivity of Ps. Positron lifetime measurements were also performed on a series of mixtures of organic liquids and on electron acceptors and charge-transfer complexes in solution. The results were is agreement with the spur model of Ps formation. (Auth.)

  1. Two-Level Solutions to Exponentially Complex Problems in Glass Science

    DEFF Research Database (Denmark)

    Mauro, John C.; Smedskjær, Morten Mattrup

    Glass poses an especially challenging problem for physicists. The key to making progress in theoretical glass science is to extract the key physics governing properties of practical interest. In this spirit, we discuss several two-level solutions to exponentially complex problems in glass science....... Topological constraint theory, originally developed by J.C. Phillips, is based on a two-level description of rigid and floppy modes in a glass network and can be used to derive quantitatively accurate and analytically solvable models for a variety of macroscopic properties. The temperature dependence...... that captures both primary and secondary relaxation modes. Such a model also offers the ability to calculate the distinguishability of particles during glass transition and relaxation processes. Two-level models can also be used to capture the distribution of various network-forming species in mixed...

  2. Molecular Complex of Lumiflavin and 2-Aminobenzoic Acid : Crystal Structure, Crystal Spectra, and Solution Properties

    OpenAIRE

    Shieh, Huey-Sheng; Ghisla, Sandro; Hanson, Louise Karle; Ludwig, Martha L.; Nordman, Christer E.

    1981-01-01

    The molecular complex lumiflavin-2-aminobenzoic acid monohydrate (C13H12N402●C7H7N02●H2O)crystallizes from aqueous solution as red triclinic prisms. The space group is P1 with cell dimensions a = 9.660 A, b = 14.866 Å, c = 7.045 Å, α = 95.44°, β = 95.86°, and γ = 105.66°. The crystal structure was solved by direct methods and refined by block-diagonal least-squares procedures to an R value of 0.050 on the basis of 1338 observed reflections. The structure is composed of stacks of alternating l...

  3. S-Adenosylmethionine conformations in solution and in protein complexes: Conformational influences of the sulfonium group

    DEFF Research Database (Denmark)

    Markham, George D.; Norrby, Per-Ola; Bock, Charles W.

    2002-01-01

    S-Adenosylmethionine (AdoMet) and other sulfonium ions play central roles in the metabolism of all organisms. The conformational preferences of AdoMet and two other biologically important sulfonium ions, S-methylmethionine and dimethylsulfonioproprionic acid, have been investigated by NMR...... and computational studies. Molecular mechanics parameters for the sulfonium center have been developed for the AMBER force field to permit analysis of NMR results and to enable comparison of the relative energies of the different conformations of AdoMet that have been found in crystal structures of complexes...... with proteins. S-Methylmethionine and S-dimethylsulfonioproprionate adopt a variety of conformations in aqueous solution; a conformation with an electrostatic interaction between the sulfonium sulfur and the carboxylate group is not noticeably favored, in contrast to the preferred conformation found by in vacuo...

  4. One Problem, Many Solutions : Simple Statistical Approaches Help Unravel the Complexity of the Immune System in an Ecological Context

    NARCIS (Netherlands)

    Buehler, Deborah M.; Versteegh, Maaike A.; Matson, Kevin D.; Tieleman, Irene

    2011-01-01

    The immune system is a complex collection of interrelated and overlapping solutions to the problem of disease. To deal with this complexity, researchers have devised multiple ways to measure immune function and to analyze the resulting data. In this way both organisms and researchers employ many

  5. The effect of boundaries on the asymptotic wavenumber of spiral wave solutions of the complex Ginzburg–Landau equation

    KAUST Repository

    Aguareles, M.

    2014-01-01

    In this paper we consider an oscillatory medium whose dynamics are modeled by the complex Ginzburg-Landau equation. In particular, we focus on n-armed spiral wave solutions of the complex Ginzburg-Landau equation in a disk of radius d

  6. One problem, many solutions: simple statistical approaches help unravel the complexity of th eimmune system in an ecological context

    NARCIS (Netherlands)

    Buehler, D.M.; Versteegh, M.A.; Matson, K.D.; Tieleman, B.I.

    2011-01-01

    The immune system is a complex collection of interrelated and overlapping solutions to the problem of disease. To deal with this complexity, researchers have devised multiple ways to measure immune function and to analyze the resulting data. In this way both organisms and researchers employ many

  7. Reactive solute transport in streams: A surface complexation approach for trace metal sorption

    Science.gov (United States)

    Runkel, Robert L.; Kimball, Briant A.; McKnight, Diane M.; Bencala, Kenneth E.

    1999-01-01

    A model for trace metals that considers in-stream transport, metal oxide precipitation-dissolution, and pH-dependent sorption is presented. Linkage between a surface complexation submodel and the stream transport equations provides a framework for modeling sorption onto static and/or dynamic surfaces. A static surface (e.g., an iron- oxide-coated streambed) is defined as a surface with a temporally constant solid concentration. Limited contact between solutes in the water column and the static surface is considered using a pseudokinetic approach. A dynamic surface (e.g., freshly precipitated metal oxides) has a temporally variable solid concentration and is in equilibrium with the water column. Transport and deposition of solute mass sorbed to the dynamic surface is represented in the stream transport equations that include precipitate settling. The model is applied to a pH-modification experiment in an acid mine drainage stream. Dissolved copper concentrations were depressed for a 3 hour period in response to the experimentally elevated pH. After passage of the pH front, copper was desorbed, and dissolved concentrations returned to ambient levels. Copper sorption is modeled by considering sorption to aged hydrous ferric oxide (HFO) on the streambed (static surface) and freshly precipitated HFO in the water column (dynamic surface). Comparison of parameter estimates with reported values suggests that naturally formed iron oxides may be more effective in removing trace metals than synthetic oxides used in laboratory studies. The model's ability to simulate pH, metal oxide precipitation-dissolution, and pH-dependent sorption provides a means of evaluating the complex interactions between trace metal chemistry and hydrologic transport at the field scale.

  8. A comparative study of UVO2+- and UVIO22+ -carbonato complexes in aqueous solution

    International Nuclear Information System (INIS)

    Ikeda, A.; Hennig, Ch.; Rossberg, A.; Scheinost, A.C.; Bernhard, G.; Takao, K.; Ikeda, Y.

    2007-01-01

    Electrochemical and spectroscopic (UV-vis and X-ray absorption) studies have been performed for the uranyl (UO 2 n+ ) species in aqueous carbonate solution in order to reveal the redox behavior of uranyl ion and to identify the structural difference between pentavalent and hexavalent UO 2 n+ . Cyclic voltammetry and bulk electrolysis experiments using a 50 mM U solution suggest that U V O 2 + , the reduction product of U VI O 2 2+ , is stabilized only in the limited concentration range of 0.8 M 2 CO 3 ] and 11.7 V O 2 + species is confirmed to be stable for at least 1 month in a sealed glass cuvette by successive UV-vis absorption measurements. X-ray absorption measurements show that both U V O 2 + and U VI O 2 2+ are co-ordinated by three carbonate ions in their equatorial planes with a bidentate arrangement, forming a tri-carbonato complex, [UO 2 (CO 3 ) 3 ] m- (m = 5 for U(V) and 4 for U(VI)). The electron density of the uranium atom affects the U-O bond lengths that lengthen upon reduction from U VI O 2 2+ to U V O 2 + . (authors)

  9. Critical Parameters of Complex Geometries of Intersecting Cylinders Containing Uranyl Nitrate Solution

    Energy Technology Data Exchange (ETDEWEB)

    J. B. Briggs (INEEL POC); R. E. Rothe

    1999-06-14

    About three dozen previously unreported critical configurations are presented for very complex geometries filled with high concentration enriched uranyl nitrate solution. These geometries resemble a tall, thin Central Column (or trunk of a ''tree'') having long, thin arms (or ''branches'') extending up to four directions off the column. Arms are equally spaced from one another in vertical planes, and that spacing ranges from arms in contact to quite wide spacings. Both the Central Column and the many different arms are critically safe by themselves with each, alone, is filled with fissile solution; but, in combination, criticality occurs due to the interactions between arms and the column. Such neutronic interactions formed the principal focus of this study. While these results are fresh to the nuclear criticality safety industry and to those seeking novel experiments against which to validate computer codes, the experiments, themselves, are not recent. Over 100 experiments were performed at the Rocky Flats Critical Mass Laboratory between September, 1967, and February of the following year.

  10. Critical Parameters of Complex Geometry Intersecting Cylinders Containing Uranyl Nitrate Solution

    Energy Technology Data Exchange (ETDEWEB)

    Rothe, Robert Emil; Briggs, Joseph Blair

    1999-06-01

    About three dozen previously unreported critical configurations are presented for very complex geometries filled with high concentration enriched uranyl nitrate solution. These geometries resemble a tall, thin Central Column (or trunk of a "tree") having long, thin arms (or "branches") extending up to four directions off the column. Arms are equally spaced from one another in vertical planes; and that spacing ranges from arms in contact to quite wide spacings. Both the Central Column and the many different arms are critically safe by themselves when each, alone, is filled with fissile solution; but, in combination, criticality occurs due to the interactions between arms and the column. Such neutronic interactions formed the principal focus of this study. While these results are fresh to the nuclear criticality safety industry and to those seeking novel experiments against which to validate computer codes, the experiments, themselves, are not recent. Over 100 experiments were performed at the Rocky Flats Critical Mass Laboratory between September, 1967, and February of the following year.

  11. Kinetics of oxidation of bilirubin and its protein complex by hydrogen peroxide in aqueous solutions

    Science.gov (United States)

    Solomonov, A. V.; Rumyantsev, E. V.; Antina, E. V.

    2010-12-01

    A comparative study of oxidation reactions of bilirubin and its complex with albumin was carried out in aqueous solutions under the action of hydrogen peroxide and molecular oxygen at different pH values. Free radical oxidation of the pigment in both free and bound forms at pH 7.4 was shown not to lead to the formation of biliverdin, but to be associated with the decomposition of the tetrapyrrole chromophore into monopyrrolic products. The effective and true rate constants of the reactions under study were determined. It was assumed that one possible mechanism of the oxidation reaction is associated with the interaction of peroxyl radicals and protons of the NH groups of bilirubin molecules at the limiting stage with the formation of a highly reactive radical intermediate. The binding of bilirubin with albumin was found to result in a considerable reduction in the rate of the oxidation reaction associated with the kinetic manifestation of the protein protection effect. It was found that the autoxidation of bilirubin by molecular oxygen with the formation of biliverdin at the intermediate stage can be observed with an increase in the pH of solutions.

  12. Critical Parameters of Complex Geometries of Intersecting Cylinders Containing Uranyl Nitrate Solution

    International Nuclear Information System (INIS)

    Rothe, R. E.

    1999-01-01

    About three dozen previously unreported critical configurations are presented for very complex geometries filled with high concentration enriched uranyl nitrate solution. These geometries resemble a tall, thin Central Column (or trunk of a ''tree'') having long, thin arms (or ''branches'') extending up to four directions off the column. Arms are equally spaced from one another in vertical planes, and that spacing ranges from arms in contact to quite wide spacings. Both the Central Column and the many different arms are critically safe by themselves with each, alone, is filled with fissile solution; but, in combination, criticality occurs due to the interactions between arms and the column. Such neutronic interactions formed the principal focus of this study. While these results are fresh to the nuclear criticality safety industry and to those seeking novel experiments against which to validate computer codes, the experiments, themselves, are not recent. Over 100 experiments were performed at the Rocky Flats Critical Mass Laboratory between September, 1967, and February of the following year

  13. Determination of low chloride values in Rocky Flats scrub alloy solutions and other complex matrices

    International Nuclear Information System (INIS)

    Holcomb, H.P.

    1985-01-01

    A turbidimetric method, using silver chloride, has been developed to determine low ppM quantities of chloride in Rocky Flats scrub alloy (RFSA) dissolver solutions. This analytical technique has also been applied to other complex matrices such as process 50% caustic and neutralized Purex low heat liquid waste concentrate. A controlled-pH precipitation with NaOH, during which chloride remains in solution, is used to pretreat samples to minimize salt effects from acids, bases, and/or hydrolyzable ions. Control of pH with bromocresol purple indicator also provides a more consistent pH for silver chloride formation, aiding in turbidity reproducibility. Disodium ethylenediaminetetraacetic acid is employed to negate covalent bonding by Hg(II) with chloride. The average standard deviation was +-17% for turbidity reproducibility in simulated sample aliquots containing a total of 10 to 100 μg chloride. For actual RFSA samples, the relative standard deviation ranged from +-14% to +-26%, depending on initial chloride values. 8 refs., 1 fig

  14. Thermodynamic and structural description of europium complexation in 1-octanol - H2O solutions

    International Nuclear Information System (INIS)

    Vu, T.H.; Charbonnel, M.C.; Boubals, N.; Couston, L.; Arnaud, F.

    2008-01-01

    Polydentate N-bearing ligands such as bis-triazinyl-pyridines (BTPs) are interesting extractants for actinide(III)/lanthanide(III) separation. A description of europium complexation in 1-octanol solutions was undertaken to enhance the knowledge of the extraction mechanisms. The first solvation shell for europium(III) nitrate, chloride, and perchlorate with different amounts of water was determined by Time-Resolved Laser-Induced Fluorescence (TRLIF) spectroscopy. Europium nitrate complexation by iPr-BTP was then studied by TRLIF and micro-calorimetry; similar stability constants related to the formation of Eu(BTP) 2 3+ and Eu(BTP) 3 3+ were obtained by both techniques (log(β 2 ) = 9.0 ± 0.3 and log(β 3 ) = 13.8 ± 0.2). The presence of water in the octanol diluent has an influence on solvation of europium and also on the [Eu(BTP) 2 3+ ] / [Eu(BTP) 3 3+ ] ratio. (authors)

  15. Thermodynamic and structural description of europium complexation in 1-octanol - H{sub 2}O solutions

    Energy Technology Data Exchange (ETDEWEB)

    Vu, T.H.; Charbonnel, M.C.; Boubals, N.; Couston, L. [CEA Marcoule, DEN/DRCP/SCPS/LCAM, BP 17171, 30207 Bagnols-sur-Ceze (France); Arnaud, F. [Laboratoire de Chimie Physique, IPHC, 25 rue Becquerel, 67087 Strasbourg (France)

    2008-07-01

    Polydentate N-bearing ligands such as bis-triazinyl-pyridines (BTPs) are interesting extractants for actinide(III)/lanthanide(III) separation. A description of europium complexation in 1-octanol solutions was undertaken to enhance the knowledge of the extraction mechanisms. The first solvation shell for europium(III) nitrate, chloride, and perchlorate with different amounts of water was determined by Time-Resolved Laser-Induced Fluorescence (TRLIF) spectroscopy. Europium nitrate complexation by iPr-BTP was then studied by TRLIF and micro-calorimetry; similar stability constants related to the formation of Eu(BTP){sub 2}{sup 3+} and Eu(BTP){sub 3}{sup 3+} were obtained by both techniques (log({beta}{sub 2}) = 9.0 {+-} 0.3 and log({beta}{sub 3}) = 13.8 {+-} 0.2). The presence of water in the octanol diluent has an influence on solvation of europium and also on the [Eu(BTP){sub 2}{sup 3+}] / [Eu(BTP){sub 3}{sup 3+}] ratio. (authors)

  16. Nitric oxide production by visible light irradiation of aqueous solution of nitrosyl ruthenium complexes.

    Science.gov (United States)

    Sauaia, Marília Gama; de Lima, Renata Galvão; Tedesco, Antonio Claudio; da Silva, Roberto Santana

    2005-12-26

    [Ru(II)L(NH(3))(4)(pz)Ru(II)(bpy)(2)(NO)](PF(6))(5) (L is NH(3), py, or 4-acpy) was prepared with good yields in a straightforward way by mixing an equimolar ratio of cis-[Ru(NO(2))(bpy)(2)(NO)](PF(6))(2), sodium azide (NaN(3)), and trans-[RuL(NH(3))(4)(pz)] (PF(6))(2) in acetone. These binuclear compounds display nu(NO) at ca. 1945 cm(-)(1), indicating that the nitrosyl group exhibits a sufficiently high degree of nitrosonium ion (NO(+)). The electronic spectrum of the [Ru(II)L(NH(3))(4)(pz)Ru(II)(bpy)(2)(NO)](5+) complex in aqueous solution displays the bands in the ultraviolet and visible regions typical of intraligand and metal-to-ligand charge transfers, respectively. Cyclic voltammograms of the binuclear complexes in acetonitrile give evidence of three one-electron redox processes consisting of one oxidation due to the Ru(2+/3+) redox couple and two reductions concerning the nitrosyl ligand. Flash photolysis of the [Ru(II)L(NH(3))(4)(pz)Ru(II)(bpy)(2)(NO)](5+) complex is capable of releasing nitric oxide (NO) upon irradiation at 355 and 532 nm. NO production was detected and quantified by an amperometric technique with a selective electrode (NOmeter). The irradiation at 532 nm leads to NO release as a consequence of a photoinduced electron transfer. All species exhibit similar photochemical behavior, a feature that makes their study extremely important for their future application in the upgrade of photodynamic therapy in living organisms.

  17. Study of ruthenium complexation by 22' bipyridine in nitric aqueous solutions

    International Nuclear Information System (INIS)

    Alozy, J.P.

    1982-01-01

    Substitution of the NO 3- , NO + ions of RuNO(NO 3 )x.yH 2 Osup((3-x)+) complexes by 22'bipyridine (bipy) in nitric aqueous solution was studied by spectrophotometry. In the absence of reducing agent we observe the species RuNO(bipy)(NO3)sub(z)sup((3-z)+) and RuNO(bipy) 2 NO 3 2 + . Most reducing agents give rise to the RuNO(bipy) 2 NO 3 2 + + e → RuNO(bipy) 2 NO 3+ reaction. The oxydation potential of the reversible couple RuNO(bipy) 2 NO 3 2 + /RuNO(bipy) 2 NO 3+ was measured by cyclic voltamperometry at the platinum electrode. Its value is + 1.02 V/NHE. Substitution of NO + ions by a (bipy) molecule is only possible in the presence of reducing agents of apparent formal potential below + 0.5 V/NHE, and anti-nitrite agents are also needed; these two functions can be fulfilled by hydrazine and ascorbic acid. The presence of HSO 3 NH 2 was necessary to obtain the substitution of NO + and NO 3- by bipy during electrochemical reductions. The intermediate complexes RuNO(bipy) 2 NO 3 2 + and RuNO(bipy) 2 NO 3+ probably include two bipy molecules in the trans position whereas RuNO(bipy) 2 2 + complexes, where the sixth coordination position is occupied by π donors stronger than NO 3- , have two bipy molecules in the cis position [fr

  18. Thermodynamics of curium(III) in concentrated electrolyte solutions: formation of sulfate complexes in NaCl/Na2SO4 solutions

    International Nuclear Information System (INIS)

    Paviet, P.; Fanghaenel, T.; Klenze, R.; Kim, J.I.

    1996-01-01

    The formation of sulfate complexes of Curium in aqueous solutions is studied by time resolved laser fluorescence spectroscopy (TRLFS) at 25 C. The species Cm 3+ , Cm(SO 4 ) - , Cm(SO 4 ) - 2 and Cm(SO 4 ) 3- 3 are quantified spectroscopically in the trace concentration range by peak deconvolution of fluorescence emission spectra. The complex formation equilibria are measured in NaCl/ Na 2 SO 4 solutions of constant ionic strength (3 molal) as a function of the sulfate concentration. The stability constants of Cm(SO 4 ) + and Cm(SO 4 ) - 2 are determined to be log β 1 = 0.93±0.08 and log β 2 = 0.61±0.08, respectively. The complex Cm(SO 4 ) 3- 3 is found to be stable only at very high sulfate concentrations (above 1 molal) and therefore not considered for further evaluation. (orig.)

  19. 5C analysis of the Epidermal Differentiation Complex locus reveals distinct chromatin interaction networks between gene-rich and gene-poor TADs in skin epithelial cells.

    Directory of Open Access Journals (Sweden)

    Krzysztof Poterlowicz

    2017-09-01

    Full Text Available Mammalian genomes contain several dozens of large (>0.5 Mbp lineage-specific gene loci harbouring functionally related genes. However, spatial chromatin folding, organization of the enhancer-promoter networks and their relevance to Topologically Associating Domains (TADs in these loci remain poorly understood. TADs are principle units of the genome folding and represents the DNA regions within which DNA interacts more frequently and less frequently across the TAD boundary. Here, we used Chromatin Conformation Capture Carbon Copy (5C technology to characterize spatial chromatin interaction network in the 3.1 Mb Epidermal Differentiation Complex (EDC locus harbouring 61 functionally related genes that show lineage-specific activation during terminal keratinocyte differentiation in the epidermis. 5C data validated by 3D-FISH demonstrate that the EDC locus is organized into several TADs showing distinct lineage-specific chromatin interaction networks based on their transcription activity and the gene-rich or gene-poor status. Correlation of the 5C results with genome-wide studies for enhancer-specific histone modifications (H3K4me1 and H3K27ac revealed that the majority of spatial chromatin interactions that involves the gene-rich TADs at the EDC locus in keratinocytes include both intra- and inter-TAD interaction networks, connecting gene promoters and enhancers. Compared to thymocytes in which the EDC locus is mostly transcriptionally inactive, these interactions were found to be keratinocyte-specific. In keratinocytes, the promoter-enhancer anchoring regions in the gene-rich transcriptionally active TADs are enriched for the binding of chromatin architectural proteins CTCF, Rad21 and chromatin remodeler Brg1. In contrast to gene-rich TADs, gene-poor TADs show preferential spatial contacts with each other, do not contain active enhancers and show decreased binding of CTCF, Rad21 and Brg1 in keratinocytes. Thus, spatial interactions between gene

  20. Complex crystals formed in the aqueous solution of copper(I) iodide and sodium iodide

    International Nuclear Information System (INIS)

    Sugasaka, Kazuhiko; Fujii, Ayako

    1977-01-01

    Crystals of different crystal habits were separated from the copper(I) iodide and sodium iodide solution and the thermal changes of the composition of copper(I) iodide and sodium iodide complexes were studied by chemical analysis, thermal analysis and X-ray diffractometry. Granular and columnar crystals were determined to be copper(I) iodide and sodium iodide dihydrate by X-ray diffraction analysis, respectively. Needle crystal (A) which was separated from the solution at 25 0 C was assumed to be Na 2 CuI 3 .6H 2 O. (A) was stable in its appearance in the air, but the X-ray diffraction pattern of (A) changed. Needle crystal (B) which was recrystallized at 10 0 C from mother liquor after the separation of crystal (A) was assumed to be NaCuI 2 .4H 2 O. (B) was hygroscopic and decomposed to precipitate copper(I) iodide with moisture in the air. (A) and (B) were found to change by heating and or drying, respectively, as follows: Na 2 CuI 3 .6H 2 O → (-2H 2 O, 80 0 C) → 2NaI.2H 2 O + CuI → (-4H 2 O, 160 0 C) → 2NaI + CuI → (+1/2O 2 , 450 0 C) → 2NaI + CuO + 1/2I 2 , NaCuI 2 .4H 2 O → (-4H 2 O, Dried) → NaI + CuI. (auth.)

  1. β-Catenin/POU5F1/SOX2 transcription factor complex mediates IGF-I receptor signaling and predicts poor prognosis in lung adenocarcinoma.

    Science.gov (United States)

    Xu, Chuan; Xie, Dan; Yu, Shi-Cang; Yang, Xiao-Jun; He, Li-Ru; Yang, Jing; Ping, Yi-Fang; Wang, Bin; Yang, Lang; Xu, Sen-Lin; Cui, Wei; Wang, Qing-Liang; Fu, Wen-Juan; Liu, Qing; Qian, Cheng; Cui, You-Hong; Rich, Jeremy N; Kung, Hsiang-Fu; Zhang, Xia; Bian, Xiu-Wu

    2013-05-15

    Cancer stem-like cells (CSLC) are crucial in tumor initiation and progression; however, the underlying mechanism for the self-renewal of cancer cells remains undefined. In the study, immunohistochemical analysis of specimens freshly excised from patients with lung adenocarcinoma showed that high expression of insulin-like growth factor I receptor (IGF-IR) in lung adenocarcinoma cells was positively correlated with the expressions of cancer stem cell markers CD133 and aldehyde dehydrogenase 1 family member A1 (ALDH1A1). IGF-IR activation enhanced POU class 5 homeobox 1 (POU5F1) expression on human lung adenocarcinoma stem-like cells (LACSLC) through PI3K/AKT/GSK3β/β-catenin cascade. POU5F1 could form a novel complex with β-catenin and SOX2 to bind Nanog promoter for transcription to maintain self-renewal of LACSLCs, which was dependent on the functional IGF-IR. Genetic and pharmacologic inhibition of IGF-IR abrogated LACSLC capabilities for self-renewal and tumorigenicity in vitro. In an in vivo xenograft tumor model, knockdown of either IGF-IR or POU5F1 impeded tumorigenic potentials of LACSLCs. By analyzing pathologic specimens excised from 200 patients with lung adenocarcinoma, we found that colocalization of highly expressed IGF-IR with β-catenin and POU5F1 predicted poor prognosis. Taken together, we show that IGF-IR-mediated POU5F1 expression to form a complex with β-catenin and SOX2 is crucial for the self-renewal and oncogenic potentials of LACSLCs, and the integrative clinical detection of the expressions of IGF-IR, β-catenin, and POU5F1 is indicatory for predicting prognosis in the patients of lung adenocarcinoma. ©2013 AACR.

  2. Solution chemistry of element 105. Pt. III. Hydrolysis and complex formation of Nb, Ta, Db and Pa in HF and HBr solutions

    International Nuclear Information System (INIS)

    Pershina, V.; Bastug, T.

    1999-01-01

    Calculations of the electronic structure of MF 6 - and MBr 6 - complexes of Nb, Ta, Pa and element 105, Db, formed in HF and HBr solutions have been performed using the Dirac-Slater Discrete Variational method. On the basis of results of these calculations, relative values of the free energy change of reactions of complex formation have been determined. The order of the complex formation for both acids is shown to be Pa >> Nb > Db > Ta. Such a sequence is defined by a predominant electrostatic energy of the metal-ligand interaction. The hydrolysis of compounds, as a reverse process, proved to change as Ta > Db > Nb >> Pa. Using the theory of metal extraction by anion exchange, the following trend in the extraction of the anionic species from both the HF and HBr aqueous solutions has been predicted: Pa >> Nb ≥ Db > Ta. The strength of the ML 6 - complexes is shown to decrease from MF 6 , to MCl 6 and further to MBr 6 - which is reflected by shifting the complex formation process to the area of higher acid concentrations. (orig.)

  3. Stability constant determinations for technetium (IV) complexation with selected amino carboxylate ligands in high nitrate solutions

    Energy Technology Data Exchange (ETDEWEB)

    Omoto, Trevor; Wall, Nathalie A. [Washington State Univ., Pullman, WA (United States). Dept. of Chemistry

    2017-10-01

    The stability constants for Tc(IV) complexation with the ligands IDA, NTA, HEDTA, and DTPA were determined in varied nitrate concentrations using liquid-liquid extraction methods. The determined log β{sub 101} stability constants at 0.5 M NaNO{sub 3} were found to be 9.2±0.3, 10.3±0.3, and 15.3±0.3 for IDA, NTA, and HEDTA, respectively. The log β{sub 111} stability constant for DTPA was determined to be 22.0±0.6. These determined stability constants show a slight decrease in magnitude as a function of increasing NaNO{sub 3} concentration. These stability constants were used to model the total dissolution of Tc(IV) in acidic aqueous solutions in the presence of each ligand. The results of these predictive models indicate that amino carboxylic ligands have a high potential for increasing the aqueous dissolution of Tc(IV); at pH 2.3, 0.01 M ligand yield dissolved Tc(IV) concentrations of 1.42.10{sup -5} M, 1.33.10{sup -5} M, 6.07.10{sup -6} M, 9.65.10{sup -7} M, for DTPA, HEDTA, NTA, and IDA, respectively.

  4. Direct protein quantification in complex sample solutions by surface-engineered nanorod probes

    KAUST Repository

    Schrittwieser, Stefan

    2017-06-30

    Detecting biomarkers from complex sample solutions is the key objective of molecular diagnostics. Being able to do so in a simple approach that does not require laborious sample preparation, sophisticated equipment and trained staff is vital for point-of-care applications. Here, we report on the specific detection of the breast cancer biomarker sHER2 directly from serum and saliva samples by a nanorod-based homogeneous biosensing approach, which is easy to operate as it only requires mixing of the samples with the nanorod probes. By careful nanorod surface engineering and homogeneous assay design, we demonstrate that the formation of a protein corona around the nanoparticles does not limit the applicability of our detection method, but on the contrary enables us to conduct in-situ reference measurements, thus further strengthening the point-of-care applicability of our method. Making use of sandwich assays on top of the nanorods, we obtain a limit of detection of 110 pM and 470 pM in 10-fold diluted spiked saliva and serum samples, respectively. In conclusion, our results open up numerous applications in direct protein biomarker quantification, specifically in point-of-care settings where resources are limited and ease-of-use is of essence.

  5. Direct protein quantification in complex sample solutions by surface-engineered nanorod probes

    KAUST Repository

    Schrittwieser, Stefan; Pelaz, Beatriz; Parak, Wolfgang J.; Lentijo Mozo, Sergio; Soulantica, Katerina; Dieckhoff, Jan; Ludwig, Frank; Schotter, Joerg

    2017-01-01

    Detecting biomarkers from complex sample solutions is the key objective of molecular diagnostics. Being able to do so in a simple approach that does not require laborious sample preparation, sophisticated equipment and trained staff is vital for point-of-care applications. Here, we report on the specific detection of the breast cancer biomarker sHER2 directly from serum and saliva samples by a nanorod-based homogeneous biosensing approach, which is easy to operate as it only requires mixing of the samples with the nanorod probes. By careful nanorod surface engineering and homogeneous assay design, we demonstrate that the formation of a protein corona around the nanoparticles does not limit the applicability of our detection method, but on the contrary enables us to conduct in-situ reference measurements, thus further strengthening the point-of-care applicability of our method. Making use of sandwich assays on top of the nanorods, we obtain a limit of detection of 110 pM and 470 pM in 10-fold diluted spiked saliva and serum samples, respectively. In conclusion, our results open up numerous applications in direct protein biomarker quantification, specifically in point-of-care settings where resources are limited and ease-of-use is of essence.

  6. The number of zero solutions for complex canonical differential equation of second order with constant coefficients in the first quadrant

    Directory of Open Access Journals (Sweden)

    Vujaković Jelena

    2016-01-01

    Full Text Available The study of complex differential equations in recent years has opened up some of questions concerning the determination of the frequency of zero solutions, the distribution of zero, oscillation of the solution, asymptotic behavior, rank growth and so on. Besides, this is solved by only some classes of differential equations. In this paper, our aim was to determine the number of zeros and their arrangement in the first quadrant, for the complex canonical differential equation of the second order. The accuracy of our results, we illustrate with two examples.

  7. Entropy-driven complex formation of malvidin-3- O-glucoside with common polyphenols in ethanol-water binary solutions

    Science.gov (United States)

    Kunsági-Máté, Sándor; Ortmann, Erika; Kollár, László; Nikfardjam, Martin Pour

    2008-09-01

    The complex formation of malvidin-3- O-glucoside with several polyphenols, the so-called "copigmentation" phenomenon, was studied in aqueous solutions. To simulate the copigmentation process during fermentation, the stability of the formed complexes was examined in dependence of the ethanol content of the aqueous solution. Results indicate that stronger and larger complexes are formed, when the ethanol content exceeds a critical margin of 8 vol.% However, the size of complexes of malvidin/procyanidin and malvidin/epicatechin is drastically reduced above this critical concentration. Fluorescence lifetime and solvent relaxation measurements give insight into the particular processes at molecular level and will help us comprehend the first important steps during winemaking in order to recommend an optimized winemaking technology to ensure extraordinary colour stability in red wines.

  8. On the role of the ground state Tb(3)/acetylacetone complex in sensitized emission of Tb(3) in ethanol solution

    International Nuclear Information System (INIS)

    Lis, S.; Elbanowski, M.; Marciniak, B.

    1989-01-01

    The Tb(3)-acetylacetone system in ethanol solution has been studied by spectroscopic methods. The formation of a Tb(3)/acetylacetone (1:1) complex in the ground state has been proved and its stability constant determined, K = (0,97 ± 0,06).10 4 dm 3 mol -1 . The role of this complex in the spectrofluorimetric determination of Ln(3) ions in the presence of acetylacetone has been discussed. (Authors)

  9. Molecular sources of residual cardiovascular risk, clinical signals, and innovative solutions: relationship with subclinical disease, undertreatment, and poor adherence: implications of new evidence upon optimizing cardiovascular patient outcomes

    Directory of Open Access Journals (Sweden)

    Kones R

    2013-10-01

    the conditional pleiotropic actions of HDL. Non-HDL cholesterol reflects the cholesterol in all atherogenic particles containing apolipoprotein B, and has outperformed LDL cholesterol as a lipid marker of cardiovascular risk and future mortality. In addition to including a measure of residual risk, the advantages of using non-HDL cholesterol as a primary lipid target are now compelling. Reinterpretation of data from the Treating to New Targets study suggests that better control of smoking, body weight, hypertension, and diabetes will help lower residual risk. Although much improved, control of risk factors other than LDL cholesterol currently remains inadequate due to shortfalls in compliance with guidelines and poor patient adherence. More efficient and greater use of proven simple therapies, such as aspirin, beta-blockers, angiotensin-converting enzyme inhibitors and angiotensin II receptor blockers, combined with statin therapy, may be more fruitful in improving outcomes than using other complex therapies. Comprehensive, intensive, multimechanistic, global, and national programs using primordial, primary, and secondary prevention to lower the total level of cardiovascular risk are necessary.Keywords: cardiovascular prevention, low-density lipoprotein, high-density lipoprotein, statin drugs, metabolic syndrome, obesity, diabetes, niacin, AIM-HIGH study, cholesteryl ester transfer protein, endothelial progenitor cells, fibrate drugs

  10. The complex synthesis and solid state chemistry of ceria-lanthana solid solutions prepared via a hexamethylenetetramine precipitation

    International Nuclear Information System (INIS)

    Fleming, P.G.; Holmes, J.D.; Otway, D.J.; Morris, M.A.

    2011-01-01

    Mixed oxide solid solutions are becoming ever more commercially important across a range of applications. However, their synthesis can be problematical. Here, we show that ceria-lanthana solid solutions can be readily prepared via simple precipitation using hexamethylenetetramine. However, the solution chemistry can be complex, which results in the precipitated particles having a complex structure and morphology. Great care must be taken in both the synthesis and characterisation to quantify the complexity of the product. Even very high heat treatments were not able to produce highly homogeneous materials and X-ray diffractions reveals the non-equilibrium form of particles prepared in this way. Unexpected crystal structures are revealed including a new metastable cubic La 2 O 3 phase. - Graphical abstract: The suggested mechanism for the formation of dual fluorite phase particles, where Step 1 corresponds to room temperature aging, Step 2; heating the solution to 90 deg. C, Step 3; cooling of the solution to room temperature, Step 4; calcination to 500 deg. C, Step 5; calcination to 700 deg. C and Step 6; calcination to 1300 deg. C. The terminology of e.g. La 1-x Ce x (OH) 3 is used to indicate the formation of a mixed oxy-hydroxy participate rather than a definitive assignment of stoichiometry. Similarly, La 1-y Ce y O 2 only implies a mixed solid solution. Highlights: → Mol% of prepared Ce-La oxides did not follow that of reactant mol%. → Complex reaction pathway found to be dependent on metal solution concentrations. → At certain concentrations core shell particles were found to form. → A reaction model was produced based on cationic solubility. → Report lanthana solubility higher than previously reported in CeO 2 .

  11. Web-based communications systems: innovate solutions to complex development challenges

    International Nuclear Information System (INIS)

    Levy, D.S.; Sordi, G.M.; Villavicencio, A.L.H.; Biazini Filho, F.

    2015-01-01

    This research work focus on the potential value of Information and Communication Technologies (ICTs) to enhance communication and education on Radiological Protection throughout Brazil. ICTs present unprecedented opportunities to innovate solutions to complex development issues, in this large country where it is a strong challenge to ensure access to information to as many people as possible, minimizing costs and optimizing results. Therefore, taking advantage of the impact of ICTs in modern Information Society and its institutions, some research works include education for workers, researchers and the public, offering conditions for learning and improving professional and personal skills. UNIPRORAD is a research work of informatization of radiological protection programs to offer unified programs and inter-related information in Portuguese. The system provides Brazilian facilities and researchers a complete repository for research, consultation and information. The content includes the best practices for optimization and monitoring programs, taking into account that in order to establish a Radiation Protection Plan or a Radiation Emergency Plan, there must be observed all procedures based on national and international recommendations published by different organizations over the past decades: International Commission on Radiological Protection (ICRP), International Atomic Energy Agency (IAEA) and National Nuclear Energy Commission (CNEN). Other than the efforts to disseminate information to radioactive facilities and researches, it is equally essential to invest in education and communication to increase public knowledge and understanding of the benefits of Nuclear Technology, such as food irradiation and social responsibility for electric power generation, for public acceptance of Nuclear Technology depends on public understanding of radiation and its effects on individuals, workers and environment. This research work aims to present several important initiatives

  12. Limitations when use chloramphenicol-bcyclodextrins complexes in ophtalmic solutions buffered with boric acid/borax system

    Directory of Open Access Journals (Sweden)

    Todoran Nicoleta

    2014-12-01

    Full Text Available Chloramphenicol eye drops are commonly prescribed in concentrations of 0.5-1% in the treatment of infectious conjunctivitis. In terms of ophthalmic solution preparation, the major disadvantage of chloramphenicol consists in its low solubility in water. The solubility is increased by substances that form chloramphenicol-complexes, for example: boric acid/borax or cyclodextrins. Objective: Experimental studies aimed to evaluate the potential advantages of enhancing the solubility and stability of chloramphenicol (API by molecular encapsulation in b-cyclodextrin (CD, in formulation of ophthalmic solutions buffered with boric acid/borax system. Methods and Results: We prepared four APIb- CD complexes, using two methods (kneading and co-precipitation and two molar ratio of API/b-cyclodextrin (1:1 and 1:2. The formation of complexes was proved by differential scanning calorimetry (DSC and the in vitro dissolution tests. Using these compounds, we prepared eight ophthalmic solutions, formulated in two variants of chloramphenicol concentrations (0.4% and 0.5%. Each solution was analyzed, by the official methods, at preparation and periodically during three months of storing in different temperature conditions (4°C, 20°C and 30°C. Conclusions: Inclusion of chloramphenicol in b-cyclodextrin only partially solves the difficulties due to the low solubility of chloramphenicol. The protection of chloramphenicol molecules is not completely ensured when the ophthalmic solutions are buffered with the boric acid/borax system.

  13. Mechanism of redox reactions induced by light and electron pulse in solutions of mixed ligand iron(II) complex cyanides

    International Nuclear Information System (INIS)

    Horvath, A.; Szoeke, J.; Wojnarovits, L.

    1991-01-01

    Redox reactions induced by light and electron pulse have been studied in aqueous solutions of mixed ligand iron(II) complex cyanides. The short lived intermediates have been identified by time resolved specroscopy, the results of detailed kinetic analysis have been discussed. (author) 6 refs.; 3 figs.; 2 tabs

  14. Theoretical predictions of hydrolysis and complex formation of group-4 elements Zr, Hf and Rf in HF and HCl solutions

    International Nuclear Information System (INIS)

    Pershina, V.; Trubert, D.; Le Naour, C.; Kratz, J.V.

    2002-01-01

    Fully relativistic molecular density-functional calculations of the electronic structures of hydrated, hydrolyzed and fluoride/chloride complexes have been performed for group-4 elements Zr, Hf, and element 104, Rf. Using the electronic density distribution data, relative values of the free energy change for hydrolysis and complex formation reactions were defined. The results show the following trend for the first hydrolysis step of the cationic species: Zr>Hf>Rf in agreement with experiments. For the complex formation in HF solutions, the trend to a decrease from Zr to Hf is continued with Rf, provided no hydrolysis takes place. At pH>0, further fluorination of hydrolyzed species or fluoro-complexes has an inversed trend in the group Rf≥Zr>Hf, with the difference between the elements being very small. For the complex formation in HCl solutions, the trend is continued with Rf, so that Zr>Hf>Rf independently of pH. A decisive energetic factor in hydrolysis or complex formation processes proved to be a predominant electrostatic metal-ligand interaction. Trends in the K d (distribution coefficient) values for the group-4 elements are expected to follow those of the complex formation

  15. Simple addition of silica to an alkane solution of Wilkinson WMe6 or Schrock W alkylidyne complex give active complex for saturated and unsaturated hydrocarbons metathesis

    KAUST Repository

    Callens, Emmanuel

    2015-08-24

    Addition of PDA silica to a solution of the Wilkinson WMe6 as well as the Schrock W neopentilidyne tris neopentyl complex catalyzes linear or cyclic alkanes to produce respectively a distribution of linear alkanes from methane up to triacontane or a mixture of cyclic and macrocyclic hydrocarbons. This single catalytic system transforms also linear α-olefins into higher and lower homologues via isomerization/metathesis mechanism (ISOMET). This complex is also efficient towards functionalized olefins. Unsaturated fatty acid esters (FAEs) are converted into diesters corresponding to self-metathesis products.

  16. Moessbauer spectroscopic evidence for iron(III) complexation and reduction in acidic aqueous solutions of indole-3-butyric acid

    International Nuclear Information System (INIS)

    Kovacs, K.; Kuzmann, E.; Vertes, A.; Kamnev, A.A.; Shchelochkov, A.G.; Medzihradszky-Schweiger, H.; Mink, J.; Hungarian Academy of Sciences, Budapest

    2004-01-01

    Moessbauer spectroscopic studies were carried out in acidic (pH 2.3) 57 Fe III nitrate containing aqueous solutions of indole-3-butyric acid (IBA), rapidly frozen in liquid nitrogen at various periods of time after mixing the reagents. The data obtained show that in solution in the presence of IBA, iron(III) forms a complex with a dimeric structure characterised by a quadrupole doublet, whereas without IBA under similar conditions iron(III) exhibits a broad spectral feature due to a slow paramagnetic spin relaxation which, at liquid nitrogen temperature, results in a large anomalous line broadening (or, at T = 4.2 K, in a hyperfine magnetic splitting). The spectra of 57 Fe III +IBA solutions, kept at ambient temperature under aerobic conditions for increasing periods of time before freezing, contained a gradually increasing contribution of a component with a higher quadrupole splitting. The Moessbauer parameters for that component are typical for iron(II) aquo complexes, thus showing that under these conditions gradual reduction of iron(III) occurs, so that the majority (85%) of dissolved iron(III) is reduced within 2 days. The Moessbauer parameters for the iron(III)-IBA complex in aqueous solution and in the solid state (separated from the solution by filtration) were found to be similar, which may indicate that the dissolved and solid complexes have the same composition and/or iron(III) coordination environment. For the solid complex, the data of elemental analysis suggest the following composition of the dimer: [L 2 Fe-(OH) 2 -FeL 2 ] (where L is indole-3-butyrate). This structure is also in agreement with the data of infrared spectroscopic study of the complex reported earlier, with the side-chain carboxylic group in indole-3-butyrate as a bidentate ligand. The Moessbauer parameters for the solid 57 Fe III -IBA complex at T = 80 K and its acetone solution rapidly frozen in liquid nitrogen were virtually identical, which indicates that the complex retains its

  17. Spectroscopic characterization of the oxyferrous complex of prostacyclin synthase in solution and in trapped sol–gel matrix

    Science.gov (United States)

    Yeh, Hui-Chun; Hsu, Pei-Yung; Tsai, Ah-Lim; Wang, Lee-Ho

    2010-01-01

    Prostacyclin synthase (PGIS) is a member of the cytochrome P450 family in which the oxyferrous complexes are generally labile in the absence of substrate. At 4 °C, the on-rate constants and off-rate constants of oxygen binding to PGIS in solution are 5.9 × 105 m−1 ·s−1 and 29 s−1, respectively. The oxyferrous complex decays to a ferric form at a rate of 12 s−1. We report, for the first time, a stable oxyferrous complex of PGIS in a transparent sol–gel monolith. The encapsulated ferric PGIS retained the same spectroscopic features as in solution. The binding capabilities of the encapsulated PGIS were demonstrated by spectral changes upon the addition of O-based, N-based and C-based ligands. The peroxidase activity of PGIS in sol–gel was three orders of magnitude slower than that in solution owing to the restricted diffusion of the substrate in sol–gel. The oxyferrous complex in sol–gel was observable for 24 h at room temperature and displayed a much red-shifted Soret peak. Stabilization of the ferrous–carbon monoxide complex in sol–gel was observed as an enrichment of the 450-nm species over the 420-nm species. This result suggests that the sol–gel method may be applied to other P450s to generate a stable intermediate in the di-oxygen activation. PMID:18397321

  18. Uniqueness of Solutions to Schrödinger Equations on Complex ...

    Indian Academy of Sciences (India)

    2006-09-05

    simple Lie groups. We show that if the initial data is a bi-invariant function that has sufficient decay and the solution has sufficient decay at another fixed value of time, then the solution has to be identically zero for all time.

  19. SIPPI: A Matlab toolbox for sampling the solution to inverse problems with complex prior information

    DEFF Research Database (Denmark)

    Hansen, Thomas Mejer; Cordua, Knud Skou; Caroline Looms, Majken

    2013-01-01

    on the solution. The combined states of information (i.e. the solution to the inverse problem) is a probability density function typically referred to as the a posteriori probability density function. We present a generic toolbox for Matlab and Gnu Octave called SIPPI that implements a number of methods...

  20. Molecular complex of lumiflavin and 2-aminobenzoic acid: crystal structure, crystal spectra, and solution properties.

    Science.gov (United States)

    Shieh, H S; Ghisla, S; Hanson, L K; Ludwig, M L; Nordman, C E

    1981-08-04

    The molecular complex lumiflavin-2-aminobenzoic acid monohydrate (C13H12N4O2.C7H7NO2.H2O) crystallizes from from aqueous solution as red triclinic prisms. The space group is P1 with cell dimensions a = 9.660 A, b = 14.866 A, c = 7.045 A, alpha = 95.44 degrees , beta = 95.86 degrees, and gamma = 105.66 degrees . The crystal structure was solved by direct methods and refined by block-diagonal least-squares procedures to an R value of 0.050 on the basis of 1338 observed reflections. The structure is composed of stacks of alternating lumiflavin adn un-ionized (neutral) 2-aminobenzoic acid molecules. Two different modes of stacking interaction are observed. In one, 2-aminobenzoic acid overlaps all three of the isoalloxazine rings, at a mean distance of 3.36 A; in the other, 2-aminobenzoic acid interacts distance of 3.36 A; in the other, 2-aminobenzoic acid interacts with the pyrazine and dimethylbenzene moieties, at a distance of 3.42 A. Perpendicular to the stacking direction, the molecules form a continuous sheet. Each flavin is hydrogen bonded via O(2) and NH(3) to two symmetrically related aminobenzoates; the water of crystallization forms three hydrogen bonds, bridging two flavins, via O(4) and N(5), and one aminobenzoic acid. The red color of the crystals results from a charge-transfer transition involving stacked flavin and 2-aminobenzoic acid. The red color of the crystals results from a charge-transfer transition involving stacked flavin and 2-aminobenzoic acid molecules. Measurements of the polarized optical absorption spectra of crystals show that the transition moment direction for the long wavelength absorbance (beyond 530 nm) contains an out-of-plane component which can only arise from a charge-transfer interaction. Since the amino N does not make exceptionally close interactions with isoalloxazine atoms in either stacking mode (minimum interatomic distance 3.52 A), the charge transfer is presumed to involve pi orbitals of the 2-aminobenzoic acid donor.

  1. Prize of the German gas-supply industry: Technical solutions poor cousin of the prize distribution. Preis der deutschen Gaswirtschaft: Handwerkliche Loesungen Stiefkinder der Preisvergabe

    Energy Technology Data Exchange (ETDEWEB)

    Will, H.

    1991-03-01

    The German gas-supply industry annually awards particularly energy-saving and environment friendly installations. Unfortunately only little attention is paid to small technical solutions. The article presents as particularly worth mentioning the work of a hvac-company which uses a condensing boiler for water heating. With layer-storage and integration of solar energy the energy savings are as high as possible. (BWI).

  2. Complexation of rhodium(II) tetracarboxylates with aliphatic diamines in solution: 1H and 13C NMR and DFT investigations.

    Science.gov (United States)

    Jaźwiński, Jarosław; Sadlej, Agnieszka

    2013-10-01

    The complexation of rhodium(II) tetraacetate, tetrakistrifluoroaceate and tetrakisoctanoate with a set of diamines (ethane-1,diamine, propane-1,3-diamine and nonane-1,9-diamine) and their N,N'-dimethyl and N,N,N',N'-tetramethyl derivatives in chloroform solution has been investigated by (1) H and (13) C NMR spectroscopy and density functional theory (DFT) modelling. A combination of two bifunctional reagents, diamines and rhodium(II) tetracarboxylates, yielded insoluble coordination polymers as main products of complexation and various adducts in the solution, being in equilibrium with insoluble material. All diamines initially formed the 2 : 1 (blue), (1 : 1)n oligomeric (red) and 1 : 2 (red) axial adducts in solution, depending on the reagents' molar ratio. Adducts of primary and secondary diamines decomposed in the presence of ligand excess, the former via unstable equatorial complexes. The complexation of secondary diamines slowed down the inversion at nitrogen atoms in NH(CH3 ) functional groups and resulted in the formation of nitrogenous stereogenic centres, detectable by NMR. Axial adducts of tertiary diamines appeared to be relatively stable. The presence of long aliphatic chains in molecules (adducts of nonane-1,9-diamines or rhodium(II) tetrakisoctanoate) increased adduct solubility. Hypothetical structures of the equatorial adduct of rhodium(II) tetraacetate with ethane-1,2-diamine and their NMR parameters were explored by means of DFT calculations. Copyright © 2013 John Wiley & Sons, Ltd.

  3. [Surgical solutions to luxation of the IOL--capsular bag--capsular tension ring complex].

    Science.gov (United States)

    Berthout, A; Turut, P; Taboureau, E; Denimal, F; Milazzo, S

    2007-02-01

    The spontaneous luxation of the intraocular lens-capsular bag-capsular tension ring complex is a serious but fortunately rare complication. The authors report a combined surgical procedure to reposition the complex in a patient who was operated on for bilateral lens subluxation 4 years before and whose enophthalmia made surgery difficult. Two surgical techniques can be considered to reposition the complex and avoid explantation. The McCannel modified stitch can capture the complex with the help of a transcorneal point and then a transscleral suture on the 12 o'clock meridian, despite the enophthalmia of the patient; the Moreno transscleral stitch. Both techniques suture the complex to the ciliary sulcus. Moreno's technique is easy and safe for the endothelium and must therefore be attempted first. In case of failure, the McCannel modified stitch remains a useful and satisfying procedure allowing transscleral fixation of the complex to the sulcus at the cost of a minimal corneal trauma.

  4. Thermodynamics of mixed-ligand complex formation of zinc nitrilotriacetate with amino acids and dipeptides in solution

    International Nuclear Information System (INIS)

    Pyreu, Dmitrii; Gruzdev, Matvey; Kumeev, Roman; Gridchin, Sergei

    2014-01-01

    Highlights: • Stable mixed ligand complexes of ZnNta with amino acids and dipeptides. • Histamine-like coordination mode of His in the complex ZnNtaHis. • Glycine-like coordination of Lys and Orn in the complexes ZnNtaL and ZnNtaHL • NH 2 , CO-coordination mode of GlyGly in the complex ZnNtaGG. • NH 2 , N − or NH2, N − , COO-coordination modes of GlyGly in the complex ZnNtaGGH −1 . - Abstract: The isothermal calorimetry, pH-potentiometric titration and 1 H and 13 C NMR methods has been used to study the mixed-ligand complex formation in the systems Zn 2+ –Nta 3– –L − (L = His, Orn, Lys, GlyGly, AlaAla) in aqueous solution at 298.15 K and the ionic strength of I = 0.5 (KNO 3 ). The thermodynamic parameters of formation of the mixed complexes have been determined. The relationship between the probable coordination modes of the complexone and amino acid or dipeptide molecules in the mixed-ligand complex and the thermodynamic parameters has been discussed

  5. Thermodynamics of mixed-ligand complex formation of zinc nitrilotriacetate with amino acids and dipeptides in solution

    Energy Technology Data Exchange (ETDEWEB)

    Pyreu, Dmitrii, E-mail: pyreu@mail.ru [Department of Inorganic and Analytic Chemistry, Ivanovo State UniversityErmak 39, Ivanovo 153025 (Russian Federation); Gruzdev, Matvey; Kumeev, Roman [G.A. Krestov Institute of Solution Chemistry of the Russian Academy of Sciences, Ivanovo (Russian Federation); Gridchin, Sergei [Ivanovo State University of Chemistry and Technology, Ivanovo (Russian Federation)

    2014-10-20

    Highlights: • Stable mixed ligand complexes of ZnNta with amino acids and dipeptides. • Histamine-like coordination mode of His in the complex ZnNtaHis. • Glycine-like coordination of Lys and Orn in the complexes ZnNtaL and ZnNtaHL • NH{sub 2}, CO-coordination mode of GlyGly in the complex ZnNtaGG. • NH{sub 2}, N{sup −} or NH2, N{sup −}, COO-coordination modes of GlyGly in the complex ZnNtaGGH{sub −1}. - Abstract: The isothermal calorimetry, pH-potentiometric titration and {sup 1}H and {sup 13}C NMR methods has been used to study the mixed-ligand complex formation in the systems Zn{sup 2+}–Nta{sup 3–}–L{sup −} (L = His, Orn, Lys, GlyGly, AlaAla) in aqueous solution at 298.15 K and the ionic strength of I = 0.5 (KNO{sub 3}). The thermodynamic parameters of formation of the mixed complexes have been determined. The relationship between the probable coordination modes of the complexone and amino acid or dipeptide molecules in the mixed-ligand complex and the thermodynamic parameters has been discussed.

  6. Redox reactions of Cu(II)-amine complexes in aqueous solutions

    International Nuclear Information System (INIS)

    Kumbhar, A.G.; Kishore, Kamal

    2003-01-01

    A number of amines can be employed for all volatile treatment (AVT) of steam generator (SG) systems of nuclear power reactors. These amines form complexes with Cu 2+ and Ni 2+ ions which come into water due to corrosion. The redox reactions of a number of Cu(II)-AVT amine complexes and the stability of the transient species formed have been studied by pulse radiolysis technique. Rate constants for the reaction of e aq - with a number of Cu(II)-amine complexes have been determined by following the decay of e aq - absorption. Stability of Cu(I)-amine complexes was studied by following the kinetics of the bleaching signal formed at the λ max of the Cu(II) amine complex. Except for Cu(I)-triethanolamine complex all other Cu(I)-amine complexes were found to be stable. One-electron oxidation of Cu(II) amine complexes was studied using azidyl radicals for the oxidation reaction as OH radicals react with the alcohol groups present in the amines used in this study. Cu(III)-amine complexes were found to be unstable and decayed by second-order kinetics

  7. Thermodynamic Characteristics of Reactions of the Formation of Complexes between Triglycine and Ni2+ Ions in Aqueous Solution

    Science.gov (United States)

    Gorboletova, G. G.; Metlin, A. A.; Bychkova, S. A.

    2018-05-01

    Thermal effects of reactions of the formation of complexes between Ni(II) and triglycine are determined via direct calorimetry in aqueous solutions at 298.15 K and ionic strengths of 0.2, 0.5, and 1.0 (KNO3). Standard thermodynamic characteristics (Δr H°, Δr G°, Δr S°) of complexing processes in the investigated systems are calculated. The structures of triglycinate complexes NiL+, NiH-1L, NiL2, NiH-2L2- 2, NiL- 3, and NiH-3L4- 3 are introduced to compare the obtained values and data on the thermodynamics of triglycinate complexes of Ni(II).

  8. An initial research on solute migration model coupled with adsorption of surface complexation in groundwater

    International Nuclear Information System (INIS)

    Qian Tianwei; Chen Fanrong

    2003-01-01

    The influence of solution chemical action in groundwater on solute migration has attracted increasing public attention, especially adsorption action occurring on surface of solid phase and liquid phase, which has play a great role in solute migration. There are various interpretations on adsorption mechanism, in which surface complexion is one of successful hypothesis. This paper first establishes a geochemical model based on surface complexion and then coupled it with traditional advection-dispersion model to constitute a solute migration model, which can deal with surface complexion action. The simulated results fit very well with those obtained by the precursors, as compared with a published famous example, which indicates that the model set up by this paper is successful. (authors)

  9. Generalist solutions to complex problems: generating practice-based evidence--the example of managing multi-morbidity.

    Science.gov (United States)

    Reeve, Joanne; Blakeman, Tom; Freeman, George K; Green, Larry A; James, Paul A; Lucassen, Peter; Martin, Carmel M; Sturmberg, Joachim P; van Weel, Chris

    2013-08-07

    A growing proportion of people are living with long term conditions. The majority have more than one. Dealing with multi-morbidity is a complex problem for health systems: for those designing and implementing healthcare as well as for those providing the evidence informing practice. Yet the concept of multi-morbidity (the presence of >2 diseases) is a product of the design of health care systems which define health care need on the basis of disease status. So does the solution lie in an alternative model of healthcare? Strengthening generalist practice has been proposed as part of the solution to tackling multi-morbidity. Generalism is a professional philosophy of practice, deeply known to many practitioners, and described as expertise in whole person medicine. But generalism lacks the evidence base needed by policy makers and planners to support service redesign. The challenge is to fill this practice-research gap in order to critically explore if and when generalist care offers a robust alternative to management of this complex problem. We need practice-based evidence to fill this gap. By recognising generalist practice as a 'complex intervention' (intervening in a complex system), we outline an approach to evaluate impact using action-research principles. We highlight the implications for those who both commission and undertake research in order to tackle this problem. Answers to the complex problem of multi-morbidity won't come from doing more of the same. We need to change systems of care, and so the systems for generating evidence to support that care. This paper contributes to that work through outlining a process for generating practice-based evidence of generalist solutions to the complex problem of person-centred care for people with multi-morbidity.

  10. Adsorption of Nucleic Acid/Protein Supramolecular Complexes on Goethite: The Influence of Solution Interactions on Behavior at the Solution-Mineral Interface

    Science.gov (United States)

    Schmidt, M.; Martinez, C. E.

    2017-12-01

    Adsorption of biomolecule rich supramolecular complexes onto mineral surfaces plays an important role in the development of organo-mineral associations in soils. In this study, a series of supramolecular complexes of a model nucleic acid (deoxyribonucleic acid (DNA)) and protein (bovine serum albumin (BSA)) are synthesized, characterized and exposed to goethite to probe their adsorption behavior. To synthesize DNA/BSA complexes, a fixed DNA concentration (0.1 mg/mL) was mixed with a range of BSA concentrations (0.025-0.5 mg/mL) in 5 mM KCl at pH=5.0. Circular dichroism spectroscopy demonstrates strong, cooperative, Hill-type binding between DNA and BSA (Ka= 4.74 x 105 M-1) with DNA saturation achieved when BSA concentration reaches 0.4 mg/mL. Dynamic light scattering measurements of DNA/BSA complexes suggest binding accompanies disruption of DNA-DNA intermolecular electrostatic repulsion, resulting in a decrease of the DNA slow relaxation mode with increasing amount of BSA. Zeta potential measurements show increasing amounts of BSA lead to a reduction of negative charge on DNA/BSA complexes, in line with light scattering results. In situ attenuated total reflectance Fourier transform infrared spectroscopic studies of adsorption of DNA/BSA complexes onto goethite show that complexation of BSA with DNA appears to hinder direct coordination of DNA backbone phosphodiester groups with goethite, relative to DNA by itself. Furthermore, increasing amount of BSA (up to 0.4 mg/mL) in DNA/BSA complexes enhances DNA adsorption, possibly as a result of reduced repulsion between adsorbed DNA helices. When BSA concentration exceeds 0.4 mg/mL, a decrease in adsorbed DNA is observed. We hypothesize that this discrepancy in behavior between systems with BSA concentrations below and above saturation of DNA is caused by initial fast adsorption of loosely associated BSA on goethite, restricting access to goethite surface sites. Overall, these results highlight the impact of solution

  11. Inner- and outer-sphere complexation of ions at the goethite-solution interface

    NARCIS (Netherlands)

    Rahnemaie, R.; Hiemstra, T.; Riemsdijk, van W.H.

    2006-01-01

    Formation of inner- and outer-sphere complexes of environmentally important divalent ions on the goethite surface was examined by applying the charge distribution CD model for inner- and outer-sphere complexation. The model assumes spatial charge distribution between the surface (0-plane) and the

  12. Solution Strategies and Achievement in Dutch Complex Arithmetic: Latent Variable Modeling of Change

    Science.gov (United States)

    Hickendorff, Marian; Heiser, Willem J.; van Putten, Cornelis M.; Verhelst, Norman D.

    2009-01-01

    In the Netherlands, national assessments at the end of primary school (Grade 6) show a decline of achievement on problems of complex or written arithmetic over the last two decades. The present study aims at contributing to an explanation of the large achievement decrease on complex division, by investigating the strategies students used in…

  13. The Mechanism of Redox Reaction between Palladium(II Complex Ions and Potassium Formate in Acidic Aqueous Solution

    Directory of Open Access Journals (Sweden)

    Wojnicki M.

    2017-06-01

    Full Text Available The kinetics studies of redox reaction between palladium(II chloride complex ions and potassium formate in acidic aqueous solutions was investigated. It was shown, that the reduction reaction of Pd(II is selective in respect to Pd(II complex structure. The kinetic of the process was monitored spectrophotometrically. The influence of chloride ions concentration, Pd(II initial concentration, reductant concentration, ionic strength as well as the temperature were investigated in respect to the process dynamics. Arrhenius equation parameters were determined and are equal to 65.8 kJ/mol, and A = 1.12×1011 s−1.

  14. Structural organization of C{sub 60} fullerene, doxorubicin, and their complex in physiological solution as promising antitumor agents

    Energy Technology Data Exchange (ETDEWEB)

    Prylutskyy, Yu. I. [Taras Shevchenko National University of Kyiv (Ukraine); Evstigneev, M. P., E-mail: max-evstigneev@mail.ru [Belgorod State University, Department of Biology and Chemistry (Russian Federation); Cherepanov, V. V. [Institute of Physics of NAS of Ukraine (Ukraine); Kyzyma, O. A.; Bulavin, L. A.; Davidenko, N. A. [Taras Shevchenko National University of Kyiv (Ukraine); Scharff, P. [Ilmenau University of Technology (Germany)

    2015-01-15

    Specific features of structural self-organization of C{sub 60} fullerene (1 nm size range), antitumor antibiotic doxorubicin (Dox) and their complex in physiological solution (0.9 % NaCl) have been investigated by means of atomic-force microscopy, dynamic light scattering, and small-angle X-ray scattering. Significant ordering of the mixed system, C{sub 60} + Dox, was observed, suggesting the complexation between these drugs, and giving insight into the mechanism of enhancement of Dox antitumor effect on simultaneous administration with C{sub 60} fullerene.

  15. Carbon-13 magnetic relaxation rates or iron (III) complexes of some biogenic amines and parent compounds in aqueous solutions

    International Nuclear Information System (INIS)

    Lai, A.; Monduzzi, M.; Saba, G.

    1980-01-01

    Spin-lattice relaxation rates (R 1 ) from naturally occuring C-13 F.T. N.M.R. spectra of some catecholamines and parent compounds with Iron(III) at pD = 4 were determined in order to elucidate the molecular mechanism underlying their association in aqueous solutions. Complexation was observed only for catecholic ligands. The R 1 values were used to calculate iron-carbon scaled distances, and two complexation models were proposed where the catecholic function binds Fe(III) in the first and second coordination spheres respectively. The latter case was shown to be the consistent with the molecular geometries. (orig.)

  16. HF effect on dissociation kinetics of plutonium and neptunium complexes with 1,2-diaminocyclohexanetetraacetic acid in nitric acid solutions

    Energy Technology Data Exchange (ETDEWEB)

    Nikitina, S.A.; Stepanov, A.V.

    1982-01-01

    Dissociation kinetics of Pusup((4)) and Np sup((4)) complexes with DCTA were investigated in HNO/sub 3/ solutions in the presence of HF and arsenazo 3. It was found that HF or NaF produced a differentiating effect on the reactivity of the complexes at (HNO/sub 3/)=1-6 mol/l as well as inhibiting effect at (HNO/sub 3/)=0.01 mol/l. Conditions of the differential kinetic analysis of plutonium and neptunium in the mixture and differential spectrophotometric analysis of uranium (6) during the camouflage of neptunium (4) and plutonium (4) were determined.

  17. HF effect on dissociation kinetics of plutonium and neptunium complexes with 1,2-diaminocyclohexanetetraacetic acid in nitric acid solutions

    International Nuclear Information System (INIS)

    Nikitina, S.A.; Stepanov, A.V.

    1982-01-01

    Dissociation kinetics of Pusup((4)) and Np sup((4)) complexes with DCTA were investigated in HNO 3 solutions in the presence of HF and arsenazo 3. It was found that HF or NaF produced a differentiating effect on the reactivity of the complexes at [HNO 3 ]=1-6 mol/l as well as inhibiting effect at [HNO 3 ]=0.01 mol/l. Conditions of the differential kinetic analysis of plutonium and neptunium in the mixture and differential spectrophotometric analysis of uranium (6) during the camouflage of neptunium (4) and plutonium (4) were determined

  18. Ruthenium nitrosyl complexes in radioactive waste solutions in reprocessing plants. Pt. 3

    International Nuclear Information System (INIS)

    Blasius, E.; Mueller, K.

    1984-01-01

    With capillary isotachophoresis and free-flow isotachophoresis it is possible to separate and isolate preparatively the mononuclear cationic ruthenium nitrosyl nitrato complexes. The behaviour of these complexes during storage, concentration and calcination is studied: The conversion of six ruthenium nitrosyl nitrato complexes as a function of time is studied at -36 0 C, 0 0 C, +3 0 C and 100 0 C. The percentage of ruthenium nitrosyl complexes with NO 3 - as ligand increased markedly during concentration experiments. Above 250 0 C NOsub(x) is liberated and the colour of the residue changes from brown to brownish-grey. At 400 0 C ruthenium complexes are no longer detected and the inner walls of the apparatus are covered with RuO 2 . (orig.)

  19. Study of substitution reactions of ligands in VO2+ complexes in toluene solutions by ESR method

    International Nuclear Information System (INIS)

    Lundkvist, R.; Panfilov, A.T.; Kalinichenko, N.B.; Marov, I.N.; AN SSSR, Moscow. Inst. Geokhimii i Analiticheskoj Khimii)

    1976-01-01

    Kinetics and equilibrium of stepwise substitution of ligands have been investigated at different temperatures for the complexes of oxovanadium (4) with salicylaldoxime, 8-oxyquinoline, acetylacetone, benzoylacetone, and tenoyltrifluoroacetone. The relative complexability of these ligands in toluene has been studied. The parameters of spin-Hamiltonian of EPR spectra of the VO 2+ complexes have been determined. The equilibrium constants, the rate constants, and activation energy have been found for the substitution reactions of ligands in the complexes VOA 2 : VOA 2 +HB=VOAB+HA; VOAB+HB=VOB 2 +HA, where HA and HB are the ligands with different donor atoms. The mixed complexes have been detected of the general formula VOAB, where HA is salicylaldoxime or 8-oxyquinoline and HB is β-diketone

  20. Solution equilibrium of metal ions-binary complexes with 3-(2-ethylamino-1-hydroxyethyl] phenol (Effortil

    Directory of Open Access Journals (Sweden)

    Mohamed Magdy Khalil

    2016-11-01

    Full Text Available Formation of binary complexes of Al(III, Cr(III, Fe(III, Th(IV, UO2(II, Ce(III, La(III, and Gd(III with 3-(2-ethylamino-1-hydroxyethyl] phenol (Effortil were studied potentiometrically at 37.0 °C and I = 0.16 mol dm−3 NaNO3 in aqueous solution. The acid–base properties of Effortil were investigated and discussed. The order of stability of the complexes was investigated and is discussed in terms of the metal ion. The experimental pH titration data were analyzed in order to evaluate the formation constants of various intermediate species formed. The concentration distribution of various species formed in solution was evaluated.

  1. Complex problems require complex solutions: the utility of social quality theory for addressing the Social Determinants of Health

    Directory of Open Access Journals (Sweden)

    Ward Paul R

    2011-08-01

    Full Text Available Abstract Background In order to improve the health of the most vulnerable groups in society, the WHO Commission on Social Determinants of Health (CSDH called for multi-sectoral action, which requires research and policy on the multiple and inter-linking factors shaping health outcomes. Most conceptual tools available to researchers tend to focus on singular and specific social determinants of health (SDH (e.g. social capital, empowerment, social inclusion. However, a new and innovative conceptual framework, known as social quality theory, facilitates a more complex and complete understanding of the SDH, with its focus on four domains: social cohesion, social inclusion, social empowerment and socioeconomic security, all within the same conceptual framework. This paper provides both an overview of social quality theory in addition to findings from a national survey of social quality in Australia, as a means of demonstrating the operationalisation of the theory. Methods Data were collected using a national random postal survey of 1044 respondents in September, 2009. Multivariate logistic regression analysis was conducted. Results Statistical analysis revealed that people on lower incomes (less than $45000 experience worse social quality across all of the four domains: lower socio-economic security, lower levels of membership of organisations (lower social cohesion, higher levels of discrimination and less political action (lower social inclusion and lower social empowerment. The findings were mixed in terms of age, with people over 65 years experiencing lower socio-economic security, but having higher levels of social cohesion, experiencing lower levels of discrimination (higher social inclusion and engaging in more political action (higher social empowerment. In terms of gender, women had higher social cohesion than men, although also experienced more discrimination (lower social inclusion. Conclusions Applying social quality theory allows

  2. Limitations when use chloramphenicol-bcyclodextrins complexes in ophtalmic solutions buffered with boric acid/borax system

    OpenAIRE

    Todoran Nicoleta; Ciurba Adriana; Rédai Emőke; Ion V.; Lazăr Luminița; Sipos Emese

    2014-01-01

    Chloramphenicol eye drops are commonly prescribed in concentrations of 0.5-1% in the treatment of infectious conjunctivitis. In terms of ophthalmic solution preparation, the major disadvantage of chloramphenicol consists in its low solubility in water. The solubility is increased by substances that form chloramphenicol-complexes, for example: boric acid/borax or cyclodextrins. Objective: Experimental studies aimed to evaluate the potential advantages of enhancing the solubility and stability ...

  3. Complex formation of CdSe/ZnS/TOPO nanocrystal vs. molecular chaperone in aqueous solution by hydrophobic interaction

    International Nuclear Information System (INIS)

    Horiuchi, Hiromi; Iwami, Noriya; Tachibana, Fumi; Ohtaki, Akashi; Iizuka, Ryo; Zako, Tamotsu; Oda, Masaru; Yohda, Masafumi; Tani, Toshiro

    2007-01-01

    Feasibilities to stabilize CdSe/ZnS/trioctylphosphineoxide (TOPO) nanocrystals (quantum dots, QDs) in aqueous solutions with prefoldin macromolecules in their bioactive states are reported. Prefoldin is a jellyfish-shaped hexameric co-chaperone of the group II chaperonins. As a protein folding intermediate is captured within its central cavity, so CdSe/ZnS/TOPO QDs would also be included within this cavity. It is also found the QDs can be much more dispersed in aqueous solutions and suspended for certain period of time by adding trace amount of t-butanol in the buffer prior to the mixing of the QDs mother solution. While biochemical procedures are evaluated with ordinary fluorescence measurements, possible complex formations are also evaluated with TIRFM single-molecule detection techniques

  4. Application of membrane LaF3 electrode in the determination of stability constants of Uranyl Fluoride complex in solution

    International Nuclear Information System (INIS)

    Muzakky; Iswani GS; Mintolo

    1996-01-01

    A membrane electrode LaF 3 has been applied in the determination of uranyl fluoride complex stability constant in solution. The determination is based on the detection of free F ion in solution as a result of hydrolysis reaction (process) of uranyl ions into the uranyl hydroxide form at low pH. The experiment results showed that there was no effect of ammonium carbonate 2 M titran, flow rate on the electrode response. The F release is optimum at pH 1. The free F ion in solution is calculated from the standard curve at pH 1, after the fluoride concentration at the same pH has been corrected. Using the plot of average number of ligand binding (n) versus minus log of free ligand (-log F) the value of β1 = 4.4, β2 = 7.48, β3=9.73, and β4 = 11.67

  5. Possibilities of application of perfect solution model to calculation of equilibrium composition of complex carbonitrides and their solubility in steels

    International Nuclear Information System (INIS)

    Gol'dshtejn, M.I.; Popov, V.V.; Cheremnykh, V.G.

    1980-01-01

    Using the Fe-Nb-V-C-N and Fe-Ti-V-C-N systems' low carbon steels, the earlier suggested model of perfect solid solutions has been experimentally researched. Also studied has been the feasibility to calculate the composition of carbonitrides in steels by the derived equations, that comprise, as parameters, products of respective compounds' solubility and coefficients of components interaction in iron-based solid solutions. A conclusion is drawn that perfect solutions models may be used adequately for complex carbonitrides like Nbsub(p)Vsub(1-p)Csub(q)Nsub(1-q) and Tisub(p)Vsub(1-p)Csub(q)Nsub(1-q) during the calculations of their equilibrium composition and solubility in steels

  6. Investigation of holmium(5) complexing in hydrofluoric acid solutions in the presence of alkali metal and ammonium fluorides

    International Nuclear Information System (INIS)

    Tsikaeva, D.V.; Agulyanskij, A.I.; Balabanov, Yu.I.; Kuznetsov, V.Ya.; Kalinnikov, V.T.

    1989-01-01

    Method of vibrational spectroscopy is used to study niobium-containing solutions of hydrofluoric acid in the presence of alkali metal and ammonium fluorides. It is shown that NbF 6 - and NbOF 5 2- ions co-exists in solutions, therewith, additions shift equilibrium to the second complex side. Methods of IR spectroscopy, roentgenometry, crystal optics and chemical analysis are used to identify precipitated from solutions solid phases. Three new phases, which composition by chemical analysis corresponds to M 3 Nb 2 OF 11 , where M=NH 4 , K, Rb, are detected. Their roentgenometric data displayed in tetragonal crystal system with a and c parameters equalling 15,710 and 7,744; 14,877 and 7,697; 15,511 and 7,785 A respectively, are presented

  7. Root finding in the complex plane for seismo-acoustic propagation scenarios with Green's function solutions.

    Science.gov (United States)

    McCollom, Brittany A; Collis, Jon M

    2014-09-01

    A normal mode solution to the ocean acoustic problem of the Pekeris waveguide with an elastic bottom using a Green's function formulation for a compressional wave point source is considered. Analytic solutions to these types of waveguide propagation problems are strongly dependent on the eigenvalues of the problem; these eigenvalues represent horizontal wavenumbers, corresponding to propagating modes of energy. The eigenvalues arise as singularities in the inverse Hankel transform integral and are specified by roots to a characteristic equation. These roots manifest themselves as poles in the inverse transform integral and can be both subtle and difficult to determine. Following methods previously developed [S. Ivansson et al., J. Sound Vib. 161 (1993)], a root finding routine has been implemented using the argument principle. Using the roots to the characteristic equation in the Green's function formulation, full-field solutions are calculated for scenarios where an acoustic source lies in either the water column or elastic half space. Solutions are benchmarked against laboratory data and existing numerical solutions.

  8. Deposition of crystalline hydroxyapatite nano-particle on zirconia ceramic: a potential solution for the poor bonding characteristic of zirconia ceramics to resin cement.

    Science.gov (United States)

    Azari, Abbas; Nikzad, Sakineh; Yazdani, Arash; Atri, Faezeh; Fazel Anvari-Yazdi, Abbas

    2017-07-01

    The poor bonding strength of zirconia to different dental substrates is one of the challenging issues in restorative dentistry. Hydroxyapatite is an excellent biocompatible material with fine bonding properties. In this study, it was hypothesized that hydroxyapatite coating on zirconia would improve its bond strength. Forty-five zirconia blocks were prepared and randomly divided into three groups: hydroxyapatite coating, sandblasting, and no preparation (control). The blocks were bonded to cement and the micro-shear bond strength was measured following load application. The bond strength values were analyzed with the Kruskal-Wallis test in 3 groups and paired comparisons were made using the Mann-Whitney U test. The failure patterns of the specimens were studied by a stereomicroscope and a scanning electron microscope and then analyzed by the chi-square test (significance level = 0.05). Deposition of hydroxyapatite on the zirconia surface significantly improved its bond strength to the resin cement in comparison with the control specimens (p improved the bond strength quality and values.

  9. Charge-transfer complexes between p-toluidine and iodine in solution: a kinetic study

    International Nuclear Information System (INIS)

    Beggiato, G.; Casalbore, G.; Marconi, G.; Baraldi, C.

    1985-01-01

    The kinetics of charge-transfer interaction between p-toluidine and iodine in methylene chloride was investigated in depth. The thermal process of formation of the 'inner' complex was found to proceed to an equilibrium. The photochemical process follows a different reaction coordinate, going through the formation of an exciplex between the excited 'outer' complex and the amine ground state. In both cases the same ionic complex (Am 2 I + I - 3 , where Am stands for p-toluidine) was detected as the final product. (Author)

  10. Estimated glomerular filtration rate is a poor predictor of the concentration of middle molecular weight uremic solutes in chronic kidney disease.

    Directory of Open Access Journals (Sweden)

    Nathalie Neirynck

    Full Text Available BACKGROUND: Uremic solute concentration increases as Glomerular Filtration Rate (GFR declines. Weak associations were demonstrated between estimated GFR (eGFR and the concentrations of several small water-soluble and protein-bound uremic solutes (MW500 Da. MATERIALS AND METHODS: In 95 CKD-patients (CKD-stage 2-5 not on dialysis, associations between different eGFR-formulae (creatinine, Cystatin C-based or both and the natural logarithm of the concentration of several LMWP's were analyzed: i.e. parathyroid hormone (PTH, Cystatin C (CystC, interleukin-6 (IL-6, tumor necrosis factor-alpha (TNF-α, leptin, retinol binding protein (RbP, immunoglobin light chains kappa and lambda (Ig-κ and Ig-λ, beta-2-microglobulin (β(2M, myoglobin and fibroblast growth factor-23 (FGF-23. RESULTS: The regression coefficients (R(2 between eGFR, based on the CKD-EPI-Crea-CystC-formula as reference, and the examined LMWP's could be divided into three groups. Most of the LMWP's associated weakly (R(2 0.7. Almost identical R(2-values were found per LMWP for all eGFR-formulae, with exception of CystC and β(2M which showed weaker associations with creatinine-based than with CystC-based eGFR. CONCLUSION: The association between eGFR and the concentration of several LMWP's is inconsistent, with in general low R(2-values. Thus, the use of eGFR to evaluate kidney function does not reflect the concentration of several LMWP's with proven toxic impact in CKD.

  11. Influence of ionic strength and OH(-) ion concentration on the Cu(II) complex formation with EDTA in alkaline solutions.

    Science.gov (United States)

    Norkus, E; Vaskelis, A; Zakaite, I

    1996-03-01

    D.c. polarographic data show that the complex formation of copper ions with EDTA depends markedly on the ionic strength of the solution at pH 8-10. This is primarily associated with the dependence of the fourth deprotonization constant of EDTA on the solution ionic strength: when it increases from 0.4 to 3.4, the pK(a4) value decreases from 9.5 to 8.2. According to polarographic and spectrophotometric data the degree of Cu(II) complexation increases at pH>10 due to transformation of the complex CuY(2-) to the more stable CuY(OH)(3-) (Y(4-), a fully deprotonized anion of EDTA), but it decreases with increase in alkalinity in a highly alkaline solution (pH>13.5). The latter result could be explained by the decrease in the EDTA anion activity. The calculated values of the activity coefficient are lower than 0.05 at pH>14.

  12. Solid solutions of platinum(II) and palladium(II) oxalato-complex salt as precursors of nanoalloys

    Science.gov (United States)

    Zadesenets, A. V.; Asanova, T. I.; Vikulova, E. S.; Filatov, E. Yu.; Plyusnin, P. E.; Baidina, I. A.; Asanov, I. P.; Korenev, S. V.

    2013-03-01

    A solid solution of platinum (II) and palladium (II) oxalato-complex salt, (NH4)2[Pt0.5Pd0.5(C2O4)2]·2H2O, has been synthesized and studied as a precursor for preparing bimetallic PtPd nanoparticles through its thermal decomposition. The smallest homogenous bimetallic PtPd nanoparticles were found to form in hydrogen and helium atmospheres. The annealing temperature and time have low effect on the bimetallic particles size. Comparative analysis of structural and thermal properties of the solid solution and individual Pt, Pd oxalato-complex salts was performed to investigate a mechanism of thermal decomposition of (NH4)2[Pt0.5Pd0.5(C2O4)2]·2H2O. Based on in situ X-ray photoemission spectroscopy investigation it was proposed a mechanism of formation of bimetallic PtPd nanoparticles from the solid-solution oxalato-complex salt during thermal decomposition.

  13. Spectroscopic investigation of solutions temperature effect on structure of americium(3) complexes with ethylenediaminetetraacetate and hydroxyethylethylenediaminetriacetate

    International Nuclear Information System (INIS)

    Nikitenko, S.I.; Martynenko, L.I.; Pechurova, N.I.

    1985-01-01

    Temperature dependence of absorption band intensity in spectra of solutions AmA - and AmX, where A 4- - ethylenediaminetetraacetate, X 3- - hydroxyethyl ethylenediaminetriacetate, has been studied spectrophotometrically. It is detected, that with the increase in solution temperature in the range 25-86 deg C a redistribution of absorption band intensities in AmA - X and AmX spectra is observed. Spectrum of Am 3+ never varies in the studied temperature range. It is assumed, that the observed phenomenon is explained by the change in the structure of Am 3+ complexonates during solution heating. Values of ΔH of the processes of internal coordination sphere rebuilding are calculated: 3.3+-0.9 (AmA - ), 2.2+-0.8 (AmX) kJ/mol

  14. Calcium-dependent stoichiometries of the KCa2.2 (SK) intracellular domain/calmodulin complex in solution.

    Science.gov (United States)

    Halling, D Brent; Kenrick, Sophia A; Riggs, Austen F; Aldrich, Richard W

    2014-02-01

    Ca(2+) activates SK Ca(2+)-activated K(+) channels through the protein Ca(2+) sensor, calmodulin (CaM). To understand how SK channels operate, it is necessary to determine how Ca(2+) regulates CaM binding to its target on SK. Tagless, recombinant SK peptide (SKp), was purified for binding studies with CaM at low and high Ca(2+) concentrations. Composition gradient multi-angle light scattering accurately measures the molar mass, stoichiometry, and affinity of protein complexes. In 2 mM Ca(2+), SKp and CaM bind with three different stoichiometries that depend on the molar ratio of SKp:CaM in solution. These complexes include 28 kD 1SKp/1CaM, 39 kD 2SKp/1CaM, and 44 kD 1SKp/2CaM. A 2SKp/2CaM complex, observed in prior crystallographic studies, is absent. At sedimentation coefficient is smaller for a 1SKp:1CaM solution than it is for either 2SKp:1CaM or 1SKp:2CaM. At low Ca(2+) and at >100 µM protein concentrations, a molar excess of SKp over CaM causes aggregation. Aggregation is not observed in Ca(2+) or with CaM in molar excess. In low Ca(2+) both 1SKp:1CaM and 1SKp:2CaM solutions have similar sedimentation coefficients, which is consistent with the absence of a 1SKp/2CaM complex in low Ca(2+). These results suggest that complexes with stoichiometries other than 2SKp/2CaM are important in gating.

  15. Exact solutions of time-fractional heat conduction equation by the fractional complex transform

    Directory of Open Access Journals (Sweden)

    Li Zheng-Biao

    2012-01-01

    Full Text Available The Fractional Complex Transform is extended to solve exactly time-fractional differential equations with the modified Riemann-Liouville derivative. How to incorporate suitable boundary/initial conditions is also discussed.

  16. Investigation of complex formation processes of hydroxypropylmethylcellulose and polymethacrylic acid in aqueous solutions

    Directory of Open Access Journals (Sweden)

    M. Katayeva

    2012-12-01

    Full Text Available The complex formation process of hydroxypropylcellulose (HPC with polymethacrylic acid (PMA have been studied using methods of turbidimetric and viscosimetric titration. Position of maximum depending on polymer concentration and molecular mass of polysaccharide have different values.

  17. Investigation of complex formation processes of hydroxypropylmethylcellulose and polymethacrylic acid in aqueous solutions

    OpenAIRE

    M. Katayeva; R. Mangazbayeva; R. Abdykalykova

    2012-01-01

    The complex formation process of hydroxypropylcellulose (HPC) with polymethacrylic acid (PMA) have been studied using methods of turbidimetric and viscosimetric titration. Position of maximum depending on polymer concentration and molecular mass of polysaccharide have different values.

  18. OptiPrep? Density Gradient Solutions for Macromolecules and Macromolecular Complexes

    Directory of Open Access Journals (Sweden)

    John Graham

    2002-01-01

    Full Text Available Any density gradient for the isolation of mammalian cells should ideally only expose the sedimenting particles to an increasing concentration of the gradient solute. Thus they will experience only an increasing density and viscosity, other parameters such as osmolality, pH, ionic strength and the concentration of important additives (such as EDTA or divalent cations should remain as close to constant as possible. This Protocol Article describes the strategies for the dilution of OptiPrep™ in order to prepare such solutions for mammalian cells.

  19. Ligand exchange in uranyl complexes in non-aqueous solutions: equilibrium properties

    International Nuclear Information System (INIS)

    Egozy, Y.; Weiss, S.

    1976-01-01

    The systems uranyl nitrate, tributylphosphate and 8-hydroxyquinoline or diphenylcarbazone were studied in chloroform, carbon tetrachloride and 1,2-dichloroethane at a number of temperatures. The nature of the complexes formed was determined and the equilibrium constants and several thermodynamic functions were measured. 8-hydroxyquinoline and diphenylcarbazone will be valuable as indicators for uranyl in kinetic studies. They are also interesting since they participate, along with tributylphosphate, in formation of synergistic complexes. (author)

  20. Formation of poly(ethylene glycol) inclusion complexes in aqueous solutions of mixed cyclodextrins

    Czech Academy of Sciences Publication Activity Database

    Horský, Jiří; Walterová, Zuzana

    2003-01-01

    Roč. 203, - (2003), s. 259-264 ISSN 1022-1360. [International Conference on Polymer-Solvent Complexes and Intercalates /4./. Prague, 22.07.2002-25.07.2002] R&D Projects: GA AV ČR IAA1050101 Institutional research plan: CEZ:AV0Z4050913 Keywords : cyclodextrins * inclusion complexes * phase separation Subject RIV: BO - Biophysics Impact factor: 0.895, year: 2003

  1. Definition of an intramolecular Eu-to-Eu energy transfer within a discrete [Eu2L] complex in solution.

    Science.gov (United States)

    Nonat, Aline; Regueiro-Figueroa, Martín; Esteban-Gómez, David; de Blas, Andrés; Rodríguez-Blas, Teresa; Platas-Iglesias, Carlos; Charbonnière, Loïc J

    2012-06-25

    Ligand L, based on two do3a moieties linked by the methylene groups of 6,6'-dimethyl-2,2'-bipyridine, was synthesized and characterized. The addition of Ln salts to an aqueous solution of L (0.01 M Tris-HCl, pH 7.4) led to the successive formation of [LnL] and [Ln(2)L] complexes, as evidenced by UV/Vis and fluorescence titration experiments. Homodinuclear [Ln(2)L] complexes (Ln = Eu, Gd, Tb, Yb, and Lu) were prepared and characterized. The (1)H and (13)C NMR spectra of the Lu and Yb complexes in D(2)O solution (pD = 7.0) showed C(1) symmetry of these species in solution, pointing to two different chemical environments for the two lanthanide cations. The analysis of the chemical shifts of the Yb complex indicated that the two coordination sites present square antiprismatic (SAP) coordination environments around the metal ions. The spectroscopic properties of the [Tb(2)L] complex upon ligand excitation revealed conventional behavior with τ(H2O) = 2.05(1) ms and ϕ(H2O) = 51%, except for the calculation of the hydration number obtained from the luminescent lifetimes in H(2)O and D(2)O, which pointed to a non-integer value of 0.6 water molecules per Tb(III) ion. In contrast, the Eu complex revealed surprising features such as: 1) the presence of two and up to five components in the (5)D(0)→(7)F(0) and (5)D(0)→(7)F(1) emission bands, respectively; 2) marked differences between the normalized spectra obtained in H(2)O and D(2)O solutions; and 3) unconventional temporal evolution of the luminescence intensity at certain wavelengths, the intensity profile first displaying a rising step before the occurrence of the expected decay. Additional spectroscopic experiments performed on [Gd(2-x)Eu(x)L] complexes (x = 0.1 and 1.9) confirmed the presence of two distinct Eu sites with hydration numbers of 0 (site I) and 2 (site II), and showed that the unconventional temporal evolution of the emission intensity is the result of an unprecedented intramolecular Eu

  2. Protonation of D-gluconate and its complexation with Np(V) in acidic to nearly neutral solutions

    International Nuclear Information System (INIS)

    Zhang, Z.; Clark, S.B.; Tian, G.; Rao, L.; Zanonato, P.L.

    2006-01-01

    Thermodynamic properties of the protonation of D-gluconic acid (HGH 4 (aq)) and its complexation with Np(V) have been studied in acidic to nearly neutral solutions at t = 25 C and I = 1 M NaClO 4 by potentiometry, spectrophotometry and calorimetry. The protonation constant (log K H ) and enthalpy (ΔH H ) of the carboxylate group are determined to be (3.30 ± 0.10) and -(4.03 ± 0.07) kJ mol -1 , respectively. Gluconate forms two Np(V) complexes in nearly neutral solutions. The formation constants and enthalpies of complexation are: log β 1 = (1.48 ± 0.03) and ΔH 1 = -(7.42 ± 0.13) kJ mol -1 for NpO 2 (GH 4 )(aq), log β = (2.14 ± 0.09) and ΔH 2 = -(12.08 ± 0.45) kJ mol -1 for NpO 2 (GH 4 ) 2 - . The thermodynamic parameters indicate that gluconic acid, like isosaccharinic acid and other α-hydroxycarboxylic acids, is a slightly stronger acid and forms stronger complexes with Np(V) than simple monocarboxylic acids. (orig.)

  3. Evaluation of Cognitive Complexity of Tasks for the Topic Hydrogen Exponent in the Solutions of Acids and Bases

    Directory of Open Access Journals (Sweden)

    Saša Horvat

    2018-02-01

    Full Text Available The aim of this study was evaluation of cognitive complexity of tasks for the topic hydrogen exponent in the solutions of acids and bases and its validation. The created procedure included an assessment of the difficulty of concepts and an assessment of their interactivity. There were 48 freshmen students enrolled in the study program Basic academic studies in chemistry. As a research instrument for assessing performance, test of knowledge was specifically constructed for this research. Each task in the test was followed by a seven-point Likert scale for the evaluation of invested mental effort. The evaluation of cognitive complexity was confirmed by a series of linear regression analysis where high values of correlation coefficients are obtained among the examined variables: student’s performance and invested mental effort (dependent variables and cognitive complexity (independent variable.

  4. Thermodynamics of the complex formation between thorium(IV) and some polydentate ligands in aqueous solution

    International Nuclear Information System (INIS)

    Di Bernado, P.; Cassol, A.; Tomat, G.; Bismondo, A.; Magon, L.

    1983-01-01

    The changes in free energy, enthalpy, and entropy for the formation of thorium(IV)-oxydiacetate, -iminodiacetate, -thiodiacetate, and -succinate complexes have been determined by potentiometric and calorimetric titrations at 25 deg C in aqueous 1 mol dm - 3 sodium perchlorate. All the ligands form 1:1 chelate complexes with the thorium(IV) ion the stability of which is dependent on both the chelate ring dimensions and the nature of the donor group in the chain. The order of the relative stabilities (iminodiacetate > oxydiacetate > thiodiacetate > succinate) is mainly dependent on the reaction enthalpies, since the δS values are close to each other. In the thorium(IV)-oxydiacetate system the maximum number of three ligands for every metal ion was reached. Because of precipitation of solid compounds in the other systems, it was only possible to define complexes with a lower number of co-ordinated ligands: two for succinate and thiodiacetate, and one for iminodiacetate. Owing to the lower stability of the chelate ring of thiodiacetate and succinate complexes and the high basicity of the amino-group of iminodiacetate, these ligands form also unchelated protonated complexes. (author)

  5. Theoretical and experimental study of actinide complexes with monoamides and organophosphorus ligands in solution

    International Nuclear Information System (INIS)

    Ribokaite, Kristina

    2013-01-01

    Monoamides and organophosphate are of great interest for the nuclear fuel cycle. Such ligands can selectively extract actinides in liquid-liquid extraction processes. The structure of the extractant (its functional group and its alkyl substituents) has a predominant role in the selective separation of actinides. This thesis concerns the theoretical and experimental studies of model systems in the aim of better understanding of the effect on molecular structures of the complexes. Structures of actinides complexes formed with model ligands in simple media (water or methanol in the presence of nitrate ions) have been characterized. At first, the complexation of uranyl by monoamide and phosphine oxide was studied in water and methanol. Molecular Dynamics simulations and DFT calculations were used to quantify the stability of uranyl complexes with those ligands, and to determine their structural properties. The theoretical results were then compared with experimental results obtained by UV-visible, infrared, Raman and EXAFS on the same chemical systems. The results were used to highlight the greater stability of uranyl complexes with phosphine oxide and monoamides. Further spectroscopic measurements combined with molecular modeling were used to gain a better understanding of the coordination mode of nitrate ion around the uranyl in both water and methanol. Finally, DFT calculations were used to study the influence of the structure of the monoamide or organophosphorus ligand and their interaction with the actinides (IV, VI) including steric effects in the first coordination sphere. (author) [fr

  6. Iterative methods for the solution of very large complex symmetric linear systems of equations in electrodynamics

    Energy Technology Data Exchange (ETDEWEB)

    Clemens, M.; Weiland, T. [Technische Hochschule Darmstadt (Germany)

    1996-12-31

    In the field of computational electrodynamics the discretization of Maxwell`s equations using the Finite Integration Theory (FIT) yields very large, sparse, complex symmetric linear systems of equations. For this class of complex non-Hermitian systems a number of conjugate gradient-type algorithms is considered. The complex version of the biconjugate gradient (BiCG) method by Jacobs can be extended to a whole class of methods for complex-symmetric algorithms SCBiCG(T, n), which only require one matrix vector multiplication per iteration step. In this class the well-known conjugate orthogonal conjugate gradient (COCG) method for complex-symmetric systems corresponds to the case n = 0. The case n = 1 yields the BiCGCR method which corresponds to the conjugate residual algorithm for the real-valued case. These methods in combination with a minimal residual smoothing process are applied separately to practical 3D electro-quasistatical and eddy-current problems in electrodynamics. The practical performance of the SCBiCG methods is compared with other methods such as QMR and TFQMR.

  7. Oxidation of ascorbic acid by a (salen)ruthenium(VI) nitrido complex in aqueous solution.

    Science.gov (United States)

    Wang, Qian; Man, Wai-Lun; Lam, William W Y; Lau, Tai-Chu

    2014-12-25

    The oxidation of ascorbic acid (H2A) by [Ru(VI)(N)(L)(MeOH)](+) in aqueous acidic solutions has the following stoichiometry: 2[Ru(VI)(N)] + 3H2A → 2[Ru(III)(NH2-HA)](+) + A. Mechanisms involving HAT/N-rebound at low pH (≤2) and nucleophilic attack at the nitride at high pH (≥5) are proposed.

  8. Spectroscopic and DFT Study of RhIII Chloro Complex Transformation in Alkaline Solutions.

    Science.gov (United States)

    Vasilchenko, Danila B; Berdyugin, Semen N; Korenev, Sergey V; O'Kennedy, Sean; Gerber, Wilhelmus J

    2017-09-05

    The hydrolysis of [RhCl 6 ] 3- in NaOH-water solutions was studied by spectrophotometric methods. The reaction proceeds via successive substitution of chloride with hydroxide to quantitatively form [Rh(OH) 6 ] 3- . Ligand substitution kinetics was studied in an aqueous 0.434-1.085 M NaOH matrix in the temperature range 5.5-15.3 °C. Transformation of [RhCl 6 ] 3- into [RhCl 5 (OH)] 3- was found to be the rate-determining step with activation parameters of ΔH † = 105 ± 4 kJ mol -1 and ΔS † = 59 ± 10 J K -1 mol -1 . The coordinated hydroxo ligand(s) induces rapid ligand substitution to form [Rh(OH) 6 ] 3- . By simulating ligand substitution as a dissociative mechanism, using density functional theory (DFT), we can now explain the relatively fast and slow kinetics of chloride substitution in basic and acidic matrices, respectively. Moreover, the DFT calculated activation energies corroborated experimental data that the kinetic stereochemical sequence of [RhCl 6 ] 3- hydrolysis in an acidic solution proceeds as [RhCl 6 ] 3- → [RhCl 5 (H 2 O)] 2- → cis-[RhCl 4 (H 2 O) 2 ] - . However, DFT calculations predict in a basic solution the trans route of substitution [RhCl 6 ] 3- → [RhCl 5 (OH)] 3- → trans-[RhCl 4 (OH) 2 ] 3- is kinetically favored.

  9. Zirconium bisamidinate complexes with sterically demanding ligands : structure, solution dynamics, and reactivity

    NARCIS (Netherlands)

    Otten, Edwin; Dijkstra, Peter; Visser, Cindy; Meetsma, Auke; Hessen, Bart

    2005-01-01

    Bisamidinate zirconium dichloride and dimethyl complexes with the sterically demanding amidinate ligands [PhC(NAr)(2))](-) (A) and [PhC(NAr)(NAr')](-) (B) (Ar = 2,6-(Pr2C6H3)-Pr-i; Ar' = 2,6-Me2C6H3) were prepared. The steric demand of ligand A induces the unusual trans geometry in

  10. Complexation of lysozyme with sodium caseinate and micellar casein in aqueous buffered solutions

    NARCIS (Netherlands)

    Antonov, Y.A.; Moldenaers, P.; Cardinaels, R.M.

    We present an extended structural and morphological study of the complexation of lysozyme (Lys) with sodium caseinate (SC) and micellar casein (MC) by means of turbidity measurements, phase analysis, dynamic, static and electrophoretic light scattering, bright-field and confocal laser scanning

  11. Using remote substituents to control solution structure and anion binding in lanthanide complexes

    DEFF Research Database (Denmark)

    Tropiano, Manuel; Blackburn, Octavia A.; Tilney, James A.

    2013-01-01

    A study of the anion-binding properties of three structurally related lanthanide complexes, which all contain chemically identical anion-binding motifs, has revealed dramatic differences in their anion affinity. These arise as a consequence of changes in the substitution pattern on the periphery ...

  12. Exploring Fluorescence Antibunching in Solution To Determine the Stoichiometry of Molecular Complexes

    Czech Academy of Sciences Publication Activity Database

    Sýkora, Jan; Kaiser, K.; Gregor, I.; Bönigk, W.; Schmalzing, G.; Enderlain, J.

    2007-01-01

    Roč. 79, - (2007), s. 4040-4049 ISSN 0003-2700 R&D Projects: GA MŠk(CZ) LC06063 Institutional research plan: CEZ:AV0Z40400503 Keywords : exploring fluorescence antibunching * molecular complex es * biophysical methods Subject RIV: CF - Physical ; Theoretical Chemistry Impact factor: 5.287, year: 2007

  13. Novel bi-metallic uranyl complexes - Redox chemistry in aqueous solutions

    International Nuclear Information System (INIS)

    Yardeni, A.; Mizrahi, E.; Maimon, I.; Zilbermann, G.; Meyerstein, D.; Zehavi-cohen, A.Z.

    2014-01-01

    The synthesis of organic ligands which can accommodate two uranium atoms at different oxidation states, mixed valency being then achieved by redox chemistry at room temperature is definitely a challenge in coordination chemistry. The following complexes were synthesized and characterized by elemental analysis, NMR, MS, IR and UV-vis

  14. Preparation and tribological properties of inclusion complex of β-cyclodextrin/dialkyl pentasulfide as additive in PEG-600 aqueous solution

    International Nuclear Information System (INIS)

    Guan, Jiju; Xu, Xuefeng; Li, Gan; Peng, Wei

    2014-01-01

    The inclusion complex of β-cyclodextrin (β-CD) and dialkyl pentasulfide (DPS), in which DPS was incorporated into β-CD cavities, was prepared by a co-precipitation method. The tribological properties of the complex used as lubricant additive in PEG 600 aqueous solution were investigated by a four-ball tester. The complex exhibited better tribological properties than β-CD under different loads, and also showed better anti-friction performance than DPS in the latter half of the test duration. The tribological action mechanism of the complex on a steel surface was studied according to the X-ray photoelectron spectroscopy (XPS) analyses. The β-CD molecules of the complexes were decomposed into various molecular fragments and the DPS molecules were released under the friction condition. It revealed that thiolate and ferrous sulfide (FeS) films formed by DPS played a major role, and iron alkoxide and carbon deposition films formed by the friction fragments of β-CD mainly exhibited anti-friction property on FeS-to-FeS interface. The interactions among different films led to the formation of a mixed boundary lubrication film.

  15. Electrochemical reactions of uranyl(VI) complexes in aqueous solution, non-aqueous solvents, and ionic liquids

    International Nuclear Information System (INIS)

    Ikeda, Yasuhisa

    2006-01-01

    Author's recent experimental results on the chemistry of U(V) in aqueous solution, non-aqueous solvents, and ionic solvents by cyclic voltametry are described. The U(V) was produced by electrochemical reduction of uranyl U(VI) ions or complexes such as carbonates, DMF(N, N-dimethylformamide), DMSO(dimethylsulfoxide), acetylacetonato, and other organic polydental ligands. The produced U(V) complexes were studied by spectrophotometry using optical-transmission thin-layer electrode. The U(V) complexes in non-aqueous solvents were found to be rather stable, they undergo ligand-dissociation reaction but not disproportionation reaction. The structure and electronic spectra as well as IR spectra of the complexes were studied. The present method was further developed to study the behavior of U(V) complexes in ionic liquids as molten salts, e.g., alkaline metals chlorides. Thus, the present research contributes to understanding the chemistry of 5fl system. Application to such nuclear technology as spent fuel reprocessing is discussed. (S. Ohno)

  16. The facile synthesis of a chitosan Cu(II) complex by solution plasma process and evaluation of their antioxidant activities.

    Science.gov (United States)

    Ma, Fengming; Li, Pu; Zhang, Baiqing; Wang, Zhenyu

    2017-10-01

    Synthesis of chitosan-Cu(II) complex by solution plasma process (SPP) irradiation was investigated. The effects of the distance between the electrodes, initial Cu(II) concentration, and initial pH on the Cu(II) adsorption capacity were evaluated. The results showed that narrower distance between the electrodes, higher initial Cu(II) concentration and higher initial pH (at pHchitosan-Cu(II) complex by ultraviolet-visible (UV-vis), fourier transform infrared (FT-IR) and electron spin resonance (ESR) spectroscopy revealed that the main structure of chitosan was not changed after irradiation. Thermogravimetry (TG) analysis indicated that Cu(II) ions were well incorporated into the chitosan. The antioxidant activity of the chitosan-Cu(II) complex was evaluated by DPPH, ABTS, and reducing power assays. The chitosan-Cu(II) complex exhibited greater antioxidant activity than the original chitosan. Thus, SPP could be used for preparation of chitosan-Cu(II) complexes. Copyright © 2017. Published by Elsevier B.V.

  17. Synthesis of titanium oxide nanoparticles using DNA-complex as template for solution-processable hybrid dielectric composites

    Energy Technology Data Exchange (ETDEWEB)

    Ramos, J.C. [Center for Sustainable Materials Chemistry, 153 Gilbert Hall, Oregon State University, Corvallis, OR (United States); Mejia, I.; Murphy, J.; Quevedo, M. [Department of Materials Science and Engineering, University of Texas at Dallas, Dallas, TX (United States); Garcia, P.; Martinez, C.A. [Engineering and Technology Institute, Autonomous University of Ciudad Juarez, Ciudad Juarez, Chihuahua (Mexico)

    2015-09-15

    Highlights: • We developed a synthesis method to produce TiO{sub 2} nanoparticles using a DNA complex. • The nanoparticles were anatase phase (~6 nm diameter), and stable in alcohols. • Composites showed a k of 13.4, 4.6 times larger than the k of polycarbonate. • Maximum processing temperature was 90 °C. • Low temperature enables their use in low-voltage, low-cost, flexible electronics. - Abstract: We report the synthesis of TiO{sub 2} nanoparticles prepared by the hydrolysis of titanium isopropoxide (TTIP) in the presence of a DNA complex for solution processable dielectric composites. The nanoparticles were incorporated as fillers in polycarbonate at low concentrations (1.5, 5 and 7 wt%) to produce hybrid dielectric films with dielectric constant higher than thermally grown silicon oxide. It was found that the DNA complex plays an important role as capping agent in the formation and suspension stability of nanocrystalline anatase phase TiO{sub 2} at room temperature with uniform size (∼6 nm) and narrow distribution. The effective dielectric constant of spin-cast polycarbonate thin-films increased from 2.84 to 13.43 with the incorporation of TiO{sub 2} nanoparticles into the polymer host. These composites can be solution processed with a maximum temperature of 90 °C and could be potential candidates for its application in low-cost macro-electronics.

  18. Thermal and volumetric properties of complex aqueous electrolyte solutions using the Pitzer formalism - The PhreeSCALE code

    Science.gov (United States)

    Lach, Adeline; Boulahya, Faïza; André, Laurent; Lassin, Arnault; Azaroual, Mohamed; Serin, Jean-Paul; Cézac, Pierre

    2016-07-01

    The thermal and volumetric properties of complex aqueous solutions are described according to the Pitzer equation, explicitly taking into account the speciation in the aqueous solutions. The thermal properties are the apparent relative molar enthalpy (Lϕ) and the apparent molar heat capacity (Cp,ϕ). The volumetric property is the apparent molar volume (Vϕ). Equations describing these properties are obtained from the temperature or pressure derivatives of the excess Gibbs energy and make it possible to calculate the dilution enthalpy (∆HD), the heat capacity (cp) and the density (ρ) of aqueous solutions up to high concentrations. Their implementation in PHREEQC V.3 (Parkhurst and Appelo, 2013) is described and has led to a new numerical tool, called PhreeSCALE. It was tested first, using a set of parameters (specific interaction parameters and standard properties) from the literature for two binary systems (Na2SO4-H2O and MgSO4-H2O), for the quaternary K-Na-Cl-SO4 system (heat capacity only) and for the Na-K-Ca-Mg-Cl-SO4-HCO3 system (density only). The results obtained with PhreeSCALE are in agreement with the literature data when the same standard solution heat capacity (Cp0) and volume (V0) values are used. For further applications of this improved computation tool, these standard solution properties were calculated independently, using the Helgeson-Kirkham-Flowers (HKF) equations. By using this kind of approach, most of the Pitzer interaction parameters coming from literature become obsolete since they are not coherent with the standard properties calculated according to the HKF formalism. Consequently a new set of interaction parameters must be determined. This approach was successfully applied to the Na2SO4-H2O and MgSO4-H2O binary systems, providing a new set of optimized interaction parameters, consistent with the standard solution properties derived from the HKF equations.

  19. Optimal non-coherent data detection for massive SIMO wireless systems: A polynomial complexity solution

    KAUST Repository

    Alshamary, Haider Ali Jasim

    2016-01-04

    © 2015 IEEE. This paper considers the joint maximum likelihood (ML) channel estimation and data detection problem for massive SIMO (single input multiple output) wireless systems. We propose efficient algorithms achieving the exact ML non-coherent data detection, for both constant-modulus constellations and nonconstant-modulus constellations. Despite a large number of unknown channel coefficients in massive SIMO systems, we show that the expected computational complexity is linear in the number of receive antennas and polynomial in channel coherence time. To the best of our knowledge, our algorithms are the first efficient algorithms to achieve the exact joint ML channel estimation and data detection performance for massive SIMO systems with general constellations. Simulation results show our algorithms achieve considerable performance gains at a low computational complexity.

  20. Optimal non-coherent data detection for massive SIMO wireless systems: A polynomial complexity solution

    KAUST Repository

    Alshamary, Haider Ali Jasim; Al-Naffouri, Tareq Y.; Zaib, Alam; Xu, Weiyu

    2016-01-01

    © 2015 IEEE. This paper considers the joint maximum likelihood (ML) channel estimation and data detection problem for massive SIMO (single input multiple output) wireless systems. We propose efficient algorithms achieving the exact ML non-coherent data detection, for both constant-modulus constellations and nonconstant-modulus constellations. Despite a large number of unknown channel coefficients in massive SIMO systems, we show that the expected computational complexity is linear in the number of receive antennas and polynomial in channel coherence time. To the best of our knowledge, our algorithms are the first efficient algorithms to achieve the exact joint ML channel estimation and data detection performance for massive SIMO systems with general constellations. Simulation results show our algorithms achieve considerable performance gains at a low computational complexity.

  1. Quantitative HPLC-ICP-MS analysis of antimony redox speciation in complex sample matrices: new insights into the Sb-chemistry causing poor chromatographic recoveries

    DEFF Research Database (Denmark)

    Hansen, Claus; Schmidt, Bjørn; Larsen, Erik Huusfeldt

    2011-01-01

    In solution antimony exists either in the pentavalent or trivalent oxidation state. As Sb(III) is more toxic than Sb(V), it is important to be able to perform a quantitative speciation analysis of Sb’s oxidation state. The most commonly applied chromatographic methods used for this redox speciation...

  2. Innovative solutions for the extraction of technology metals from complex primary and secondary raw materials

    Directory of Open Access Journals (Sweden)

    Kamberović Željko J.

    2016-01-01

    Full Text Available Presented compilation of scientific, theoretical and experimental results, promotes an innovative synergy of various metals and industrial activities in metallurgy, resulting in profitable transformation of by­products and waste materials into resources. Focusing on treatment of specific by-products from zinc and copper primary production, as well on specific waste streams like WEEE and waste automotive catalysts, group is actively contribute to the Serbia, region and EU sustainability policies. In terms of sustainable development, metallurgy is a traditional part of the solution rather than part of the problem, so it is necessary to take the chance and centuries-old tradition.

  3. Kinetic speciation of mercury–humate complexes in aqueous solutions by using competing ligand exchange method

    Digital Repository Service at National Institute of Oceanography (India)

    Vudamala, K.; Chakraborty, P.

    with ultrapure water (of resistivity 18.2 MΩ cm-1) acidified to contain 1 % (v/v) ultrapure HNO3 (Merck, Germany). Stock solutions of humic acid (HA) was prepared using HA from Fluka (commercialized by Sigma-Aldrich, cat. No. 53680, Sigma-Aldrich, Inc... river emptying into Cochin backwaters, Indian J. Mar. Sci. 15 (1986) 253–259. http://cat.inist.fr/?aModele=afficheN&cpsidt=8219806 (accessed September 4, 2015). [25] P.K. Krishnakumar, V.K. Pillai, Mercury Near a Caustic Soda plant at karwar,India, Mar...

  4. Conservation of vibrational coherence in ultrafast electronic relaxation: The case of diplatinum complexes in solution

    Czech Academy of Sciences Publication Activity Database

    Monni, R.; Auböck, G.; Kinschel, D.; Aziz-Lange, K. M.; Gray, H. B.; Vlček, Antonín; Chergui, M.

    2017-01-01

    Roč. 683, SEP 2017 (2017), s. 112-120 ISSN 0009-2614 R&D Projects: GA MŠk LD14129; GA ČR GA17-01137S Grant - others:COST(XE) CM1201 Institutional support: RVO:61388955 Keywords : vibrational energy * electronic energy * diplatinum complexes Subject RIV: CG - Electrochemistry OBOR OECD: Electrochemistry (dry cells, batteries, fuel cells, corrosion metals, electrolysis) Impact factor: 1.815, year: 2016

  5. Synthesis of complex oxides with garnet structure by spray drying of an aqueous salt solution

    Science.gov (United States)

    Makeenko, A. V.; Larionova, T. V.; Klimova-Korsmik, O. G.; Starykh, R. V.; Galkin, V. V.; Tolochko, O. V.

    2017-04-01

    The use of spray drying to obtain powders of complex oxides with a garnet structure has demonstrated. The processes occurring during heating of the synthesized oxide-salt product, leading to the formation of a material with a garnet structure, have been investigated using DTA, TGA, XPS, and XRD. It has been shown that a single-phase garnet structure of system (Y x Gd(3- x))3Al5O12 can be synthesized over the entire range of compositions.

  6. Investigation of complexing in solutions of salt mixture In(NO3)3-NaVO3

    International Nuclear Information System (INIS)

    Nakhodnova, A.N.; Listratenko, I.V.

    1987-01-01

    Spectrophotometry, conductometry and pH-metry are used to investigate properties and composition of the solid phases of isomolar series of In(NO 3 ) 3 -NaVO 3 salt mixture solutions and series of solutions having constant concentration of one of the components and varied of the other. Results of investigation are presented. It is stated that in the investigated solution series in weakly acid media HPA with the ratios [In 3+ ]:[V 5+ ] being equal to 11:1, 6:1, and 1:9, are formed. Composition of the complexes is mainly defined by the ratio of the components in In(NO 3 ) 3 and NaVO 3 salt mixture solutions and the medium acidity. Compounds of Na 2 OxIn 2 O 3 x2.5V 2 O 5 x8.5H 2 O and Cs 2 OxIn 2 O 3 x6V 2 O 5 x6.5H 2 O empirical formulae are separated. Results of IR spectroscopy, derivatography and X-ray phase analysis of the corresponding salts are presented

  7. Investigation of complexing in solutions of salt mixture In(NO/sub 3/)/sub 3/-NaVO/sub 3/

    Energy Technology Data Exchange (ETDEWEB)

    Nakhodnova, A N; Listratenko, I V

    1987-05-01

    Spectrophotometry, conductometry and pH-metry are used to investigate properties and composition of the solid phases of isomolar series of In(NO/sub 3/)/sub 3/-NaVO/sub 3/ salt mixture solutions and series of solutions having constant concentration of one of the components and varied of the other. Results of investigation are presented. It is stated that in the investigated solution series in weakly acid media HPA with the ratios (In/sup 3+/):(V/sup 5+/) being equal to 11:1, 6:1, and 1:9, are formed. Composition of the complexes is mainly defined by the ratio of the components in In(NO/sub 3/)/sub 3/ and NaVO/sub 3/ salt mixture solutions and the medium acidity. Compounds of Na/sub 2/OxIn/sub 2/O/sub 3/x2.5V/sub 2/O/sub 5/x8.5H/sub 2/O and Cs/sub 2/OxIn/sub 2/O/sub 3/x6V/sub 2/O/sub 5/x6.5H/sub 2/O empirical formulae are separated. Results of IR spectroscopy, derivatography and X-ray phase analysis of the corresponding salts are presented.

  8. A unified approach to model uptake kinetics of trace elements in complex aqueous – solid solution systems

    International Nuclear Information System (INIS)

    Thien, Bruno M.J.; Kulik, Dmitrii A.; Curti, Enzo

    2014-01-01

    Highlights: • There are several models able to describe trace element partitioning in growing minerals. • To describe complex systems, those models must be embedded in a geochemical code. • We merged two models into a unified one suitable for implementation in a geochemical code. • This unified model was tested against coprecipitation experimental data. • We explored how our model reacts to solution depletion effects. - Abstract: Thermodynamics alone is usually not sufficient to predict growth-rate dependencies of trace element partitioning into host mineral solid solutions. In this contribution, two uptake kinetic models were analyzed that are promising in terms of mechanistic understanding and potential for implementation in geochemical modelling codes. The growth Surface Entrapment Model (Watson, 2004) and the Surface Reaction Kinetic Model (DePaolo, 2011) were shown to be complementary, and under certain assumptions merged into a single analytical expression. This Unified Uptake Kinetics Model was implemented in GEMS3K and GEM-Selektor codes ( (http://gems.web.psi.ch)), a Gibbs energy minimization package for geochemical modelling. This implementation extends the applicability of the unified uptake kinetics model to accounting for non-trivial factors influencing the trace element partitioning into solid solutions, such as the changes in aqueous solution composition and speciation, or the depletion effects in closed geochemical systems

  9. A Structured Grid Based Solution-Adaptive Technique for Complex Separated Flows

    Science.gov (United States)

    Thornburg, Hugh; Soni, Bharat K.; Kishore, Boyalakuntla; Yu, Robert

    1996-01-01

    The objective of this work was to enhance the predictive capability of widely used computational fluid dynamic (CFD) codes through the use of solution adaptive gridding. Most problems of engineering interest involve multi-block grids and widely disparate length scales. Hence, it is desirable that the adaptive grid feature detection algorithm be developed to recognize flow structures of different type as well as differing intensity, and adequately address scaling and normalization across blocks. In order to study the accuracy and efficiency improvements due to the grid adaptation, it is necessary to quantify grid size and distribution requirements as well as computational times of non-adapted solutions. Flow fields about launch vehicles of practical interest often involve supersonic freestream conditions at angle of attack exhibiting large scale separate vortical flow, vortex-vortex and vortex-surface interactions, separated shear layers and multiple shocks of different intensity. In this work, a weight function and an associated mesh redistribution procedure is presented which detects and resolves these features without user intervention. Particular emphasis has been placed upon accurate resolution of expansion regions and boundary layers. Flow past a wedge at Mach=2.0 is used to illustrate the enhanced detection capabilities of this newly developed weight function.

  10. Connecting complexity with spectral entropy using the Laplace transformed solution to the fractional diffusion equation

    Science.gov (United States)

    Liang, Yingjie; Chen, Wen; Magin, Richard L.

    2016-07-01

    Analytical solutions to the fractional diffusion equation are often obtained by using Laplace and Fourier transforms, which conveniently encode the order of the time and the space derivatives (α and β) as non-integer powers of the conjugate transform variables (s, and k) for the spectral and the spatial frequencies, respectively. This study presents a new solution to the fractional diffusion equation obtained using the Laplace transform and expressed as a Fox's H-function. This result clearly illustrates the kinetics of the underlying stochastic process in terms of the Laplace spectral frequency and entropy. The spectral entropy is numerically calculated by using the direct integration method and the adaptive Gauss-Kronrod quadrature algorithm. Here, the properties of spectral entropy are investigated for the cases of sub-diffusion and super-diffusion. We find that the overall spectral entropy decreases with the increasing α and β, and that the normal or Gaussian case with α = 1 and β = 2, has the lowest spectral entropy (i.e., less information is needed to describe the state of a Gaussian process). In addition, as the neighborhood over which the entropy is calculated increases, the spectral entropy decreases, which implies a spatial averaging or coarse graining of the material properties. Consequently, the spectral entropy is shown to provide a new way to characterize the temporal correlation of anomalous diffusion. Future studies should be designed to examine changes of spectral entropy in physical, chemical and biological systems undergoing phase changes, chemical reactions and tissue regeneration.

  11. Inclusion Complexes of a New Family of Non-Ionic Amphiphilic Dendrocalix[4]arene and Poorly Water-Soluble Drugs Naproxen and Ibuprofen

    Directory of Open Access Journals (Sweden)

    Khalid Khan

    2017-05-01

    Full Text Available The inclusion complexes of a new family of nonionic amphiphilic calix[4]arenes with the anti-inflammatory hydrophobic drugs naproxen (NAP and ibuprofen (IBP were investigated. The effects of the alkyl chain’s length and the inner core of calix[4]arenes on the interaction of the two drugs with the calix[4]arenes were explored. The inclusion complexes of Amphiphiles 1a–c with NAP and IBP increased the solubility of these drugs in aqueous media. The interaction of 1a–c with the drugs in aqueous media was investigated through fluorescence, molecular modeling, and 1H-NMR analysis. TEM studies further supported the formation of inclusion complexes. The length of lipophilic alkyl chains and the intrinsic cyclic nature of cailx[4]arene derivatives 1a–c were found to have a significant impact on the solubility of NAP and IBP in pure water.

  12. Application of High-Resolution Ultrasonic Spectroscopy for analysis of complex formulations. Compressibility of solutes and solute particles in liquid mixtures

    International Nuclear Information System (INIS)

    Buckin, V

    2012-01-01

    The paper describes key aspects of interpretation of compressibility of solutes in liquid mixtures obtained through high-resolution measurements of ultrasonic parameters. It examines the fundamental relationships between the characteristics of solutes and the contributions of solutes to compressibility of liquid mixtures expressed through apparent adiabatic compressibility of solutes, and adiabatic compressibility of solute particles. In addition, it analyses relationships between the adiabatic compressibility of solutes and the measured ultrasonic characteristics of mixtures. Especial attention is given to the effects of solvents on the measured adiabatic compressibility of solutes and on concentration increment of ultrasonic velocity of solutes in mixtures.

  13. One-Photon Absorption Properties from a Hybrid Polarizable Density Embedding/Complex Polarization Propagator Approach for Polarizable Solutions

    DEFF Research Database (Denmark)

    Hršak, Dalibor; Nørby, Morten Steen; Coriani, Sonia

    2018-01-01

    We present a formulation of the polarizable density embedding (PDE) method in combination with the complex polarization propagator (CPP) method for the calculation of absorption spectra of molecules in solutions. The method is particularly useful for the calculation of near-edge X-ray absorption...... fine structure (NEXAFS) spectra. We compare the performance of PDE-CPP with the previously formulated polarizable embedding (PE)-CPP model for the calculation of the NEXAFS spectra of adenine, formamide, glycine, and adenosine triphosphate (ATP) in water at the carbon and nitrogen K-edges, as well...

  14. Radiolytic and photochemical reduction of carbon dioxide in solution catalyzed by transition metal complexes with some selected macrocycles

    International Nuclear Information System (INIS)

    Grodkowski, J.

    2004-01-01

    The main goal of the work presented in this report is an explanation of the mechanism of carbon dioxide (CO 2 ) reduction catalyzed by transition metal complexes with some selected macrocycles. The catalytic function of two electron exchange centers in the reduction of CO 2 , an inner metal and a macrocycle ring, was defined. Catalytic effects of rhodium, iron and cobalt porphyrins, cobalt and iron phthalocyanines and corroles as well as cobalt corrins have been investigated. CO 2 reduction by iron ions without presence of macrocycles and also in presence of copper compounds in aqueous solutions have been studied as well

  15. Fabrication of Chitosan-complexed Electrode and Evaluation of Its Efficiency in Removal of Copper Ion from Aqueous Solution

    Directory of Open Access Journals (Sweden)

    Yoon Young-Chan

    2016-01-01

    Full Text Available In this study, we fabricated chitosan/PVA/activated carbon complexed electrode to remove copper ion from aqueous solution. The prepared composite electrode was analyzed by BET and SEM to investigate its physicochemical properties. Electrochemical properties of prepared composite electrodes were analyzed via cyclic voltammetry. Adsorption performance of copper ion on chitosan composite complexed electrodes was evaluated. Almost similar pore size distribution results were observed in the series of ACP not included electrodes while observed differences in pore size distribution for the ACP included one. Cyclic voltammetry results exhibited that oxidation-reduction reaction does not occur in a potential range of -1.0 ~ 1.0 V. The amount of copper ion during adsroption reaction is increase according to increase of adsorption potential to 1.0 V.

  16. SIMULATION OF STRATEGIC SOLUTIONS ON FINANCIAL AND ECONOMIC PROVISION OF RUSSIAN DEFENCE INDUSTRY COMPLEX ENTERPRISES

    Directory of Open Access Journals (Sweden)

    K. B. Dobrova

    2011-01-01

    Full Text Available Creation of tools making it possible to efficiently control financial and production capability of industrial corporations making part of the Russian military-industrial complex are discussed for aviation enterprises as an example. A system of balanced indicators is proposed to be used to develop corporation’s adaptive management strategies. The enterprise production activity financial optimization task is solved on the basis of specific cost optimization criteria by means of linear programming. Economic mathematical models are proposed to optimize the scopes andtime terms of financing to be attracted over the planning intervals.

  17. Automating crystallographic structure solution and refinement of protein–ligand complexes

    International Nuclear Information System (INIS)

    Echols, Nathaniel; Moriarty, Nigel W.; Klei, Herbert E.; Afonine, Pavel V.; Bunkóczi, Gábor; Headd, Jeffrey J.; McCoy, Airlie J.; Oeffner, Robert D.; Read, Randy J.; Terwilliger, Thomas C.; Adams, Paul D.

    2013-01-01

    A software system for automated protein–ligand crystallography has been implemented in the Phenix suite. This significantly reduces the manual effort required in high-throughput crystallographic studies. High-throughput drug-discovery and mechanistic studies often require the determination of multiple related crystal structures that only differ in the bound ligands, point mutations in the protein sequence and minor conformational changes. If performed manually, solution and refinement requires extensive repetition of the same tasks for each structure. To accelerate this process and minimize manual effort, a pipeline encompassing all stages of ligand building and refinement, starting from integrated and scaled diffraction intensities, has been implemented in Phenix. The resulting system is able to successfully solve and refine large collections of structures in parallel without extensive user intervention prior to the final stages of model completion and validation

  18. Complex Kohn variational principle for the solution of Lippmann-Schwinger equations

    International Nuclear Information System (INIS)

    Adhikari, S.K.

    1992-07-01

    A recently proposed version of the Kohn variational principle for the t matrix incorporating the correct boundary condition is applied for the first time to the study of nucleon-nucleon scattering. Analytic expressions can be obtained for all the integrals in the method for a wide class of potentials and for a suitable choice of trial functions. Closed-form analytic expressions for these integrals are given for Yakawa and exponential potentials. Calculations with two commonly used S-wave nucleon-nucleon potentials show that the method may converge faster than other solution schemes not only for the phase-shifts but also for the off-shell t matrix elements if the freedom in the choice of the trial function is exploited. (author)

  19. Systematic analysis of protein–detergent complexes applying dynamic light scattering to optimize solutions for crystallization trials

    Energy Technology Data Exchange (ETDEWEB)

    Meyer, Arne [University of Hamburg, c/o DESY, Building 22a, Notkestrasse 85, 22603 Hamburg (Germany); Dierks, Karsten [University of Hamburg, c/o DESY, Building 22a, Notkestrasse 85, 22603 Hamburg (Germany); XtalConcepts, Marlowring 19, 22525 Hamburg (Germany); Hussein, Rana [University of Hamburg, c/o DESY, Building 22a, Notkestrasse 85, 22603 Hamburg (Germany); Brillet, Karl [ESBS, Pôle API, 300 Boulevard Sébastien Brant, CS10413, 67412 Illkirch CEDEX (France); Brognaro, Hevila [São Paulo State University, UNESP/IBILCE, Caixa Postal 136, São José do Rio Preto-SP, 15054 (Brazil); Betzel, Christian, E-mail: christian.betzel@uni-hamburg.de [University of Hamburg, c/o DESY, Building 22a, Notkestrasse 85, 22603 Hamburg (Germany)

    2015-01-01

    Application of in situ dynamic light scattering to solutions of protein–detergent complexes permits characterization of these complexes in samples as small as 2 µl in volume. Detergents are widely used for the isolation and solubilization of membrane proteins to support crystallization and structure determination. Detergents are amphiphilic molecules that form micelles once the characteristic critical micelle concentration (CMC) is achieved and can solubilize membrane proteins by the formation of micelles around them. The results are presented of a study of micelle formation observed by in situ dynamic light-scattering (DLS) analyses performed on selected detergent solutions using a newly designed advanced hardware device. DLS was initially applied in situ to detergent samples with a total volume of approximately 2 µl. When measured with DLS, pure detergents show a monodisperse radial distribution in water at concentrations exceeding the CMC. A series of all-transn-alkyl-β-d-maltopyranosides, from n-hexyl to n-tetradecyl, were used in the investigations. The results obtained verify that the application of DLS in situ is capable of distinguishing differences in the hydrodynamic radii of micelles formed by detergents differing in length by only a single CH{sub 2} group in their aliphatic tails. Subsequently, DLS was applied to investigate the distribution of hydrodynamic radii of membrane proteins and selected water-insoluble proteins in presence of detergent micelles. The results confirm that stable protein–detergent complexes were prepared for (i) bacteriorhodopsin and (ii) FetA in complex with a ligand as examples of transmembrane proteins. A fusion of maltose-binding protein and the Duck hepatitis B virus X protein was added to this investigation as an example of a non-membrane-associated protein with low water solubility. The increased solubility of this protein in the presence of detergent could be monitored, as well as the progress of proteolytic

  20. Removal of fission product ruthenium from purex process solutions: thiourea as complexing agent

    International Nuclear Information System (INIS)

    Floh, B.; Abrao, A.

    1980-01-01

    A new method for the treatment of spent uranium fuel is presented. It is based on the Purex Process using thiourea to increase the ruthenium decontamination factor. Thiourea exhibits a strong tendency for the formation of coordination compounds in acidic media. This tendency serves as a basis to transform nitrosyl-ruthenium species into Ru /SC(NH)(NH 2 )/ 2+ and Ru /SC(NH)(NH 2 )/ 3 complexes which are unextractable by TBP-varsol. The best conditions for the ruthenium-thiourea complex formation were found to be: thiourea-ruthenium ratio (mass/mass) close to 42, at 75 0 C, 30 minutes reaction time and aging period of 60 minutes. The ruthenium decontamination factor for a single uranium extraction are ca. 80-100, not interfering with extraction of actinides. These values are rather high in comparison to those obtained using the conventional Purex Process (e.g. F.D. sub(Ru)=10). By this reason the method developed here is suitable for the treatment of spent uranium fuels. Thiourea (100g/l) scrubbing experiments of ruthenium, partially co-extracted with actinides, confirmed the possibility of its removal from the extract. A decontamination greater than 83,5% for ruthenium as fission product is obtained in two stages with this procedure. (Author) [pt

  1. Carbon-13 NMR characterization of actinyl(VI) carbonate complexes in aqueous solution

    International Nuclear Information System (INIS)

    Clark, D.L.; Hobart, D.E.; Palmer, P.D.; Sullivan, J.C.; Stout, B.E.

    1992-01-01

    The uranyl(VI) carbonate system has been re-examined using 13 C NMR of 99.9% 13 C-enriched U VI O 2 ( 13 CO 3 ) 3 4- in millimolar concentrations. By careful control of carbonate ion concentration, we have confirmed the existence of the trimer, and observed dynamic equilibrium between the monomer and the timer. In addition, the ligand exchange reaction between free and coordinated carbonate on Pu VI O 2 ( 13 CO 3 ) 3 4- and Am VI O 2 ( 13 CO 3 ) 3 4- systems has been examined by variable temperature 13 C NMR line-broadening techniques 13 C NMR line-broadening techniques. A modified Carr-Purcell-Meiboom-Gill NMR pulse sequence was written to allow for experimental determination of ligand exchange parameters for paramagnetic actinide complexes. Preliminary Eyring analysis has provided activation parameters of ΔG double-dagger 295 = 56 kJ/M, ΔH double-dagger = 38 kJ/M, and ΔS double-dagger = -60 J/M-K for the plutonyl triscarbonate system, suggesting an associative transition state for the plutonyl (VI) carbonate complex self-exchange reaction. Experiments for determination of the activation parameters for the americium (VI) carbonate system are in progress

  2. Microalgal-biochar immobilized complex: A novel efficient biosorbent for cadmium removal from aqueous solution.

    Science.gov (United States)

    Shen, Ying; Li, Huan; Zhu, Wenzhe; Ho, Shih-Hsin; Yuan, Wenqiao; Chen, Jianfeng; Xie, Youping

    2017-11-01

    The feasibility of the bioremediation of cadmium (Cd) using microalgal-biochar immobilized complex (MBIC) was investigated. Major operating parameters (e.g., pH, biosorbent dosage, initial Cd(II) concentration and microalgal-biochar ratio) were varied to compare the treatability of viable algae (Chlorella sp.), biochar and MBIC. The biosorption isotherms obtained by using algae or biochar were found to have satisfactory Langmuir predictions, while the best fitting adsorption isotherm model for MBIC was the Sips model. The maximum Cd(II) adsorption capacity of MBIC with a Chlorella sp.: biochar ratio of 2:3 (217.41mgg -1 ) was higher than that of Chlorella sp. (169.92mgg -1 ) or biochar (95.82mgg -1 ) alone. The pseudo-second-order model fitted the biosorption process of MBIC well (R 2 >0.999). Moreover, zeta potential, SEM and FTIR studies revealed that electrostatic attraction, ion exchange and surface complexation were the main mechanisms responsible for Cd removal when using MBIC. Copyright © 2017 Elsevier Ltd. All rights reserved.

  3. Thermodynamic study of charge-transfer complex of iodine with HT18C6 in chloroform solution

    Directory of Open Access Journals (Sweden)

    Mahmoud Javadian Jazi

    2008-08-01

    Full Text Available A spectrophotometric study concerning the interaction between HT18C6 as n-donor and I2 as σ-acceptor has been performed in chloroform solution at different temperatures. The results are indicative of the formation 1:1 complex through equilibrium reaction. The stability constant of the complex at 7, 13, 19 and 25 oC is obtained by the computer-fitting of absorbance-mole ratio data in MATLAB software. The ΔHo and ΔSo values are obtained by the Vant Hoff method. The obtained data show that the complex is enthalpy stabilized and entropy destabilized. The entropy destabilitization is attributed to the decrease of the entropy of the free donor upon complexation. Comparison of the data from this work with those of previous works done on 18C6-I2 and HA18C6-I2 is indicative of different stability, stoichiometry and products. The possible reasons for such differences are discussed.

  4. Separation of the noble metals ruthenium and palladium from nitric acid solution of the nuclear fuel reprocessing containing complexing agents

    International Nuclear Information System (INIS)

    Ghafourian, H.

    1989-06-01

    Two extraction chromatographic techniques have been developed. N'N diethylthiourea (DETU), which forms complexes with ruthenium that can be retained on an AG50W-X2 ion exchanger, has proved to be a suitable reagent. The structures of these complexes were elucidated by electrophoresis, ion exchange and IR spectroscopy. Under the same conditions Pd forms an insoluble DETU-complex of the formula [Pd(DETU) 4 ] 2+ , which allows the separation of this metal quantitatively. With regard to the application of the developed technique for recovery of the mentioned noble metals from dissolver residues of the nuclear fuel reprocessing, comparative studies were carried out for accompanying fission product nuclides and actinides such as Mo, Tc, Zr, Ce, U and Pu. It was found out that no complex between diethylthiourea and the fission products zirconium, molybdenum and cerium and the actinides uranium, plutonium and americium were formed. Technetium, which was originally present as pertechnetate, is reduced to Tc(IV) and retained on the cation exchanger together with ruthenium. Ruthenium was eluted with 6 M HNO 3 . The efficiency of the developed process has been demonstrated with simulated solutions. The achieved decontamination factors ranged from 10 2 to 10 6 depending on the nuclide. (orig./RB) [de

  5. Influence of complexing on physicochemical properties of polymer-salt solutions. Vliyanie kompleksoobrazovaniya na fiziko-khimicheskie svojstva polimerno-solevykh rastvorov

    Energy Technology Data Exchange (ETDEWEB)

    Ostroushko, A A; Yushkova, S M; Koridze, N V; Skobkoreva, N V; Zhuravleva, L I; Palitskaya, T A; Antropova, S V; Ostroushko, I P [Ural' skij Gosudarstvennyj Univ., Sverdlovsk (Russian Federation) AN SSSR, Moscow (Russian Federation). Inst. Obshchej i Neorganicheskoj Khimii

    1993-06-01

    Using the methods of spectrophotometry, viscosimetry, conductometry the influence of salt-polymer complexing processes on physicochemical prperties of aqueous solutions of yttrium, barium, copper nitrates and formates with polyvinyl alcohol was studied. Change of dynamic viscosity, specific electric conductivity of solutions in the process of complexing was shown. Thermal effects of salt-polymer interaction were measured. It is shown that decrease of transition temperature of polymer to plastic state in films, temperature and effective activation energy of salt decomposition is also connected with complexing. Effective values of surface tension on the boundary with air are measured. Coefficients of cation diffusion in polymer-salt solutions are estimated.

  6. Equidistance of the complex two-dimensional anharmonic oscillator spectrum: the exact solution

    International Nuclear Information System (INIS)

    Cannata, F; Ioffe, M V; Nishnianidze, D N

    2012-01-01

    We study a class of quantum two-dimensional models with complex potentials of a specific form. They can be considered as the generalization of a recently studied model with quadratic interaction not amenable to the conventional separation of variables. In the present case, the property of shape invariance provides the equidistant form of the spectrum and the algorithm to construct eigenfunctions analytically. It is shown that the Hamiltonian is non-diagonalizable, and the resolution of identity must also include the corresponding associated functions. In the specific case of anharmonic second plus fourth-order interaction, expressions for the wavefunctions and associated functions are constructed explicitly for the lowest levels, and the recursive algorithm to produce higher level wavefunctions is given. (paper)

  7. Shells and containers under complex impact shock conditions - a practical solution concept

    International Nuclear Information System (INIS)

    Krieg, R.

    2000-01-01

    Many practically relevant impact processes are not as hard as a projectile impact but calculation or experimental assessment are difficult. Recent experiments at Karlsruhe Research Center show that many of these processes are similar, independent of geometry and scale, even for complex geometries and conditions. The preconditions and scaling factors for transfer of the model results to real dimensions are presented, and experimental facilities for investigating liquid impact on container walls are described. The latter were originally developed for analyses of serious accidents in nuclear facilities but can be used for other purposes as well. Using a concrete example, it was shown that the load of liquid impact on a shell with relatively filigrane protruding structures is lower by a factor of 14 than the impact of a comparable solid [de

  8. Investigation of detergent effects on the solution structure of spinach Light Harvesting Complex II

    Energy Technology Data Exchange (ETDEWEB)

    Cardoso, Mateus B; Smolensky, Dmitriy; Heller, William T; O' Neill, Hugh, E-mail: hellerwt@ornl.gov, E-mail: oneillhm@ornl.gov [Center for Structural Molecular Biology, Chemical Sciences Division, Oak Ridge National Laboratory, Oak Ridge, Tennessee 37831 (United States)

    2010-11-01

    The properties of spinach light harvesting complex II (LHC II), stabilized in the detergents Triton X-100 (TX100) and n-Octyl-{beta}-D-Glucoside (BOG), were investigated by small-angle neutron scattering (SANS). The LHC II-BOG scattering curve overlaid well with the theoretical scattering curve generated from the crystal structure of LHC II indicating that the protein preparation was in its native functional state. On the other hand, the simulated LHC II curve deviated significantly from the LHC II-TX100 experimental data. Analysis by circular dichroism spectroscopy supported the SANS analysis and showed that LHC II-TX100 is inactivated. This investigation has implications for extracting and stabilizing photosynthetic membrane proteins for the development of biohybrid photoconversion devices.

  9. Leadership and leadership development in healthcare settings - a simplistic solution to complex problems?

    Science.gov (United States)

    McDonald, Ruth

    2014-10-01

    There is a trend in health systems around the world to place great emphasis on and faith in improving 'leadership'. Leadership has been defined in many ways and the elitist implications of traditional notions of leadership sit uncomfortably with modern healthcare organisations. The concept of distributed leadership incorporates inclusivity, collectiveness and collaboration, with the result that, to some extent, all staff, not just those in senior management roles, are viewed as leaders. Leadership development programmes are intended to equip individuals to improve leadership skills, but we know little about their effectiveness. Furthermore, the content of these programmes varies widely and the fact that many lack a sense of how they fit with individual or organisational goals raises questions about how they are intended to achieve their aims. It is important to avoid simplistic assumptions about the ability of improved leadership to solve complex problems. It is also important to evaluate leadership development programmes in ways that go beyond descriptive accounts.

  10. The effect of boundaries on the asymptotic wavenumber of spiral wave solutions of the complex Ginzburg–Landau equation

    KAUST Repository

    Aguareles, M.

    2014-06-01

    In this paper we consider an oscillatory medium whose dynamics are modeled by the complex Ginzburg-Landau equation. In particular, we focus on n-armed spiral wave solutions of the complex Ginzburg-Landau equation in a disk of radius d with homogeneous Neumann boundary conditions. It is well-known that such solutions exist for small enough values of the twist parameter q and large enough values of d. We investigate the effect of boundaries on the rotational frequency of the spirals, which is an unknown of the problem uniquely determined by the parameters d and q. We show that there is a threshold in the parameter space where the effect of the boundary on the rotational frequency switches from being algebraic to exponentially weak. We use the method of matched asymptotic expansions to obtain explicit expressions for the asymptotic wavenumber as a function of the twist parameter and the domain size for small values of q. © 2014 Elsevier B.V. All rights reserved.

  11. Chitosan-silica complex membranes from sulfonic acid functionalized silica nanoparticles for pervaporation dehydration of ethanol-water solutions.

    Science.gov (United States)

    Liu, Ying-Ling; Hsu, Chih-Yuan; Su, Yu-Huei; Lai, Juin-Yih

    2005-01-01

    Nanosized silica particles with sulfonic acid groups (ST-GPE-S) were utilized as a cross-linker for chitosan to form a chitosan-silica complex membranes, which were applied to pervaporation dehydration of ethanol-water solutions. ST-GPE-S was obtained from reacting nanoscale silica particles with glycidyl phenyl ether, and subsequent sulfonation onto the attached phenyl groups. The chemical structure of the functionalized silica was characterized with FTIR, (1)H NMR, and energy-dispersive X-ray. Homogeneous dispersion of the silica particles in chitosan was observed with electronic microscopies, and the membranes obtained were considered as nanocomposites. The silica nanoparticles in the membranes served as spacers for polymer chains to provide extra space for water permeation, so as to bring high permeation rates to the complex membranes. With addition of 5 parts per hundred of functionalized silica into chitosan, the resulting membrane exhibited a separation factor of 919 and permeation flux of 410 g/(m(2) h) in pervaporation dehydration of 90 wt % ethanol aqueous solution at 70 degrees C.

  12. Isomerization of 2-butene-1,4-diol in aqueous solutions catalyzed by palladium(II) complexes

    Energy Technology Data Exchange (ETDEWEB)

    Kalabin, S.M.; Novikov, N.A.; Belov, A.P.

    1989-02-01

    The authors studied the isomerization of 2-butene-1,4-diol into 3-butene-1,2-diol at 18-25/degree/C. The concentrations of the diol and PdCl/sub 2/ were (1.0-5.0) /times/ 10/sup /minus/2/ mole/liter at 5-10-fold excess amounts of HCl and NaCl. These additives were used because of their inhibiting action on the oxidation of olefinic compounds. 3-Butene-1,2-diol was identified by /sup 1/H NMR method directly in the reaction solutions in which the reaction solutions in which the reactions in D/sub 2/O were carried out. It was found that palladium(II) complexes catalyze the isomerization of 2-butene-1,4-diol into 3-butene-1,2-diol. A mechanism is proposed for the reaction, which includes the intermediate formation of /eta//sup 3/-allyl complex of palladium with a coordinated hydroxyl group.

  13. Dissolution of oxide films on iron in aqueous solutions containing complexing anions

    International Nuclear Information System (INIS)

    Shoesmith, D.W.; Lee, W.; Owen, D.G.

    1981-01-01

    The dissolution, in oxalic acid and oxalic acid plus ethylenediaminetetraacetate, of magnetite films grown at high temperature on iron has been studied under varying conditions of pH and temperature. For oxalate concentrations greater than about 2 x 10 -3 mol dm -3 , magnetite dissolves by direct chemical dissolution. The mechanism appears to involve adsorption of oxalate ions at ferric ion sites in the oxide lattice, followed by proton attack and desorption of cationic species. Once metal dissolution starts, β-ferrous oxalate dihydrate is precipitated on the electrode, leading to erratic fluctuations in the electrode potential and eventually to inhibition of metal dissolution. For oxalate concentrations -3 mol dm -3 , the predominant dissolution mechanism appears to involve reduction by the metal. Also, once solution penetration to the underlying metal has occurred, and the electrode has returned to the active state, autoreductive dissolution appears to predominate even at higher oxalate concentrations. This change in mechanism from predominantly chemical dissolution to predominantly autoreductive dissolution may be due, at least in part, to the desorption of oxalate ions at the more negative potentials achieved in the active state. (author)

  14. Solute effects on edge dislocation pinning in complex alpha-Fe alloys

    Science.gov (United States)

    Pascuet, M. I.; Martínez, E.; Monnet, G.; Malerba, L.

    2017-10-01

    Reactor pressure vessel steels are well-known to harden and embrittle under neutron irradiation, mainly because of the formation of obstacles to the motion of dislocations, in particular, precipitates and clusters composed of Cu, Ni, Mn, Si and P. In this paper, we employ two complementary atomistic modelling techniques to study the heterogeneous precipitation and segregation of these elements and their effects on the edge dislocations in BCC iron. We use a special and highly computationally efficient Monte Carlo algorithm in a constrained semi-grand canonical ensemble to compute the equilibrium configurations for solute clusters around the dislocation core. Next, we use standard molecular dynamics to predict and analyze the effect of this segregation on the dislocation mobility. Consistently with expectations our results confirm that the required stress for dislocation unpinning from the precipitates formed on top of it is quite large. The identification of the precipitate resistance allows a quantitative treatment of atomistic results, enabling scale transition towards larger scale simulations, such as dislocation dynamics or phase field.

  15. High-Order Finite-Difference Solution of the Poisson Equation Involving Complex Geometries in Embedded Meshes

    Science.gov (United States)

    Marques, Alexandre; Nave, Jean-Christophe; Rosales, Ruben

    2011-11-01

    The Poisson equation is of central importance in the description of fluid flows and other physical phenomena. In prior work, Marques, Nave, and Rosales introduced the Correction Function Method (CFM) to obtain fourth-order accurate solutions for the constant coefficient Poisson problem with prescribed jump conditions for the solution and its normal derivative across arbitrary interfaces. Here we combine this method with the ideas introduced by Mayo to solve other Poisson problems involving complex geometries. In summary, we are able to rewrite the problem as a boundary integral equation in terms of a potential distribution over the boundary or interface. The solution of this integral equation is discontinuous across the boundary or interface. Hence, after this integral equation is solved using standard techniques, the potential distribution can be used to determine the jump discontinuities. We are then able to use the CFM to solve the resulting Poisson equation with jump discontinuities. The outcome is a fourth-order accurate scheme to solve general Poisson problems which, over arbitrary geometries, has a cost that is approximately twice that of a fast Poisson solver using FFT on a rectangular geometry of the same size. Details of the method and applications will be presented.

  16. Separation of polythionates and the gold thiosulfate complex in gold thiosulfate leach solutions by ion-interaction chromatography.

    Science.gov (United States)

    O'Reilly, John W; Shaw, Matthew J; Dicinoski, Greg W; Grosse, Andrew C; Miura, Yasuyuki; Haddad, Paul R

    2002-07-01

    A method for the separation of the polythionates (SxO6(2-), x = 3-5) in gold thiosulfate leach solutions using ion-interaction chromatography with conductivity and ultraviolet (UV) detection is described. Polythionates were eluted within 18 min using an eluent comprising an acetonitrile step gradient at 0.0 min from 15% v/v to 28% v/v, 3 mM TBAOH, and 2.5 mM sodium carbonate, operated using a Dionex NS1-5 micron column with guard. The developed method was capable of separating the gold thiosulfate complex ion in standard solutions, but quantification of this species in realistic leach solutions proved impractical due to a self-elution effect that caused the gold peak to be eluted as a broad band. Detection limits for polythionates using a 10 microL injection volume ranged between 1-6 mg L(-1) (5-23 microM) for conductivity and 0.8-13 mg L(-1) (4-68 microM) for UV detection, based on a signal-to-noise ratio of 2. Calibration was linear over the ranges 5-2000, 10-2000 and 25-2500 mg L(-1) for trithionate, tetrathionate and pentathionate, respectively. The technique was applied successfully to leach liquors containing 0.5 M ammonium thiosulfate, 2 M ammonia, 0.05 M copper sulfate and 20 % m/v gold ore.

  17. Low-cost copper complexes as p-dopants in solution processable hole transport layers

    Energy Technology Data Exchange (ETDEWEB)

    Kellermann, Renate [Department for Materials Science and Engineering, Chair for Materials for Electronics and Energy Technology, Friedrich-Alexander-University Erlangen-Nuremberg, Erlangen 91058 (Germany); Siemens AG – Corporate Technology, Guenther-Scharowsky-Str. 1, Erlangen 91058 (Germany); Taroata, Dan; Maltenberger, Anna; Hartmann, David; Schmid, Guenter [Siemens AG – Corporate Technology, Guenther-Scharowsky-Str. 1, Erlangen 91058 (Germany); Brabec, Christoph J. [Department for Materials Science and Engineering, Chair for Materials for Electronics and Energy Technology, Friedrich-Alexander-University Erlangen-Nuremberg, Erlangen 91058 (Germany)

    2015-09-07

    We demonstrate the usage of the Lewis-acidic copper(II)hexafluoroacetylacetonate (Cu(hfac){sub 2}) and copper(II)trifluoroacetylacetonate (Cu(tfac){sub 2}) as low-cost p-dopants for conductivity enhancement of solution processable hole transport layers based on small molecules in organic light emitting diodes (OLEDs). The materials were clearly soluble in mixtures of environmentally friendly anisole and xylene and spin-coated under ambient atmosphere. Enhancements of two and four orders of magnitude, reaching 4.0 × 10{sup −11} S/cm with a dopant concentration of only 2 mol% Cu(hfac){sub 2} and 1.5 × 10{sup −9} S/cm with 5 mol% Cu(tfac){sub 2} in 2,2′,7,7′-tetra(N,N-ditolyl)amino-9,9-spiro-bifluorene (spiro-TTB), respectively, were achieved. Red light emitting diodes were fabricated with reduced driving voltages and enhanced current and power efficiencies (8.6 lm/W with Cu(hfac){sub 2} and 5.6 lm/W with Cu(tfac){sub 2}) compared to the OLED with undoped spiro-TTB (3.9 lm/W). The OLED with Cu(hfac){sub 2} doped spiro-TTB showed an over 8 times improved LT{sub 50} lifetime of 70 h at a starting luminance of 5000 cd/m{sup 2}. The LT{sub 50} lifetime of the reference OLED with PEDOT:PSS was only 8 h. Both non-optimized OLEDs were operated at similar driving voltage and power efficiency.

  18. Experimental control versus realism: methodological solutions for simulator studies in complex operating environments

    Energy Technology Data Exchange (ETDEWEB)

    Skraaning, Gyrd Jr.

    2004-03-15

    This report is a reprint of a dr.philos. thesis written by Gyrd Skraaning Jr. The text was submitted and accepted by the Norwegian University of Science and Technology in 2003 (ISBN 82-471-5237-1). The thesis suggests a nonlinear model of the theoretical relationship between experimental control and realism, claiming that high degrees of realism and experimental control can be obtained simultaneously if the experimental methods are utilized strategically and developed further. This is in opposition to the conventional opinion that realism and experimental control are mutually excluding objectives. The thesis debates the impact of the operating task on human performance during simulator studies in HAMMLAB, and suggests how task variation can be experimentally controlled. In a within subject design, every subject is tested under all experimental conditions, and the presentation order of the conditions is counterbalanced to compensate for order effects. In realistic settings, it is essential that the experimental design imposes few artificial constrains on the research environment. At the same time, the design should be able to uncover experimental effects in situations where the number of participants is low. Within-subject design represents a reasonable compromise between these aspirations. In this respect, an alternative counterbalancing method is proposed (dis-ORDER). A theoretical analysis of the human performance concept and a discussion about performance measurement in complex operating environments, are followed by a debate on the shortcomings of traditional performance indicators. Two specialized operator performance assessment techniques are then presented and evaluated (OPAS and ORT). (Author)

  19. Fuzzy logic: A “simple” solution for complexities in neurosciences?

    Science.gov (United States)

    Godil, Saniya Siraj; Shamim, Muhammad Shahzad; Enam, Syed Ather; Qidwai, Uvais

    2011-01-01

    Background: Fuzzy logic is a multi-valued logic which is similar to human thinking and interpretation. It has the potential of combining human heuristics into computer-assisted decision making, which is applicable to individual patients as it takes into account all the factors and complexities of individuals. Fuzzy logic has been applied in all disciplines of medicine in some form and recently its applicability in neurosciences has also gained momentum. Methods: This review focuses on the use of this concept in various branches of neurosciences including basic neuroscience, neurology, neurosurgery, psychiatry and psychology. Results: The applicability of fuzzy logic is not limited to research related to neuroanatomy, imaging nerve fibers and understanding neurophysiology, but it is also a sensitive and specific tool for interpretation of EEGs, EMGs and MRIs and an effective controller device in intensive care units. It has been used for risk stratification of stroke, diagnosis of different psychiatric illnesses and even planning neurosurgical procedures. Conclusions: In the future, fuzzy logic has the potential of becoming the basis of all clinical decision making and our understanding of neurosciences. PMID:21541006

  20. Experimental control versus realism: methodological solutions for simulator studies in complex operating environments

    International Nuclear Information System (INIS)

    Skraaning, Gyrd Jr.

    2004-03-01

    This report is a reprint of a dr.philos. thesis written by Gyrd Skraaning Jr. The text was submitted and accepted by the Norwegian University of Science and Technology in 2003 (ISBN 82-471-5237-1). The thesis suggests a nonlinear model of the theoretical relationship between experimental control and realism, claiming that high degrees of realism and experimental control can be obtained simultaneously if the experimental methods are utilized strategically and developed further. This is in opposition to the conventional opinion that realism and experimental control are mutually excluding objectives. The thesis debates the impact of the operating task on human performance during simulator studies in HAMMLAB, and suggests how task variation can be experimentally controlled. In a within subject design, every subject is tested under all experimental conditions, and the presentation order of the conditions is counterbalanced to compensate for order effects. In realistic settings, it is essential that the experimental design imposes few artificial constrains on the research environment. At the same time, the design should be able to uncover experimental effects in situations where the number of participants is low. Within-subject design represents a reasonable compromise between these aspirations. In this respect, an alternative counterbalancing method is proposed (dis-ORDER). A theoretical analysis of the human performance concept and a discussion about performance measurement in complex operating environments, are followed by a debate on the shortcomings of traditional performance indicators. Two specialized operator performance assessment techniques are then presented and evaluated (OPAS and ORT). (Author)

  1. Studies on some mixed ligand complexes of UO2(VI) in solution

    International Nuclear Information System (INIS)

    Katkar, V.S.; Munshi, K.N.

    1987-01-01

    Potentiometric studies on some mixed ligand complexes of UO 2 (VI) with ethylenediamine N,N' diacetic acid as primary ligand and succinic acid, malic acid, maleic acid, fumaric acid, malonic acid, adipic acid, itaconic acid, phthalic acid and mandelic acid as secondary ligands have been carried out employing modified form of Irving-Rossotti's pH titration technique. The study was carried out at three different temperatures, viz. 5deg, 25deg and 45degC and at fixed ionic strength of 0.2M KNO 3 . Thermodynamic parameters, e.g. ΔG, ΔH and ΔS have been evaluated and further ΔG and ΔH values have been separated into their electrostatic components, ΔGe and ΔHe and cratic components, ΔGsub(c) and ΔHsub(c). The effect of change in dielectric constant and change in ionic strength of the medium have also been investigated. The sequence of stability constants has been correlated with the properties of secondary ligands. (author). 21 refs., 5 tabs

  2. Instant and supersaturated dissolution of naproxen and sesamin (poorly water-soluble drugs and supplements) nanoparticles prepared by continuous expansion of liquid carbon dioxide solution through long dielectric nozzle

    Energy Technology Data Exchange (ETDEWEB)

    Arita, Toshihiko, E-mail: tarita@tagen.tohoku.ac.jp [Tohoku University, Institute of Multidisciplinary Research for Advanced Materials (Japan); Manabe, Noriyoshi [Tohoku University, Graduate School of Engineering (Japan); Nakahara, Koichi [Suntory Bussiness Expert Limited, Frontier Center for Value Creation (Japan)

    2012-11-15

    Nanoparticles (NPs) of naproxen (a nonsteroidal anti-inflammatory drug, BCS Class 2) and sesamin (a poorly water-soluble lignan) were investigated. By applying a newly developed rapid expansion system of liquid carbon dioxide solutions equipped with a dielectric nozzle, well-separated and fine both naproxen NPs (averaged particle size (APS) = 46.9 nm) and sesamin NPs (APS = 60.2 nm) were obtained without heating, surfactants, and co-solvents. Obtained naproxen and sesamin NPs had large surface/weight ratio, therefore, they showed instant dissolution to water until about ten percent higher than the saturated concentrations. In addition, the technique developed in the study has big advantage on producing especially drug NPs because the NPs produced by the method never includes neither poisonous additives (especially co-solvents and detergents) nor thermally denatured compounds.

  3. Breaking down barriers to communicating complex retinoblastoma information: can graphics be the solution?

    Science.gov (United States)

    Chiu, Hannah H; Dimaras, Helen; Downie, Rob; Gallie, Brenda

    2015-06-01

    To investigate the impact of a graphical timeline summarizing bilateral retinoblastoma disease and treatment outcomes on parents' understanding of complex medical information. Cross-sectional survey. Parents of children with retinoblastoma who were being actively managed at The Hospital for Sick Children were recruited. Forty-five parents from 42 families participated. After a standardized presentation on retinoblastoma and visual tool named Disease-Specific electronic Patient Illustrated Clinical Timeline (DePICT), parents completed a 19-item questionnaire designed to assess their understanding of treatment choices for 2 eyes in bilateral retinoblastoma as communicated using DePICT. SPSS was used to perform statistical analysis. Forty-five parents from 42 families participated (65% female). Median age of participants was 34 years. Median level of participant education was completion of college/trade school. The median level of annual income was $40,000 to $70,000 CDN. Median time since diagnosis of retinoblastoma in their child was 13.5 months. Twenty-three (51%) participants were parents of children with unilateral retinoblastoma, and 22 (49%) were parents of children with bilateral retinoblastoma. Median number of correct answers was 15 of 19, and mean score was 77%. Normal distribution of scores was noted. English as a first language was significantly associated with score (p = 0.01). No significant association was observed between other variables and score in all analyses. This study builds on the validation of DePICT by demonstrating that parents can achieve good comprehension even when considering choices for treatment for 2 eyes with bilateral retinoblastoma. Clinical application of this tool can enhance the consent process. Copyright © 2015 Canadian Ophthalmological Society. Published by Elsevier Inc. All rights reserved.

  4. Modeling of Flow, Transport and Controlled Sedimentation Phenomena during Mixing of Salt Solutions in Complex Porous Formations

    Science.gov (United States)

    Skouras, Eugene D.; Jaho, Sofia; Pavlakou, Efstathia I.; Sygouni, Varvara; Petsi, Anastasia; Paraskeva, Christakis A.

    2015-04-01

    The deposition of salts in porous media is a major engineering phenomenon encountered in a plethora of industrial and environmental applications where in some cases is desirable and in other not (oil production, geothermal systems, soil stabilization etc). Systematic approach of these problems requires knowledge of the key mechanisms of precipitating salts within the porous structures, in order to develop new methods to control the process. In this work, the development and the solution of spatiotemporally variable mass balances during salt solution mixing along specific pores were performed. Both analytical models and finite differences CFD models were applied for the study of flow and transport with simultaneous homogeneous and heterogeneous nucleation (by crystal growth on the surface of the pores) in simple geometries, while unstructured finite elements and meshless methods were developed and implemented for spatial discretization, reconstruction, and solution of transport equations and homogeneous / heterogeneous reactions in more complex geometries. At initial stages of this work, critical problem parameters were identified, such as the characteristics of the porosity, the number of dissolved components, etc. The parameters were then used for solving problems which correspond to available experimental data. For each combination of ions and materials, specific data and process characteristics were included: (a) crystal kinetics (nucleation, growth rates or reaction surface rates of crystals, critical suspension concentrations), (b) physico-chemical properties (bulk density, dimensions of generated crystals, ion diffusion coefficients in the solution), (c) operating parameters (macroscopic velocity, flow, or pressure gradient of the solution, ion concentration) (d) microfluidic data (geometry, flow area), (e) porosity data in Darcy description (initial porosity, specific surface area, tortuosity). During the modeling of flow and transport in three

  5. Study of complex formation of cobalt (II) and cobalt (III) in acrylamide aqueous solutions and in the phase of acrylamide hydrogel

    International Nuclear Information System (INIS)

    Ismailova, M.M.; Egorova, L.A.; Khamidov, B.O.

    1993-01-01

    Present article is devoted to study of complex formation of cobalt (II) and cobalt (III) in acrylamide aqueous solutions and in the phase of acrylamide hydrogel. The condition of cobalt in various rate of oxidation in acrylamide aqueous solutions was studied. The concentration conditions of stability of system Co(II)-Co(III) were defined. The composition of coordination compounds of cobalt (II) and cobalt (III) in acrylamide aqueous solutions and in the phase of acrylamide hydrogel was determined.

  6. Highly luminescent pure-red-emitting fluorinated β-diketonate europium(III) complex for full solution-processed OLEDs

    Energy Technology Data Exchange (ETDEWEB)

    Martins, Joao P. [CEMDRX, Physics Department, Universidade de Coimbra, Rua Larga, Coimbra P-3004-516 (Portugal); Serviço de Medicina Nuclear, SESARAM E.P.E., Avenida Luís de Camões 57, Funchal 9004-514, Madeira (Portugal); Martín-Ramos, Pablo [CEMDRX, Physics Department, Universidade de Coimbra, Rua Larga, Coimbra P-3004-516 (Portugal); Higher Technical School of Telecommunications Engineering, Universidad de Valladolid, Campus Miguel Delibes, Paseo Belén 15, Valladolid 47011 (Spain); Coya, Carmen, E-mail: carmen.coya@urjc.es [Escuela Superior de Ciencias Experimentales y Tecnología (ESCET), Universidad Rey Juan Carlos, Madrid 28933 (Spain); Silva, Manuela Ramos [CEMDRX, Physics Department, Universidade de Coimbra, Rua Larga, Coimbra P-3004-516 (Portugal); Eusebio, M. Ermelinda S. [Chemistry Department, Faculdade de Ciências e Tecnologia, Universidade de Coimbra, Coimbra P-3004-535 (Portugal); Andrés, Alicia de [Instituto de Ciencia de Materiales de Madrid, Consejo Superior de Investigaciones Científicas (CSIC), Cantoblanco, Madrid 28049 (Spain); Álvarez, Ángel L. [Escuela Superior de Ciencias Experimentales y Tecnología (ESCET), Universidad Rey Juan Carlos, Madrid 28933 (Spain); Martín-Gil, Jesús [Advanced Materials Laboratory, ETSIIAA, Universidad de Valladolid, Avenida de Madrid 44, Palencia 34004 (Spain)

    2015-03-15

    Current manufacturing technologies for OLEDs involve the use of expensive high vacuum techniques and call for thermal stability requirements which are not fulfilled by many materials. These problems disappear when the OLED films are deposited directly from solution. In this study, we have designed, synthesized and characterized a novel octacoordinated complex, Tris(1-(4-chlorophenyl)-4,4,4-trifluoro-1, 3-butanedionate)mono(bathophenanthroline) europium(III), to be used as a “complex-only” emissive layer in wet-processed OLEDs. Upon excitation in the UV region, very efficient energy transfer from the ligands to Eu{sup 3+} takes place, giving rise to intense red emission with very high monochromaticity (R=19), both in powder and as a thin film. The decay times of 754 µs (powder) and 620 µs (thin film) are comparable to those of the most efficient Eu{sup 3+} β-diketonate complexes reported to date. The same energy transfer leading to saturated red and narrow emission is also observed in the OLED device (glass/ITO/PEDOT:PSS/[Eu(cbtfa){sub 3}(bath)]/Ca/Al) when biased at >5.2 V. Its high quantum efficiency (∼60%), good thermal stability up to 200 °C and adequate thin film forming properties make this material a promising chromophore for cost-effective OLEDs. - Highlights: • A highly fluorinated europium(III) octacoordinated complex, [Eu(cbtfa)3(bath)], has been synthesized and its structure elucidated by single crystal X-ray diffraction. • The chosen coordination environment is well-suited for sensitizing the luminescence of the Eu{sup 3+} ion, achieving very efficient energy transfer from the organic ligands (excited in the UV region) to the rare earth ion, leading to highly efficient (Q∼60% in crystalline powder and Q∼50% in thin film) and saturated red photoluminescence. • The material has also been integrated into a single active layer, full solution-processed OLED, with ITO/PEDOT:PSS/[Eu(cbtfa)3(bath)]/ Ca/Al structure.

  7. CD147-CD98hc complex contributes to poor prognosis of non-small cell lung cancer patients through promoting cell proliferation via the PI3K/Akt signaling pathway.

    Science.gov (United States)

    Fei, Fei; Li, Xiaofei; Xu, Li; Li, Deyang; Zhang, Zhipei; Guo, Xu; Yang, Hushan; Chen, Zhinan; Xing, Jinliang

    2014-12-01

    It has been reported that CD147 and CD98 heavy chain (CD98hc) form a complex on the cell plasma membrane of several cancers; however, whether this complex exists in non-small cell lung cancer (NSCLC) cells and affects the prognosis of patients remains to be elucidated. The expression of CD147 and CD98hc was assessed in tissue samples from 241 NSCLC patients and NSCLC cell lines. The correlation between CD147 and CD98hc expression and their association with the prognosis of NSCLC patients were analyzed. We also evaluated the impact of CD147 and CD98hc on the growth of NSCLC cells as well as Akt phosphorylation. Both CD147 and CD98hc were significantly upregulated in NSCLC cells, and their expression levels were significantly correlated (p CD147 and CD98hc could form a complex on NSCLC cells. Compared with NSCLC patients with CD147-/CD98hc-, those with CD147+/CD98hc+ exhibited a significantly poor overall survival (OS) with a hazard ratio (HR) of 1.92 (p = 0.010), and a significantly increased risk of recurrence with a HR of 1.97 (p = 0.004). Also, we demonstrated that the proliferation of lung cancer cell lines was significantly affected by knockdown and force-expression of the CD147-CD98hc complex. Western blot analysis indicated that the phosphorylation of Akt in NSCLC cells was significantly affected by knockdown and overexpression of either or both CD147 and CD98hc. Our findings indicate that the CD147-CD98hc complex significantly contributes to poor prognosis of NSCLC patients through promoting cell proliferation via the PI3K/Akt pathway.

  8. 1H NMR analysis of complexation of hydrotropic agents nicotinamide and caffeine with aromatic biologically active molecules in aqueous solution

    Science.gov (United States)

    Lantushenko, Anastasia O.; Mukhina, Yulia V.; Veselkov, Kyrill A.; Davies, David B.; Veselkov, Alexei N.

    2004-07-01

    NMR spectroscopy has been used to elucidate the molecular mechanism of solubilization action of hydrotropic agents nicotinamide (NA) and caffeine (CAF). Hetero-association of NA with riboflavine-mononucleotide (FMN) and CAF with low soluble in aqueous solution synthetic analogue of antibiotic actinomycin D, actinocyl-bis-(3-dimethylaminopropyl) amine (Actill), has been investigated by 500 MHz 1H NMR spectroscopy. Concentration and temperature dependences of proton chemical shifts have been analysed in terms of a statistical-thermodynamic model of indefinite self- and heteroassociation of aromatic molecules. The obtained results enable to conclude that NA-FMN and CAF-Actill intermolecular complexes are mainly stabilized by the stacking interactions of the aromatic chromophores. Hetero-association of the investigated molecules plays an important role in solubilization of aromatic drugs by hydrotropic agents nicotinamide and caffeine.

  9. Solution stabilities of some mixed ligand complexes of UO22+ and Th4+ with complexones and salicylic acids

    International Nuclear Information System (INIS)

    Singh, R.K.; Saxena, M.C.

    1991-01-01

    Formation constants (log Ksub(MAL)sup(MA)) of mixed ligands complexes (MAL), where M = UO 2 2+ or Th 4+ , A = IMDA, NTA, HEDTA, EDTA, CDTA or DTPA, L = salicylic acid (SA) or 5-sulphosalicylic acid (SSA), have been determined by pH titrations using Irving-Rossotti approach at 25 o C and at I =0.2 (mol dm -3 , KNO 3 ). The solution stabilities exhibit the sequence (i) Th 4+ >UO 2 2+ , (ii) IMDA>NTA>HEDTA>EDTA>CDTA>DTPA, and (iii) SA>SSA with respect to metal ions, primary ligands and secondary ligands, respectively. The formation constants log Ksub(ML)sup(M) and log Ksub(ML 2 )sup(ML) have also been determined. The Δlog K values have been found to be negative-increasing numerically with the negative charge on the deprotonated primary ligand (A n- ). (author). 17 refs., 1 tab

  10. Infants with complex congenital heart diseases show poor short-term memory in the mobile paradigm at 3 months of age.

    Science.gov (United States)

    Chen, Chao-Ying; Harrison, Tondi; Heathcock, Jill

    2015-08-01

    The purpose of this study was to examine learning, short-term memory and general development including cognitive, motor, and language domains in infants with Complex Congenital Heart Defects (CCDH). Ten infants with CCHD (4 males, 6 females) and 14 infants with typical development (TD) were examined at 3 months of age. The mobile paradigm, where an infant's leg is tethered to an overhead mobile, was used to evaluate learning and short-term memory. The Bayley Scales of Infant Development 3rd edition (Bayley-III) was used to evaluate general development in cognitive, motor, and language domains. Infants with CCHD and infants with TD both showed learning with significant increase in kicking rate (pshort-term memory (p=0.017) in the mobile paradigm. There were no differences on cognitive, motor, and language development between infants with CCHD and infants with TD on the Bayley-III. Early assessment is necessary to guide targeted treatment in infants with CCHD. One-time assessment may fail to detect potential cognitive impairments during early infancy in infants with CCHD. Supportive intervention programs for infants with CCHD that focuses on enhancing short-term memory are recommended. Copyright © 2015 Elsevier Inc. All rights reserved.

  11. Complexation of some trivalent lanthanides, scandium(III) and thorium(IV) by benzylidenepyruvates in aqueous solution

    International Nuclear Information System (INIS)

    Marques, R.N.; Moraes, M. de; Ionashiro, M.

    1997-01-01

    The protonation constants of 4-methylbenzylidenepyruvate (4Me-BP) and 4-isopropylbenzylidenepyruvate (4IP-BP) as well as the stability constants of their binary 1:1 complexes with Cu(II), La(III), Pr(III), Sm(III), Eu(III), Yb(III), Sc(III) and Th(IV) have been determined spectrophotometrically in aqueous solution at 25 C and ionic strength 0.500 M, maintained with sodium perchlorate. For all metal ions considered, the stability changes move in the same direction as the pK a of the ligands. Linear free energy relationships, as applied to oxygen donor substances, suggest the -COCOO - moiety as the metal binding site of the ligands. The results are discussed mainly taking into account that benzylidenepyruvates, besides the α-keto canonical form, may display other forms in aqueous solution with changing pH and the possible occurrence of extra intra-ligand charge polarization, induced by metal ions. (orig.)

  12. The Importance of and the Complexities Associated With Measuring Continuity of Care During Resident Training: Possible Solutions Do Exist.

    Science.gov (United States)

    Carney, Patricia A; Conry, Colleen M; Mitchell, Karen B; Ericson, Annie; Dickinson, W Perry; Martin, James C; Carek, Peter J; Douglass, Alan B; Eiff, M Patrice

    2016-04-01

    Evolutions in care delivery toward the patient-centered medical home have influenced important aspects of care continuity. Primary responsibility for a panel of continuity patients is a foundational requirement in family medicine residencies. In this paper we characterize challenges in measuring continuity of care in residency training in this new era of primary care. We synthesized the literature and analyzed information from key informant interviews and group discussions with residency faculty and staff to identify the challenges and possible solutions for measuring continuity of care during family medicine training. We specifically focused on measuring interpersonal continuity at the patient level, resident level, and health care team level. Challenges identified in accurately measuring interpersonal continuity of care during residency training include: (1) variability in empanelment approaches for all patients, (2) scheduling complexity in different types of visits, (3) variability in ability to attain continuity counts at the level of the resident, and (4) shifting make-up of health care teams, especially in residency training. Possible solutions for each challenge are presented. Philosophical issues related to continuity are discussed, including whether true continuity can be achieved during residency training and whether qualitative rather than quantitative measures of continuity are better suited to residencies. Measuring continuity of care in residency training is challenging but possible, though improvements in precision and assessment of the comprehensive nature of the relationships are needed. Definitions of continuity during training and the role continuity measurement plays in residency need further study.

  13. Efficiency Evaluation of Food Waste Materials for the Removal of Metals and Metalloids from Complex Multi-Element Solutions

    Science.gov (United States)

    Giuliano, Antonella; Astolfi, Maria Luisa; Congedo, Rossana; Masotti, Andrea; Canepari, Silvia

    2018-01-01

    Recent studies have shown the potential of food waste materials as low cost adsorbents for the removal of heavy metals and toxic elements from wastewater. However, the adsorption experiments have been performed in heterogeneous conditions, consequently it is difficult to compare the efficiency of the individual adsorbents. In this study, the adsorption capacities of 12 food waste materials were evaluated by comparing the adsorbents’ efficiency for the removal of 23 elements from complex multi-element solutions, maintaining homogeneous experimental conditions. The examined materials resulted to be extremely efficient for the adsorption of many elements from synthetic multi-element solutions as well as from a heavy metal wastewater. The 12 adsorbent surfaces were analyzed by Fourier transform infrared spectroscopy and showed different types and amounts of functional groups, which demonstrated to act as adsorption active sites for various elements. By multivariate statistical computations of the obtained data, the 12 food waste materials were grouped in five clusters characterized by different elements’ removal efficiency which resulted to be in correlation with the specific adsorbents’ chemical structures. Banana peel, watermelon peel and grape waste resulted the least selective and the most efficient food waste materials for the removal of most of the elements. PMID:29495363

  14. Efficiency Evaluation of Food Waste Materials for the Removal of Metals and Metalloids from Complex Multi-Element Solutions.

    Science.gov (United States)

    Massimi, Lorenzo; Giuliano, Antonella; Astolfi, Maria Luisa; Congedo, Rossana; Masotti, Andrea; Canepari, Silvia

    2018-02-26

    Recent studies have shown the potential of food waste materials as low cost adsorbents for the removal of heavy metals and toxic elements from wastewater. However, the adsorption experiments have been performed in heterogeneous conditions, consequently it is difficult to compare the efficiency of the individual adsorbents. In this study, the adsorption capacities of 12 food waste materials were evaluated by comparing the adsorbents' efficiency for the removal of 23 elements from complex multi-element solutions, maintaining homogeneous experimental conditions. The examined materials resulted to be extremely efficient for the adsorption of many elements from synthetic multi-element solutions as well as from a heavy metal wastewater. The 12 adsorbent surfaces were analyzed by Fourier transform infrared spectroscopy and showed different types and amounts of functional groups, which demonstrated to act as adsorption active sites for various elements. By multivariate statistical computations of the obtained data, the 12 food waste materials were grouped in five clusters characterized by different elements' removal efficiency which resulted to be in correlation with the specific adsorbents' chemical structures. Banana peel, watermelon peel and grape waste resulted the least selective and the most efficient food waste materials for the removal of most of the elements.

  15. Efficiency Evaluation of Food Waste Materials for the Removal of Metals and Metalloids from Complex Multi-Element Solutions

    Directory of Open Access Journals (Sweden)

    Lorenzo Massimi

    2018-02-01

    Full Text Available Recent studies have shown the potential of food waste materials as low cost adsorbents for the removal of heavy metals and toxic elements from wastewater. However, the adsorption experiments have been performed in heterogeneous conditions, consequently it is difficult to compare the efficiency of the individual adsorbents. In this study, the adsorption capacities of 12 food waste materials were evaluated by comparing the adsorbents’ efficiency for the removal of 23 elements from complex multi-element solutions, maintaining homogeneous experimental conditions. The examined materials resulted to be extremely efficient for the adsorption of many elements from synthetic multi-element solutions as well as from a heavy metal wastewater. The 12 adsorbent surfaces were analyzed by Fourier transform infrared spectroscopy and showed different types and amounts of functional groups, which demonstrated to act as adsorption active sites for various elements. By multivariate statistical computations of the obtained data, the 12 food waste materials were grouped in five clusters characterized by different elements’ removal efficiency which resulted to be in correlation with the specific adsorbents’ chemical structures. Banana peel, watermelon peel and grape waste resulted the least selective and the most efficient food waste materials for the removal of most of the elements.

  16. Enhanced electrical stability of nitrate ligand-based hexaaqua complexes solution-processed ultrathin a-IGZO transistors

    Science.gov (United States)

    Choi, C.; Baek, Y.; Lee, B. M.; Kim, K. H.; Rim, Y. S.

    2017-12-01

    We report solution-processed, amorphous indium-gallium-zinc-oxide-based (a-IGZO-based) thin-film transistors (TFTs). Our proposed solution-processed a-IGZO films, using a simple spin-coating method, were formed through nitrate ligand-based metal complexes, and they were annealed at low temperature (250 °C) to achieve high-quality oxide films and devices. We investigated solution-processed a-IGZO TFTs with various thicknesses, ranging from 4 to 16 nm. The 4 nm-thick TFT films had smooth morphology and high-density, and they exhibited excellent performance, i.e. a high saturation mobility of 7.73  ±  0.44 cm2 V-1 s-1, a sub-threshold swing of 0.27 V dec-1, an on/off ratio of ~108, and a low threshold voltage of 3.10  ±  0.30 V. However, the performance of the TFTs degraded as the film thickness was increased. We further performed positive and negative bias stress tests to examine their electrical stability, and it was noted that the operating behavior of the devices was highly stable. Despite a small number of free charges, the high performance of the ultrathin a-IGZO TFTs was attributed to the small effect of the thickness of the channel, low bulk resistance, the quality of the a-IGZO/SiO2 interface, and high film density.

  17. Simultaneous treatment of chlorinated organics and removal of metals and radionuclides with bimetals and complexing acids - application to surfactant solutions

    Energy Technology Data Exchange (ETDEWEB)

    Korte, N.E.; Gu, B. [Oak Ridge National Lab., TN (United States)

    1997-10-01

    Currently available methods for separation and treatment of radioactive mixed waste are typically energy-intensive, and often require high temperatures. Passive methods that operate at ambient temperatures are needed. The purpose of this task is to develop bimetallic substrates, using a base metal such as iron and a promoter metal such as palladium (Pd), to provide a passive, low-energy solution to a substantial portion of DOE`s mixed-waste problem. This technology consists of a porous medium that can simultaneously dechlorinate hazardous organics such as TCE and polychlorinated biphenyls (PCBs) at the same time that it removes metallic and hazardous wastes from a solvent/surfactant solution. The porous medium consists of a bimetallic substrate such as palladized iron (Pd/Fe). Palladium is readily chemically plated on iron and preliminary studies suggest that only 0.05 to 0.1% Pd is needed for an efficient reaction. Thus, the cost of the material is reasonable especially is it is long-lived or can be regenerated. Field implementation would consist of the passage of a surfactant-laden, mixed waste through a column or bed of the bimetallic substrate. The organic component of this mixed waste may contain semivolatile compounds such as PCBs or pesticides and herbicides. The bimetal simultaneously removes radionuclides and metals and degrades halogenated hydrocarbons. Virtually any concentration can be treated. Following reaction of the bimetal with the waste stream, the resulting effluent will consist of an uncontaminated aqueous solution of surfactant or solvent that can be reused. The bimetal would then be rinsed with a dilute mineral acid or a mild complexing acid (e.g., oxalic or citric acid) to regenerate the surface and to remove sorbed metals and non-hazardous organic residue. The latter effluent would be low-level radioactive waste in some cases, but it would now be much easier to manage and be of a lower volume than the original mixed waste.

  18. Condensed, solution and gas phase behaviour of mono- and dinuclear 2,6-diacetylpyridine (dap) hydrazone copper complexes probed by X-ray, mass spectrometry and theoretical calculations.

    Science.gov (United States)

    Neto, Brenno A D; Viana, Barbara F L; Rodrigues, Thyago S; Lalli, Priscila M; Eberlin, Marcos N; da Silva, Wender A; de Oliveira, Heibbe C B; Gatto, Claudia C

    2013-08-28

    We describe the synthesis of novel mononuclear and dinuclear copper complexes and an investigation of their behaviour in solution using mass spectrometry (ESI-MS and ESI-MS/MS) and in the solid state using X-ray crystallography. The complexes were synthesized from two widely used diacetylpryridine (dap) ligands, i.e. 2,6-diacetylpyridinebis(benzoic acid hydrazone) and 2,6-diacetylpyridinebis(2-aminobenzoic acid hydrazone). Theoretical calculations (DFT) were used to predict the complex geometries of these new structures, their equilibrium in solution and energies associated with the transformations.

  19. Ultrafast excited-state relaxation of a binuclear Ag(i) phosphine complex in gas phase and solution.

    Science.gov (United States)

    Kruppa, S V; Bäppler, F; Klopper, W; Walg, S P; Thiel, W R; Diller, R; Riehn, C

    2017-08-30

    The binuclear complex [Ag 2 (dcpm) 2 ](PF 6 ) 2 (dcpm = bis(dicyclohexylphosphino)methane) exhibits a structure with a close silver-silver contact mediated by the bridging ligand and thus a weak argentophilic interaction. Upon electronic excitation this cooperative effect is strongly increased and determines the optical and luminescence properties of the compound. We have studied here the ultrafast electronic dynamics in parallel in gas phase by transient photodissociation and in solution by transient absorption. In particular, we report the diverse photofragmentation pathways of isolated [Ag 2 (dcpm) 2 ] 2+ in an ion trap and its gas phase UV photodissociation spectrum. By pump-probe fragmentation action spectroscopy (λ ex = 260 nm) in the gas phase, we have obtained fragment-specific transients which exhibit a common ultrafast multiexponential decay. This is fitted to four time constants (0.6/5.8/100/>1000 ps), highlighting complex intrinsic photophysical processes. Remarkably, multiexponential dynamics (0.9/8.5/73/604 ps) are as well found for the relaxation dynamics in acetonitrile solution. Ab initio calculations at the level of approximate coupled-cluster singles-doubles (CC2) theory of ground and electronically excited states of the reduced model system [Ag 2 (dmpm) 2 ] 2+ (dmpm = bis(dimethylphosphino)methane) indicate a shortening of the Ag-Ag distance upon excitation by 0.3-0.4 Å. In C 2 geometry two close-lying singlet states S 1 ( 1 MC(dσ*-pπ), 1 B, 4.13 eV) and S 2 ( 1 MC(dσ*-pσ), 1 A, 4.45 eV) are found. The nearly dark S 1 state has not been reported so far. The excitation of the S 2 state carries a large oscillator strength for the calculated vertical transition (266 nm). Two related triplets are calculated at T 1 (3.87 eV) and T 2 (3.90 eV). From these findings we suggest possible relaxation pathways with the two short time constants ascribed to ISC/IVR and propose from the obtained similar values in gas phase that the fast solution dynamics

  20. The enthalpies of interactions of Ca2+(aq) and C2O{4/2-} (aq) ions in complexon solutions: Competition between complexation and precipitation

    Science.gov (United States)

    Kustov, A. V.; Smirnova, N. L.; Berezin, B. D.; Trostin, V. N.

    2010-04-01

    The thermal effects of mixing of aqueous calcium chloride with sodium citrate and ethylenedi-aminetetraacetate in the absence and presence of sodium oxalate have been measured at 25°C. The thermal effects of dilution of aqueous calcium chloride solutions were determined. The thermal effects of calcium oxalate precipitation and formation of calcium complexes with citrate and ethylenediaminetetraacetate ions were calculated. The 1% solution of sodium citrate inhibited the formation of CaC2O4 (s); in a 1% solution of sodium ethylenediaminetetraacetate with [Ca2+][C2O{4/2-}] > 10-5, the endothermal formation of the [CaEdta]2- complex quickly changed to exothermal precipitation. The 3 and 5% solutions of complexons showed a pronounced inhibiting effect on the formation of urinary stones even when the concentration of calcium and oxalate ions in solution exceeded the product of solubility of CaC2O4 by four and more orders of magnitude.

  1. Cation-Poor Complex Metallic Alloys in Ba(Eu)-Au-Al(Ga) Systems: Identifying the Keys that Control Structural Arrangements and Atom Distributions at the Atomic Level.

    Science.gov (United States)

    Smetana, Volodymyr; Steinberg, Simon; Mudryk, Yaroslav; Pecharsky, Vitalij; Miller, Gordon J; Mudring, Anja-Verena

    2015-11-02

    Four complex intermetallic compounds BaAu(6±x)Ga(6±y) (x = 1, y = 0.9) (I), BaAu(6±x)Al(6±y) (x = 0.9, y = 0.6) (II), EuAu6.2Ga5.8 (III), and EuAu6.1Al5.9 (IV) have been synthesized, and their structures and homogeneity ranges have been determined by single crystal and powder X-ray diffraction. Whereas I and II originate from the NaZn13-type structure (cF104-112, Fm3̅c), III (tP52, P4/nbm) is derived from the tetragonal Ce2Ni17Si9-type, and IV (oP104, Pbcm) crystallizes in a new orthorhombic structure type. Both I and II feature formally anionic networks with completely mixed site occupation by Au and triel (Tr = Al, Ga) atoms, while a successive decrease of local symmetry from the parental structures of I and II to III and, ultimately, to IV correlates with increasing separation of Au and Tr on individual crystallographic sites. Density functional theory-based calculations were employed to determine the crystallographic site preferences of Au and the respective triel element to elucidate reasons for the atom distribution ("coloring scheme"). Chemical bonding analyses for two different "EuAu6Tr6" models reveal maximization of the number of heteroatomic Au-Tr bonds as the driving force for atom organization. The Fermi levels fall in broad pseudogaps for both models allowing some electronic flexibility. Spin-polarized band structure calculations on the "EuAu6Tr6" models hint to singlet ground states for europium and long-range magnetic coupling for both EuAu6.2Ga5.8 (III) and EuAu6.1Al5.9 (IV). This is substantiated by experimental evidence because both compounds show nearly identical magnetic behavior with ferromagnetic transitions at TC = 6 K and net magnetic moments of 7.35 μB/f.u. at 2 K. The effective moments of 8.3 μB/f.u., determined from Curie-Weiss fits, point to divalent oxidation states for europium in both III and IV.

  2. A DFT/TDDFT study of the structural and spectroscopic properties of Al(III) complexes with 4-nitrocatechol in acidic aqueous solution

    International Nuclear Information System (INIS)

    Cornard, Jean-Paul; Lapouge, Christine; Merlin, Jean-Claude

    2007-01-01

    The complexation of 4-nitrocatechol in aqueous solution at pH 5 has been studied by molecular spectroscopy combined with quantum chemical calculations. In these physico-chemical conditions, the formation of the two complexes [4ncatAl(H 2 O) 4 ] + and [(4ncat) 2 Al(H 2 O) 2 ] - has been highlighted. The electronic absorption spectra of the 1:1 and 1:2 complexes of Al(III) with 4-nitrocatechol have been computed using the time-dependent density functional theory and the polarizable continuum model. It turns out that the 6-311+G(d,p) basis set provides a good agreement between experimental and theoretical absorption spectra. This good agreement has allowed the determination of the preferential conformation of the 1:2 complex in aqueous solution. A complete assignment of the UV-Vis absorption and Raman spectra of the complexes has been proposed

  3. Experimental investigation of aluminum complexing with sodium ion and of gallium and iron (III) speciation in natural solutions

    International Nuclear Information System (INIS)

    Diakonov, Igor

    1995-01-01

    The aim of this work is to acquire thermodynamic data on the aqueous complexes forming between sodium and aluminum, gallium and hydroxide, and iron (III) and hydroxide. These data will provide for a better understanding of the transport and distribution of these elements in surface and hydrothermal fluids. Stability constants of the sodium-aluminate complex (Na Al(OH) 4 deg.) were obtained from boehmite solubility measurements at temperatures from 125 to 350 deg. C in alkaline solutions containing from 0.1 to 1 mol/L sodium. Complementary potentiometric measurements were performed with a sodium selective electrode, between 75 and 200 deg C (the potentiometric study was carried out by Gleb Pokrovski). Analyses of these data within the framework of the revised Helgeson-Kirkham-Flowers (HKF) model allowed determination of the HKF parameters for Na Al(OH) 4 deg. and calculation of its thermodynamic properties to 800 deg. C and 5 kb. The results of this work show that Na Al(OH) 4 deg. complex formation increases significantly the solubility of aluminum-bearing minerals and consequently aluminum mobility in hydrothermal fluids. Gallium speciation in surface and hydrothermal fluids is dominated by the negatively charged species, Ga(OH) 4 - . The thermodynamic properties of this species were determined from of OEGaOOH solubility measurements as a function of pH and temperature from 25 to 250 deg. C. In general, the variation of gallium aqueous speciation with pH is similar to that of aluminum other than at temperatures less than 200 deg. C over the pH range 3 - 6. This difference can account for the independent behavior of gallium versus aluminum in numerous low temperature natural systems. The thermodynamic properties of Fe(OH) 3 deg. which dominates the speciation of Fe(III) in surface waters and Fe(OH) 4 - were determined from hematite solubility measurements as a function of pH, oxygen pressure and temperature from 110 to 300 deg. C. The available thermodynamic data on

  4. Origin of poor doping efficiency in solution processed organic semiconductors† †Electronic supplementary information (ESI) available: Additional details on sample characterization, quantum chemistry calculations to obtain transition dipole moments of the ions and determine the strength of the Coulomb interaction, two-dimensional correlation analysis has been provided. In addition, this document also contains details of the calculations used to simulate 2D electronic spectra. See DOI: 10.1039/c8sc00758f

    Science.gov (United States)

    Jha, Ajay; Duan, Hong-Guang; Tiwari, Vandana; Thorwart, Michael

    2018-01-01

    Doping is an extremely important process where intentional insertion of impurities in semiconductors controls their electronic properties. In organic semiconductors, one of the convenient, but inefficient, ways of doping is the spin casting of a precursor mixture of components in solution, followed by solvent evaporation. Active control over this process holds the key to significant improvements over current poor doping efficiencies. Yet, an optimized control can only come from a detailed understanding of electronic interactions responsible for the low doping efficiencies. Here, we use two-dimensional nonlinear optical spectroscopy to examine these interactions in the course of the doping process by probing the solution mixture of doped organic semiconductors. A dopant accepts an electron from the semiconductor and the two ions form a duplex of interacting charges known as ion-pair complexes. Well-resolved off-diagonal peaks in the two-dimensional spectra clearly demonstrate the electronic connectivity among the ions in solution. This electronic interaction represents a well resolved electrostatically bound state, as opposed to a random distribution of ions. We developed a theoretical model to recover the experimental data, which reveals an unexpectedly strong electronic coupling of ∼250 cm–1 with an intermolecular distance of ∼4.5 Å between ions in solution, which is approximately the expected distance in processed films. The fact that this relationship persists from solution to the processed film gives direct evidence that Coulomb interactions are retained from the precursor solution to the processed films. This memory effect renders the charge carriers equally bound also in the film and, hence, results in poor doping efficiencies. This new insight will help pave the way towards rational tailoring of the electronic interactions to improve doping efficiencies in processed organic semiconductor thin films. PMID:29896388

  5. Multisensor system for determination of iron(II), iron(III) and uranium(VI) in complex solutions

    International Nuclear Information System (INIS)

    Legin, A.V.; Seleznev, B.L.; Rudnitskaya, A.M.; Vlasov, Yu.G.

    1998-01-01

    The aim of the present paper is the development and analytical evaluation of a multisensor system for determination of low content of iron(II), iron(III) and uranium(VI) in complex aqueous media. Sensor array included sensors on the basis of chalcogenide vitreous materials with redox and ionic cross-sensitivities, crystalline silver sulphide electrode, noble metal electrodes Pt, Au, Ag and redox sensor on the basis of oxide glass. Potentiometric measurements have been taken in a conventional electrochemical cell vs. a standard Ag/AgCl reference electrode. All measurements have been taken at room temperature. Calibration solutions contained UO 2 (NO 3 ) 2 in concentration range 10 -6 -1,610 -5 mol/L, K 3 Fe(CN) 6 and K 4 Fe(CN) 6 or FeSO 4 (NH 4 ) 2 SO 4 and FeCl 3 , with the ratio of Fe(II)/Fe(III) concentration from 100:1 to 1:100, the total concentration of Fe was 10 -4 and 10 -5 mol/L. All solutions have been made on the background electrolyte of calcium and magnesium chlorides and sulphates with the fixed content of 5-27 mmol/L of each component which is a typical one for groundwater or mining water. Sensor potentials have been processed by a back-propagation artificial neural net. Average error of determination of Fe(II) and Fe(III) is about 20 %, of uranium(VI) - 40 %. It was found that sensitivity of the sensor array to iron and uranium is irrespective of the chemical form of these species

  6. Contribution of electro-spray mass spectrometry to the study of the organic species and metal-ligand complexes in solution

    International Nuclear Information System (INIS)

    Berthon, L.; Piveteau, B.

    2000-01-01

    Electro-spray ionization mass spectrometry (ESI-MS) has quickly become a versatile method of qualitative analysis of a wide variety of species in solution. This technique (with positive and negative ionization modes) is used to analyze organic solutions in the frame of the DIAMEX process. Degraded solvent had been studied without any preliminary sample treatment (separation or derivation) and neutral complexes 'uranyl nitrate - malonamide' had been observed. (authors)

  7. Structure and dynamics of the uranyl tricarbonate complex in aqueous solution: insights from quantum mechanical charge field molecular dynamics.

    Science.gov (United States)

    Tirler, Andreas O; Hofer, Thomas S

    2014-11-13

    This investigation presents the characterization of structural and dynamical properties of uranyl tricarbonate in aqueous solution employing an extended hybrid quantum mechanical/molecular mechanical (QM/MM) approach. It is shown that the inclusion of explicit solvent molecules in the quantum chemical treatment is essential to mimic the complex interaction occurring in an aqueous environment. Thus, in contrast to gas phase cluster calculations on a quantum chemical level proposing a 6-fold coordination of the three carbonates, the QMCF MD simulation proposes a 5-fold coordination. An extensive comparison of the simulation results to structural and dynamical data available in the literature was found to be in excellent agreement. Furthermore, this work is the first theoretical study on a quantum chemical level of theory able to observe the conversion of carbonate (CO₃²⁻) to bicarbonate (HCO₃⁻) in the equatorial coordination sphere of the uranyl ion. From a comparison of the free energy ΔG values for the unprotonated educt [UO₂(CO₃)₃]⁴⁻ and the protonated [UO₂(CO₃)₂(HCO₃)]³⁻, it could be concluded that the reaction equilibrium is strongly shifted toward the product state confirming the benignity for the observed protonation reaction. Structural properties and the three-dimensional arrangement of carbonate ligands were analyzed via pair-, three-body, and angular distributions, the dynamical properties were evaluated by hydrogen-bond correlation functions and vibrational power spectra.

  8. A novel aggregation induced emission active cyclometalated Ir(III) complex as a luminescent probe for detection of copper(II) ion in aqueous solution

    Energy Technology Data Exchange (ETDEWEB)

    Shen, Wei; Yan, Liqiang; Tian, Wenwen; Cui, Xia; Qi, Zhengjian, E-mail: qizhengjian@seu.edu.cn; Sun, Yueming, E-mail: sun@seu.edu.cn

    2016-09-15

    We report the synthesis and characterization of a novel aggregation induced emission (AIE) active cyclometalated Ir(III) complex, namely [Ir(dfppy){sub 2}(phen-DPA)]PF{sub 6}, where dfppy and phen-DPA represent 2-(2,4-difluorophenyl)pyridine and 2-(bis(pyridin-2-ylmethyl)amino)-N-(1,10-phenanthrolin-5-yl)acetamide, respectively. The complex showed remarkable selectivity for copper(II) in aqueous solution over other competitive ions. Furthermore, this sensor showed a rapid and reversible response to copper(II) in aqueous solution with a detection limit of 65 nM.

  9. Study of complex formation between C18H36N2O6 and UO22+ cation in some binary mixed non-aqueous solutions

    Directory of Open Access Journals (Sweden)

    G.H. Rounaghi

    2017-02-01

    Full Text Available The complexation reaction between UO22+ cation and the macrobicyclic ligand C18H36N2O6 was studied in acetonitrile–dimethylformamide (AN–DMF, acetonitrile–tetrahydrofuran (AN–THF, acetonitrile–dichloromethane (AN–DCM binary solvent solutions at different temperatures using the coductometric method. In most cases, C18H36N2O6 forms a 1:1 [M:L] complex with the UO22+ cation. But in some of the studied solvent systems, in addition to formation of a 1:1 complex, a 1:2 [M:L2] complex is formed in solution. A non-linear behavior was observed for changes of logKf of the (C18H36N2O6·UO22+ complex versus the composition of the binary mixed solvents. The sequence of the stability of the (C18H36N2O6·UO22+ complex in pure solvent systems at 25 °C decreases in the order: AN > THF > DMF. In the case of binary solvent solutions, the stability constant of the complex at 25 °C was found to be: AN–DCM > AN–THF > AN–DMF. The values of thermodynamic quantities (ΔSc°,ΔHc°, for the formation of the complex were obtained from temperature dependence of the stability constant of the complex using the van't Hoff plots. The results show that in all cases, the complex is both entropy and enthalpy stabilized and both of these parameters are affected by the nature and composition of the mixed solvent systems.

  10. EPR studies on binuclear copper(II) complexes with N,N',N'',N'''-tetrakis(2-pyridylmethyl)-1,4,8,11-tetraaza-cyclotetradecane in solutions

    International Nuclear Information System (INIS)

    Jezierska, J.; Ozarowski, A.; Vuckovic, G.

    1997-01-01

    Binuclear copper(II) complexes of macrocyclic ligand TMPC (tetraazamacrocycle with four pendant 2-pirydylmethyl groups attached to the ring nitrogen atoms) with various anions forming bridge between copper ions, or coordinating to copper(II) ions at the apex, were prepared and their frozen solutions in DMF and NMF were investigated by EPR. The spectroscopic results have been interpreted in terms of molecular structure of investigated complexes

  11. On the complexity of determining tolerances for ->e--optimal solutions to min-max combinatorial optimization problems

    NARCIS (Netherlands)

    Ghosh, D.; Sierksma, G.

    2000-01-01

    Sensitivity analysis of e-optimal solutions is the problem of calculating the range within which a problem parameter may lie so that the given solution re-mains e-optimal. In this paper we study the sensitivity analysis problem for e-optimal solutions tocombinatorial optimization problems with

  12. Gold(III) complexes with 2-substituted pyridines as experimental anticancer agents: solution behavior, reactions with model proteins, antiproliferative properties.

    Science.gov (United States)

    Maiore, Laura; Cinellu, Maria Agostina; Nobili, Stefania; Landini, Ida; Mini, Enrico; Gabbiani, Chiara; Messori, Luigi

    2012-03-01

    Gold(III) compounds form a family of promising cytotoxic and potentially anticancer agents that are currently undergoing intense preclinical investigations. Four recently synthesized and characterized gold(III) derivatives of 2-substituted pyridines are evaluated here for their biological and pharmacological behavior. These include two cationic adducts with 2-pyridinyl-oxazolines, [Au(pyox(R))Cl(2)][PF(6)], [pyox(R)=(S)-4-benzyl-2-(pyridin-2-yl)-4,5-dihydrooxazole, I; (S)-4-iso-propyl-2-(pyridin-2-yl)-4,5-dihydrooxazole, II] and two neutral complexes [Au(N,N'OH)Cl(2)], III, and [Au(N,N',O)Cl], IV, containing the deprotonated ligand N-(1-hydroxy-3-iso-propyl-2-yl)pyridine-2-carboxamide, N,N'H,OH, resulting from ring opening of bound pyox(R) ligand of complex II by hydroxide ions. The solution behavior of these compounds was analyzed. These behave as classical prodrugs: activation of the metal center typically takes place through release of the labile chloride ligands while the rest of the molecule is not altered; alternatively, activation may occur through gold(III) reduction. All compounds react eagerly with the model protein cyt c leading to extensive protein metalation. ESI MS experiments revealed details of gold-cyt c interactions and allowed us to establish the nature of protein bound metal containing fragments. The different behavior displayed by I and II compared to III and IV is highlighted. Remarkable cytotoxic properties, against the reference human ovarian carcinoma cell lines A2780/S and A2780/R were disclosed for all tested compounds with IC(50) values ranging from 1.43 to 6.18 μM in the sensitive cell line and from 1.59 to 10.86 μM in the resistant one. The common ability of these compounds to overcome cisplatin resistance is highlighted. The obtained results are thoroughly discussed in the frame of current knowledge on cytotoxic gold compounds. Copyright © 2011 Elsevier Inc. All rights reserved.

  13. Estimating Prion Adsorption Capacity of Soil by BioAssay of Subtracted Infectivity from Complex Solutions (BASICS)

    Science.gov (United States)

    Wyckoff, A. Christy; Lockwood, Krista L.; Meyerett-Reid, Crystal; Michel, Brady A.; Bender, Heather; VerCauteren, Kurt C.; Zabel, Mark D.

    2013-01-01

    Prions, the infectious agent of scrapie, chronic wasting disease and other transmissible spongiform encephalopathies, are misfolded proteins that are highly stable and resistant to degradation. Prions are known to associate with clay and other soil components, enhancing their persistence and surprisingly, transmissibility. Currently, few detection and quantification methods exist for prions in soil, hindering an understanding of prion persistence and infectivity in the environment. Variability in apparent infectious titers of prions when bound to soil has complicated attempts to quantify the binding capacity of soil for prion infectivity. Here, we quantify the prion adsorption capacity of whole, sandy loam soil (SLS) typically found in CWD endemic areas in Colorado; and purified montmorillonite clay (Mte), previously shown to bind prions, by BioAssay of Subtracted Infectivity in Complex Solutions (BASICS). We incubated prion positive 10% brain homogenate from terminally sick mice infected with the Rocky Mountain Lab strain of mouse-adapted prions (RML) with 10% SLS or Mte. After 24 hours samples were centrifuged five minutes at 200×g and soil-free supernatant was intracerebrally inoculated into prion susceptible indicator mice. We used the number of days post inoculation to clinical disease to calculate the infectious titer remaining in the supernatant, which we subtracted from the starting titer to determine the infectious prion binding capacity of SLS and Mte. BASICS indicated SLS bound and removed ≥ 95% of infectivity. Mte bound and removed lethal doses (99.98%) of prions from inocula, effectively preventing disease in the mice. Our data reveal significant prion-binding capacity of soil and the utility of BASICS to estimate prion loads and investigate persistence and decomposition in the environment. Additionally, since Mte successfully rescued the mice from prion disease, Mte might be used for remediation and decontamination protocols. PMID:23484043

  14. Enhanced detection of explosives by turn-on resonance Raman upon host-guest complexation in solution and the solid state

    DEFF Research Database (Denmark)

    Witlicki, Edward H.; Bähring, Steffen; Johnsen, Carsten

    2017-01-01

    complexation occur via a mechanism of resonance between the 785 nm laser line and the strongly absorbing charge-transfer chromophore arising from the complex between electron-donating TTF-C[4]P and electron-accepting nitroaromatic explosives. The addition of chloride forms the Cl-·TTF-C[4]P complex resetting......The recognition of nitroaromatic explosives by a tetrakis-tetrathiafulvalene-calix[4]pyrrole receptor (TTF-C[4]P) yields a "turn on" and fingerprinting response in the resonance Raman scattering observed in solution and the solid state. Intensity changes in nitro vibrations with analyte...

  15. Luminescent zinc(ii) and copper(i) complexes for high-performance solution-processed monochromic and white organic light-emitting devices.

    Science.gov (United States)

    Cheng, Gang; So, Gary Kwok-Ming; To, Wai-Pong; Chen, Yong; Kwok, Chi-Chung; Ma, Chensheng; Guan, Xiangguo; Chang, Xiaoyong; Kwok, Wai-Ming; Che, Chi-Ming

    2015-08-01

    The synthesis and spectroscopic properties of luminescent tetranuclear zinc(ii) complexes of substituted 7-azaindoles and a series of luminescent copper(i) complexes containing 7,8-bis(diphenylphosphino)-7,8-dicarba- nido -undecaborate ligand are described. These complexes are stable towards air and moisture. Thin film samples of the luminescent copper(i) complexes in 2,6-dicarbazolo-1,5-pyridine and zinc(ii) complexes in poly(methyl methacrylate) showed emission quantum yields of up to 0.60 (for Cu-3 ) and 0.96 (for Zn-1 ), respectively. Their photophysical properties were examined by ultrafast time-resolved emission spectroscopy, temperature dependent emission lifetime measurements and density functional theory calculations. Monochromic blue and orange solution-processed OLEDs with these Zn(ii) and Cu(i) complexes as light-emitting dopants have been fabricated, respectively. Maximum external quantum efficiency (EQE) of 5.55% and Commission Internationale de l'Eclairage (CIE) coordinates of (0.16, 0.19) were accomplished with the optimized Zn-1 -OLED while these values were, respectively 15.64% and (0.48, 0.51) for the optimized Cu-3 -OLED. Solution-processed white OLEDs having maximum EQE of 6.88%, CIE coordinates of (0.42, 0.44), and colour rendering index of 81 were fabricated by using these luminescent Zn(ii) and Cu(i) complexes as blue and orange light-emitting dopant materials, respectively.

  16. Complexes in solution of o-phenanthroline with the ions of 4f and 5f elements at valencies II, III, V, VI

    International Nuclear Information System (INIS)

    Le Marois, Gilles.

    1980-06-01

    Slight differences between the complexation in aqueous solution of 4f and 5f series ions are revealed by the use of a soft, aromatic and chelating ligand of the o-phenanthroline type. Trivalent actinide ions are extrated selectively in the presence of a carboxylic acid. This extraction takes place at high pH and does not require large quantities of salts in aqueous solution, which increase the volume of radioactive wastes for storage. Only the first two o-phenanthroline complexes of these ions are obtained in aqueous solution. Determination of the constants of formation of such complexes shows the stronger affinity of the ligand for actinide ions. An inversion of the usual order of complexation of the different actinide valencies is also observed: pentavalent ions are most complexed than trivalent, o-phenanthroline stabilises actinide ions preferentially because they are more liable to form bonds with delocalised electrons. Finally a slight stabilisation of europium at valency II shows the participation of electrons by back bonding of the metal, due to the strong conjugation of the ligand π electrons [fr

  17. Solution structures of lipoyl domains of the 2-oxo acid dehydrogenase complexes from Azotobacter vinelandii : implications for molecular recognition

    NARCIS (Netherlands)

    Berg, A.

    1997-01-01

    The 2-oxo acid dehydrogenase complexes are large multienzyme complexes that catalyse the irreversible oxidative decarboxylation of a specific 2-oxo acid to the corresponding acyl-CoA derivative. The pyruvate dehydrogenase complex (PDHC) converts the product of the glycolysis, pyruvate, to

  18. Bäcklund transformation, analytic soliton solutions and numerical simulation for a (2+1)-dimensional complex Ginzburg-Landau equation in a nonlinear fiber

    Science.gov (United States)

    Yu, Ming-Xiao; Tian, Bo; Chai, Jun; Yin, Hui-Min; Du, Zhong

    2017-10-01

    In this paper, we investigate a nonlinear fiber described by a (2+1)-dimensional complex Ginzburg-Landau equation with the chromatic dispersion, optical filtering, nonlinear and linear gain. Bäcklund transformation in the bilinear form is constructed. With the modified bilinear method, analytic soliton solutions are obtained. For the soliton, the amplitude can decrease or increase when the absolute value of the nonlinear or linear gain is enlarged, and the width can be compressed or amplified when the absolute value of the chromatic dispersion or optical filtering is enhanced. We study the stability of the numerical solutions numerically by applying the increasing amplitude, embedding the white noise and adding the Gaussian pulse to the initial values based on the analytic solutions, which shows that the numerical solutions are stable, not influenced by the finite initial perturbations.

  19. Project management and institutional complexity in domestic housing refurbishment with innovative energy solutions : a case study analysis

    NARCIS (Netherlands)

    Hoppe, Thomas; Lulofs, Kristiaan R.D.

    2011-01-01

    Applying innovative energy solutions (IES) in dense residential areas in the Netherlands is a challenge. This paper presents a typology that supports the analysis and understanding of policy implementation processes to encourage the adoption of innovative energy solutions in urban residential areas.

  20. Comparative density functional study of the complexes [UO2(CO3)3]4- and [(UO2)3(CO3)6]6- in aqueous solution.

    Science.gov (United States)

    Schlosser, Florian; Moskaleva, Lyudmila V; Kremleva, Alena; Krüger, Sven; Rösch, Notker

    2010-06-28

    With a relativistic all-electron density functional method, we studied two anionic uranium(VI) carbonate complexes that are important for uranium speciation and transport in aqueous medium, the mononuclear tris(carbonato) complex [UO(2)(CO(3))(3)](4-) and the trinuclear hexa(carbonato) complex [(UO(2))(3)(CO(3))(6)](6-). Focusing on the structures in solution, we applied for the first time a full solvation treatment to these complexes. We approximated short-range effects by explicit aqua ligands and described long-range electrostatic interactions via a polarizable continuum model. Structures and vibrational frequencies of "gas-phase" models with explicit aqua ligands agree best with experiment. This is accidental because the continuum model of the solvent to some extent overestimates the electrostatic interactions of these highly anionic systems with the bulk solvent. The calculated free energy change when three mono-nuclear complexes associate to the trinuclear complex, agrees well with experiment and supports the formation of the latter species upon acidification of a uranyl carbonate solution.

  1. Kinetics and mechanisms of the oxidation of iodide and bromide in aqueous solutions by a trans-dioxoruthenium(VI) complex.

    Science.gov (United States)

    Lam, William W Y; Man, Wai-Lun; Wang, Yi-Ning; Lau, Tai-Chu

    2008-08-04

    The kinetics and mechanisms of the oxidation of I (-) and Br (-) by trans-[Ru (VI)(N 2O 2)(O) 2] (2+) have been investigated in aqueous solutions. The reactions have the following stoichiometry: trans-[Ru (VI)(N 2O 2)(O) 2] (2+) + 3X (-) + 2H (+) --> trans-[Ru (IV)(N 2O 2)(O)(OH 2)] (2+) + X 3 (-) (X = Br, I). In the oxidation of I (-) the I 3 (-)is produced in two distinct phases. The first phase produces 45% of I 3 (-) with the rate law d[I 3 (-)]/dt = ( k a + k b[H (+)])[Ru (VI)][I (-)]. The remaining I 3 (-) is produced in the second phase which is much slower, and it follows first-order kinetics but the rate constant is independent of [I (-)], [H (+)], and ionic strength. In the proposed mechanism the first phase involves formation of a charge-transfer complex between Ru (VI) and I (-), which then undergoes a parallel acid-catalyzed oxygen atom transfer to produce [Ru (IV)(N 2O 2)(O)(OHI)] (2+), and a one electron transfer to give [Ru (V)(N 2O 2)(O)(OH)] (2+) and I (*). [Ru (V)(N 2O 2)(O)(OH)] (2+) is a stronger oxidant than [Ru (VI)(N 2O 2)(O) 2] (2+) and will rapidly oxidize another I (-) to I (*). In the second phase the [Ru (IV)(N 2O 2)(O)(OHI)] (2+) undergoes rate-limiting aquation to produce HOI which reacts rapidly with I (-) to produce I 2. In the oxidation of Br (-) the rate law is -d[Ru (VI)]/d t = {( k a2 + k b2[H (+)]) + ( k a3 + k b3[H (+)]) [Br (-)]}[Ru (VI)][Br (-)]. At 298.0 K and I = 0.1 M, k a2 = (2.03 +/- 0.03) x 10 (-2) M (-1) s (-1), k b2 = (1.50 +/- 0.07) x 10 (-1) M (-2) s (-1), k a3 = (7.22 +/- 2.19) x 10 (-1) M (-2) s (-1) and k b3 = (4.85 +/- 0.04) x 10 (2) M (-3) s (-1). The proposed mechanism involves initial oxygen atom transfer from trans-[Ru (VI)(N 2O 2)(O) 2] (2+) to Br (-) to give trans-[Ru (IV)(N 2O 2)(O)(OBr)] (+), which then undergoes parallel aquation and oxidation of Br (-), and both reactions are acid-catalyzed.

  2. A revised estimate of the distance to the clouds in the Chamaeleon complex using the Tycho-Gaia Astrometric Solution

    Science.gov (United States)

    Voirin, Jordan; Manara, Carlo F.; Prusti, Timo

    2018-03-01

    Context. The determination of the distance to dark star-forming clouds is a key parameter to derive the properties of the cloud itself and of its stellar content. This parameter is still loosely constrained even in nearby star-forming regions. Aim. We want to determine the distances to the clouds in the Chamaeleon-Musca complex and explore the connection between these clouds and the large-scale cloud structures in the Galaxy. Methods: We used the newly estimated distances obtained from the parallaxes measured by the Gaia satellite and included in the Tycho-Gaia Astrometric Solution catalog. When known members of a region are included in this catalog we used their distances to infer the distance to the cloud. Otherwise, we analyzed the dependence of the color excess on the distance of the stars and looked for a turn-on of this excess, which is a proxy of the position of the front-edge of the star-forming cloud. Results: We are able to measure the distance to the three Chamaeleon clouds. The distance to Chamaeleon I is 179-10-10+11+11 pc, where the quoted uncertainties are statistical and systematic uncertainties, respectively, 20 pc further away than previously assumed. The Chamaeleon II cloud is located at the distance of 181-5-10+6+11 pc, which agrees with previous estimates. We are able to measure for the first time a distance to the Chamaeleon III cloud of 199-7-11+8+12 pc. Finally, the distance of the Musca cloud is smaller than 603-70-92+91+133 pc. These estimates do not allow us to distinguish between the possibility that the Chamaeleon clouds are part of a sheet of clouds parallel to the Galactic plane, or perpendicular to it. Conclusions: We measured a larger distance to the Chamaeleon I cloud than assumed in the past, confirmed the distance to the Chamaeleon II region, and measured for the first time the distance to the Chamaleon III cloud. These values are consistent with the scenario in which the three clouds are part of a single large-scale structure

  3. Correlation of Solid State and Solution Coordination Numbers with Infrared Spectroscopy in Five-, Six-, and Eight-Coordinate Transition Metal Complexes of DOTAM.

    Science.gov (United States)

    Nagata, Maika K C T; Brauchle, Paul S; Wang, Sen; Briggs, Sarah K; Hong, Young Soo; Laorenza, Daniel W; Lee, Andrea G; Westmoreland, T David

    2016-08-16

    Three new DOTAM (1,4,7,10-tetrakis(acetamido)-1,4,7,10-tetraazacyclododecane) complexes have been synthesized and characterized by X-ray crystallography: [Co(DOTAM)]Cl 2 •3H 2 O, [Ni(DOTAM)]Cl 2 •4H 2 O, and [Cu(DOTAM)](ClO 4 ) 2 •H 2 O. Solid state and solution IR spectroscopic features for a series of [M(DOTAM)] 2+ complexes (M=Mn, Co, Cu, Ni, Ca, Zn) correlate with solid state and solution coordination numbers. [Co(DOTAM)] 2+ , [Ni(DOTAM)] 2+ , and [Zn(DOTAM)] 2+ are demonstrated to be six-coordinate in both the solid state and in solution, while [Mn(DOTAM)] 2+ and [Ca(DOTAM)] 2+ are eight-coordinate in the solid state and remain so in solution. [Cu(DOTAM)] 2+ , which is five-coordinate by X-ray crystallography, is shown to increase its coordination number in solution to six-coordinate.

  4. The effect of specific solvent-solute interactions on complexation of alkali-metal cations by a lower-rim calix[4]arene amide derivative.

    Science.gov (United States)

    Horvat, Gordan; Stilinović, Vladimir; Kaitner, Branko; Frkanec, Leo; Tomišić, Vladislav

    2013-11-04

    Complexation of alkali-metal cations with calix[4]arene secondary-amide derivative, 5,11,17,23-tetra(tert-butyl)-25,26,27,28-tetra(N-hexylcarbamoylmethoxy)calix[4]arene (L), in benzonitrile (PhCN) and methanol (MeOH) was studied by means of microcalorimetry, UV and NMR spectroscopies, and in the solid state by X-ray crystallography. The inclusion of solvent molecules (including acetonitrile, MeCN) in the calixarene hydrophobic cavity was also investigated. The classical molecular dynamics (MD) simulations of the systems studied were carried out. By combining the results obtained using the mentioned experimental and computational techniques, an attempt was made to get an as detailed insight into the complexation reactions as possible. The thermodynamic parameters, that is, equilibrium constants, reaction Gibbs energies, enthalpies, and entropies, of the investigated processes were determined and discussed. The stability constants of the 1:1 (metal:ligand) complexes measured by different methods were in very good agreement. Solution Gibbs energies of the ligand and its complexes with Na(+) and K(+) in methanol and acetonitrile were determined. It was established that from the thermodynamic point of view, apart from cation solvation, the most important reason for the huge difference in the stability of these complexes in the two solvents lay in the fact that the transfer of complex species from MeOH to MeCN was quite favorable. That could be at least partly explained by a more exergonic inclusion of the solvent molecule in the complexed calixarene cone in MeCN as compared to MeOH, which was supported by MD simulations. Molecular and crystal structures of the lithium cation complex of L with the benzonitrile molecule bound in the hydrophobic calixarene cavity were determined by single-crystal X-ray diffraction. As far as we are aware, for the first time the alkali-metal cation was found to be coordinated by the solvent nitrile group in a calixarene adduct. According to

  5. Determination of stability constants of K and Cs nitrate complex with dicyclohexyl-18-crown-6 and dibenzo-18-crown-6 in isopropanol aqueous solutions

    International Nuclear Information System (INIS)

    Myasoedova, T.G.; Ponomareva, A.V.; Zagorets, P.A.; Filippov, E.A.

    1984-01-01

    Total stability constants of K and Cs nitrate complexes with dicyclohexyl-18-crown-6 and dibenzo-18-crown-6 in isopropanol aqueous solutions were determined by the method of low-frequency contact conductometry. Clearly defined K/Cs selectivity is observed for the system with dibenzo-18-crown-6. It is shown that lgβ depends on permittivity of the solvent. The decrease of permittivity of isopropanol aqueous solutions results in reduction of K/Cs selectivity of DB18C6

  6. Determination of stability constants of K and Cs nitrate complex with dicyclohexyl-18-crown-6 and dibenzo-18-crown-6 in isopropanol aqueous solutions

    Energy Technology Data Exchange (ETDEWEB)

    Myasoedova, T G; Ponomareva, A V; Zagorets, P A; Filippov, E A [Moskovskij Khimiko-Tekhnologicheskij Inst. (USSR)

    1984-08-01

    Total stability constants of K and Cs nitrate complexes with dicyclohexyl-18-crown-6 and dibenzo-18-crown-6 in isopropanol aqueous solutions were determined by the method of low-frequency contact conductometry. Clearly defined K/Cs selectivity is observed for the system with dibenzo-18-crown-6. It is shown that lg..beta.. depends on permittivity of the solvent. The decrease of permittivity of isopropanol aqueous solutions results in reduction of K/Cs selectivity of DB18C6.

  7. Effect of applied hydrostatic pressure on the quenching kinetics, and electronic and molecular structure of eight and nine-coordinate lanthanide complexes in solution

    International Nuclear Information System (INIS)

    Maupin, C.L.; Riehl, J.P.

    1998-01-01

    Full text: Applied hydrostatic pressure may be used as a probe of the reaction mechanism for various solution reactions involving lanthanide ions. In this work we report on the use of high pressure to probe the mechanism of enantioselective quenching between racemic luminescent lanthanide complexes containing Dy(III) Tb(III) and Eu(III), and optically active transition metal complexes as quenchers. Diastereomeric rate constants are obtained from a biexponential fit of the luminescence decay. Particular attention will be given to solvation effects on the measured diastereomeric rate constants. The source of chirality is ascribed to a enantioselective rearrangement step within a bimolecular 'encounter' complex yielding a intermolecular geometry in which the energy transfer is efficient. The effect of high pressure on the molecular and electronic structure of these complexes will also be discussed

  8. Solid state and solution photoluminescence properties of a novel meso–meso-linked porphyrin dimer Schiff base ligand and its metal complexes

    Energy Technology Data Exchange (ETDEWEB)

    Tümer, Mehmet, E-mail: mtumer@ksu.edu.tr; Ali Güngör, S.; Raşit Çiftaslan, A.

    2016-02-15

    We prepared novel meso-meso linked 4-bromo-2,6-bis[5-(4-iminophenyl)-10,15,20-triphenylporphyrin]phenol (HL) and its Cu(II), Fe(III), Mn(III), Pt(II) and Zn(II) transition metal complexes. Structural characterizations of the ligand (HL) and its metal complexes were done by the spectroscopic and analytical methods. The electronic absorption and photoluminescence spectra of the ligand, its metal complexes and the metal salts used for preparing of the complexes were investigated in the solid and solution state. The emission and excitation data of the CuCl{sub 2}·2H{sub 2}O in both solid and the solution state were obsrved in the longest wavelenght. On the other hand, the emission value of the ZnCl{sub 2} salt was shown at the shortest wavelenght. The emission values of the [LCu{sub 4}Cl{sub 3}(H{sub 2}O){sub 2}]H{sub 2}O and LPt{sub 4}Cl{sub 3} complexes in the solid state are bigger than the other metal salts. The ligand and its metal complexes show the very interesting absorption spectral properties in the solid state. Metal complexes have less number Q bands in the solid state. The electrochemical properties of the ligand and its metal complexes were investigated and found that they show the reversible or irreversible redox processes at the different scan rates. Thermal properties of the compopunds were investigated in the 20–900 °C temperature range.

  9. Inference in `poor` languages

    Energy Technology Data Exchange (ETDEWEB)

    Petrov, S.

    1996-10-01

    Languages with a solvable implication problem but without complete and consistent systems of inference rules (`poor` languages) are considered. The problem of existence of finite complete and consistent inference rule system for a ``poor`` language is stated independently of the language or rules syntax. Several properties of the problem arc proved. An application of results to the language of join dependencies is given.

  10. Contributions to the chemistry of highly concentrated electrolyte solutions. XXXIX. Investigation of Be/sup 2 +/ complex formation by the method of molar volumes

    Energy Technology Data Exchange (ETDEWEB)

    Jedinakova, V [Vysoka Skola Chemicko-Technologicka, Prague (Czechoslovakia). Katedra Technologie Jadernych Paliv a Radiochemie

    1974-01-01

    The formation of aquo- and acido-complexes of the Be/sup 2 +/ ion in aqueous solutions of strong electrolytes was studied by densimetry. In all the systems studied, HClO/sub 4/, HNO/sub 3/, NaNO/sub 3/, KOH, Ca(ClO/sub 4/)/sub 2/, CaCl/sub 2/, the overall coordination number 4 was confirmed for the complex forms of the Be/sup 2 +/ ion. If BeSO/sub 4/ is used as the differential addition in a solvent not forming complexes, dissociation of the sulfate proceeds under the formation of the aquo-complex (Be(H/sub 2/O)/sub 4/)/sup 2 +/. If beryllium perchlorate is used, the Be/sup 2 +/ ion remains in that form, in which it is added to the solution (i.e. the complex form (Be(H/sub 2/O)/sub 2/(ClO/sub 4/)/sub 2/)), in the whole concentration range of the applied isomolar series Ca(ClO/sub 4/)/sub 2/-CaCl/sub 2/, NaClO/sub 4/-NaBr, and NaClO/sub 4/-NaI.

  11. ESR investigation of alkali metal complexes of galvinoxyl-labeled benzo-15-crown-5 in frozen solution

    International Nuclear Information System (INIS)

    Mukai, Kazuo; Iida, Nobuhito; Ishizu, Kazuhiko

    1982-01-01

    A stable galvinoxyl derivative (1) of benzo-15-crown-5 was prepared and the complex formation between the spin labeled crown ether 1 and the alkali metal and ammonium salts was studied by the ESR technique. Existence of the (2:1) complex of 1 with potassium, rubidium, and ammonium salts was confirmed by the observation of the triplet ESR spectra in ethanol rigid matrix at 77K. Essentially the same g- and D-tensor values are observed for all the (2:1) complexes, indicating similar conformation of the ligand mole cule 1. The zero-field splitting parameters (D and E) are calculated on the basis of the spin distribution of 1 and the assumed molecular structures for the (2:1) complex. By comparing the observed D and E parameters with the calculated ones, the structure of the (2:1) complex in ethanol rigid matrix is discussed. On the other hand, the sodium complexes of 1 show a slightly asymmetric single line, suggesting the (1:1) complex formation btween 1 and the sodium salts. No anions (SCN - , Br - , and I - ) have any appreciable effect on the ESR spectra of both the (2:1) and (1:1) complexes. (author)

  12. Changes in magnetic properties from solid state to solution in a trinuclear linear copper(II) complex

    NARCIS (Netherlands)

    Koval, I.A.; Akhideno, H.; Tanase, S.; Belle, C.; Duboc, C.; Saint-Aman, E.; Gamez, P.; Tooke, D.M.; Spek, A.L.; Pierre, J.-L.; Reedijk, J.

    2007-01-01

    A linear trinuclear copper(II) complex containing phenoxido- and alkoxido-bridges between the metal centers has been isolated and structurally characterized. The complex cation consists of a linear array of three copper ions, assembled by means of two doubly deprotonated ligands. The octahedral

  13. Preparation and properties of chitosan-metal complex: Some factors influencing the adsorption capacity for dyes in aqueous solution.

    Science.gov (United States)

    Rashid, Sadia; Shen, Chensi; Yang, Jing; Liu, Jianshe; Li, Jing

    2018-04-01

    Chitosan-metal complexes have been widely studied in wastewater treatment, but there are still various factors in complex preparation which are collectively responsible for improving the adsorption capacity need to be further studied. Thus, this study investigates the factors affecting the adsorption ability of chitosan-metal complex adsorbents, including various kinds of metal centers, different metal salts and crosslinking degree. The results show that the chitosan-Fe(III) complex prepared by sulfate salts exhibited the best adsorption efficiency (100%) for various dyes in very short time duration (10min), and its maximum adsorption capacity achieved 349.22mg/g. The anion of the metal salt which was used in preparation played an important role to enhance the adsorption ability of chitosan-metal complex. SO 4 2- ions not only had the effect of crosslinking through electrostatic interaction with amine group of chitosan polymer, but also could facilitate the chelation of metal ions with chitosan polymer during the synthesis process. Additionally, the pH sensitivity and the sensitivity of ionic environment for chitosan-metal complex were analyzed. We hope that these factors affecting the adsorption of the chitosan-metal complex can help not only in optimizing its use but also in designing new chitosan-metal based complexes. Copyright © 2017. Published by Elsevier B.V.

  14. Adsorption of H[Ru(III) Cl2(H2EDTA)] complex on modified silica gel surface with [3-(2-aminoethyl)aminopropyl] trimethoxysilane in ethanol solutions

    International Nuclear Information System (INIS)

    Lazarin, Angelica Machi; Sernaglia, Rosana Lazara

    1999-01-01

    Silica gel was functionalized with [3-(2-aminoethyl) aminopropyl] trimethoxysilane group (SF-AEATS) and the characterization by chemical analysis (N) and infrared spectroscopy confirmed the functionalization. The capacity of the modified silica to adsorb the complex Ru (III) EDTA from ethanolic solution was studied. The selectivity coefficients of the complex formed on the support obtained was τn), 2,07 x 10 4 L/mol and the average number of ligand bonded by one metal ion on the support (n) was ∼1. (author)

  15. Comparative study of the efficiency of complex formation and extraction of thorium by solutions of certain alkylaromatic α-hydroxy acids in heptanol

    International Nuclear Information System (INIS)

    Charykov, A.K.; Aleksandrova, E.A.; Vasil'eva, O.N.

    1986-01-01

    The constants for the extraction of thorium by solutions of alkylaromatic α-hydroxy acids in heptanol occur in the order log K/sub ex/ (hydroxydiphenylacetic acid) > log K/sub ex/ (phenoxyacetic acid) > log K/sub ex/ (hydroxyphenylacetic acid). For the example of extraction equilibria involving the participation of thorium carboxylate complexes an extraction efficiency parameter is introduced which enables the efficiency of extraction to be predicted on the basis of information on the formation constants of the neutral complexes and the dissociation constants of the extractant acids in the aqueous phase

  16. Dinitrosyl iron complexes with natural thiol-containing ligands in aqueous solutions: Synthesis and some physico-chemical characteristics (A methodological review).

    Science.gov (United States)

    Vanin, Anatoly F; Borodulin, Rostislav R; Mikoyan, Vasak D

    2017-06-01

    Two approaches to the synthesis of dinitrosyl iron complexes (DNIC) with glutathione and l-cysteine in aqueous solutions based on the use of gaseous NO and appropriate S-nitrosothiols, viz., S-nitrosoglutathione (GS-NO) or S-nitrosocysteine (Cys-NO), respectively, are considered. A schematic representation of a vacuum unit for generation and accumulation of gaseous NO purified from the NO 2 admixture and its application for obtaining aqueous solutions of DNIC in a Thunberg apparatus is given. To achieve this, a solution of bivalent iron in distilled water is loaded into the upper chamber of the Thunberg apparatus, while the thiol solution in an appropriate buffer (рН 7.4) is loaded into its lower chamber. Further steps, which include degassing, addition of gaseous NO, shaking of both solutions and formation of the Fe 2+ -thiol mixture, culminate in the synthesis of DNIC. The second approach consists in a stepwise addition of Fe 2+ salts and nitrite to aqueous solutions of glutathione or cysteine. In the presence of Fe 2+ and after the increase in рН to the physiological level, GS-NO or Cys-NO generated at acid media (pH nitrosonium ions (NO + ) and the peculiar characteristics of the EPR signal of their mononuclear form (M-DNIC). Copyright © 2017. Published by Elsevier Inc.

  17. Determination of stability constants for thallium(III) cyanide complexes in aqueous solution by means of 13C and 205Ti NMR

    International Nuclear Information System (INIS)

    Blixt, J.; Gyori, B.; Glaser, J.

    1989-01-01

    In contrast to what is usually assumed, we have found and proved that thallium(III) forms very strong cyanide complexes in aqueous solution. The authors have investigated this system using 205 Tl, 13 C, and 14 N NMR and potentiometry and established the existence of four thallium(III)-cyanide complexes of the composition Tl(CN) n 3-n , n = 1-4. We have measured their chemical shifts and spin-spin coupling constants and determined their formation constants at 25 degree C in dilute (0.05 M) aqueous solution in the ionic medium ([Na + ] = 1 M, [Li + ] + [H + ] = 3 M, [ClO 4 - ] = 4 M). We have also determined the stability constant for HCN in the same ionic medium, log K a = 10.11 (5)

  18. Coprecipitation of 137Cs and 85Sr microquantities with complex compound [M(18-crown-6)]BPH4 (M=Na+, Cs+) from neutral and alkaline solutions

    International Nuclear Information System (INIS)

    Konovalova, N.A.; Rumer, I.A.; Kulyukhin, S.A.

    2009-01-01

    The paper reports the possibility of joint separation of 137 Cs and 85 Sr from neutral and alkaline aqueous solutions by their coprecipitation with the solid phase of complex compounds [M(18-crown-6)]BPh 4 (M=Na + , Cs + ), as well as to study the coprecipitation of 137 Cs and 85 Sr with the solid phase CsBPh 4 . It is found that complex compounds [M(18-crown-6)]BPh 4 (M=Na + , Cs + ) increased the degree of 85 Sr separation from solutions virtually two- to threefold vs. CsBPh 4 . Chloride and nitrate were found to have hardly any impact on the coprecipitation of 137 Cs and 85 Sr with [M(18-crown-6)]BPh 4 (M = Na + , Cs + ). (orig.)

  19. Potentiometric studies on ternary complexes involving some divalent transition metal ions, gallic acid and biologically abundant aliphatic dicarboxylic acids in aqueous solutions

    Directory of Open Access Journals (Sweden)

    Abdelatty Mohamed Radalla

    2015-06-01

    Full Text Available Formation of binary and ternary complexes of the divalent transition metal ions, Cu2+, Ni2+, Co2+ and Zn2+ with gallic acid and the biologically important aliphatic dicarboxylic acids (adipic, succinic, malic, malonic, maleic, tartaric and oxalic acids were investigated by means of the potentiometric technique at 25 °C and I = 0.10 mol dm−3 NaNO3. The acid-base properties of the ligands were investigated and discussed. The acidity constants of gallic acid and aliphatic dicarboxylic acids were determined and used for determining the stability constants of the binary and ternary complexes formed in the aqueous medium under the above experimental conditions. The formation of the different 1:1 and 1:2 binary complexes and 1:1:1 ternary complexes are inferred from the corresponding potentiometric pH-metric titration curves. The ternary complex formation was found to occur in a stepwise manner. The stability constants of these binary and ternary systems were calculated. The values of Δ log K, percentage of relative stabilization (%R.S. and log X were evaluated and discussed. The concentration distribution of the various complex species formed in solution was evaluated and discussed. The mode of chelation of ternary complexes formed was ascertained by conductivity measurements.

  20. 13C and 17O NMR binding constant studies of uranyl carbonate complexes in near-neutral aqueous solution. Yucca Mountain Project Milestone Report 3351

    International Nuclear Information System (INIS)

    Clark, D.L.; Newton, T.W.; Palmer, P.D.; Zwick, B.D.

    1995-01-01

    Valuable structural information, much of it unavailable by other methods, can be obtained about complexes in solution through NMR spectroscopy. From chemical shift and intensity measurements of complexed species, NMR can serve as a species-specific structural probe for molecules in solution and can be used to validate thermodynamic constants used in geochemical modeling. Fourier-transform nuclear magnetic resonance (FT-NMR) spectroscopy has been employed to study the speciation of uranium(VI) ions in aqueous carbonate solutions as a function of pH, ionic strength, carbonate concentration, uranium concentration, and temperature. Carbon-13 and oxygen-17 NMR spectroscopy were used to monitor the fractions, and hence thermodynamic binding constants of two different uranyl species U0 2 (CO 3 ) 3 4- and (UO 2 ) 3 (CO 3 ) 6 6- in aqueous solution. Synthetic buffer solutions were prepared under the ionic strength conditions used in the NMR studies in order to obtain an accurate measure of the hydrogen ion concentration, and a discussion of pH = -log(a H + ) versus p[H] = -log[H+] is provided. It is shown that for quantitative studies, the quantity p[H] needs to be used. Fourteen uranium(VI) binding constants recommended by the OECD NEA literature review were corrected to the ionic strengths employed in the NMR study using specific ion interaction theory (SIT), and the predicted species distributions were compared with the actual species observed by multinuclear NMR. Agreement between observed and predicted stability fields is excellent. This establishes the utility of multinuclear NMR as a species-specific tool for the study of the actinide carbonate complexation constants, and serves as a means for validating the recommendations provided by the OECD NEA

  1. Near-Infrared Fluorescence Detection of Acetylcholine in Aqueous Solution Using a Complex of Rhodamine 800 and p-Sulfonato-calix[8]arene

    Science.gov (United States)

    Jin, Takashi

    2010-01-01

    The complexing properties of p-sulfonatocalix[n]arenes (n = 4: S[4], n = 6: S[6], and n = 8: S[8]) for rhodamine 800 (Rh800) and indocyanine green (ICG) were examined to develop a near-infrared (NIR) fluorescence detection method for acetylcholine (ACh). We found that Rh800 (as a cation) forms an inclusion complex with S[n], while ICG (as a twitter ion) have no binding ability for S[n]. The binding ability of Rh800 to S[n] decreased in the order of S[8] > S[6] >> S[4]. By the formation of the complex between Rh800 and S[8], fluorescence intensity of the Rh800 was significantly decreased. From the fluorescence titration of Rh800 by S[8], stoichiometry of the Rh800-S[8] complex was determined to be 1:1 with a dissociation constant of 2.2 μM in PBS. The addition of ACh to the aqueous solution of the Rh800-S[8] complex caused a fluorescence increase of Rh800, resulting from a competitive replacement of Rh800 by ACh in the complex. From the fluorescence change by the competitive fluorophore replacement, stoichiometry of the Rh800-ACh complex was found to be 1:1 with a dissociation constant of 1.7 mM. The effects of other neurotransmitters on the fluorescence spectra of the Rh800-S[8] complex were examined for dopamine, GABA, glycine, and l-asparatic acid. Among the neurotransmitters examined, fluorescence response of the Rh800-S[8] complex was highly specific to ACh. Rh800-S[8] complexes can be used as a NIR fluorescent probe for the detection of ACh (5 × 10−4−10−3 M) in PBS buffer (pH = 7.2). PMID:22294934

  2. Complexation study of NpO2+ and UO22+ ions with several organic ligands in aqueous solutions of high ionic strength

    International Nuclear Information System (INIS)

    Borkowski, M.; Lis, S.; Choppin, G.R.

    1995-01-01

    The acid dissociation constants, pK a , and the stability constants for NpO 2 + and UO 2 2+ have been measured for certain organic ligands [acetate, α-hydroxyisobutyrate, lactate, ascorbate, oxalate, citrate, EDTA, 8-hydroxyquinoline, 1, 10-phenanthroline, and thenoyltrifluoroacetone] in 5 m (NaCl) ionic strength solution. The pK a values were determined by potentiometry or spectrometry. These methods, as well as solvent extraction with 233 U and 237 Np radiotracers, were used to measure the stability constants of the 1:1 and 1:2 complexes of dioxo cations. These constants were used to estimate the concentrations required to result in 10 % competition with hydrolysis in the 5 m NaCl solution. Such estimates are of value in assessing the solubility from radioactive waste of AnO 2 + and AnO 2 2+ in brine solutions in contact with nuclear waste in a salt-bed repository

  3. Oil-soluble and water-soluble BTPhens and their europium complexes in octanol/water solutions: interface crossing studied by MD and PMF simulations.

    Science.gov (United States)

    Benay, G; Wipff, G

    2013-01-31

    Bistriazinyl-phenantroline "BTPhen" ligands L display the remarkable feature to complex trivalent lanthanide and actinide ions, with a marked selectivity for the latter. We report on molecular dynamics studies of tetrasubstituted X(4)BTPhens: L(4+) (X = (+)Et(3)NCH(2)-), L(4-) (X = (-)SO(3)Ph-), and L(0) (X = CyMe(4)) and their complexes with Eu(III) in binary octanol/water solutions. Changes in free energies upon interface crossing are also calculated for typical solutes by potential of mean force PMF simulations. The ligands and their complexes partition, as expected, to either the aqueous or the oil phase, depending on the "solubilizing" group X. Furthermore, most of them are found to be surface active. The water-soluble L(4+) and L(4-) ligands and their (L)Eu(NO(3))(3) complexes adsorb at the aqueous side of the interface, more with L(4-) than with L(4+). The oil soluble ligand L(0) is not surface active in its endo-endo form but adsorbs on the oil side of the interface in its most polar endo-exo form, as well as in its protonated L(0)H(+) and complexed (L(0))Eu(NO(3))(3) states. Furthermore, comparing PMFs of the Eu(III) complexes with and without nitric acid shows that acidifying the aqueous phase has different effects, depending on the ligand charge. In particular, acid promotes the Eu(III) extraction by L(0) via the (L(0))(2)Eu(NO(3))(2+) complex, as observed experimentally. Overall, the results point to the importance of interfacial adsorption for the liquid-liquid extraction of trivalent lanthanide and actinide cations by BTPhens and analogues.

  4. Complexation of trivalent cationic lanthanides by N.O donor ligands: physico-chemical studies of the association and selectivity in solution

    International Nuclear Information System (INIS)

    Bravard, F.

    2004-01-01

    The aim of this work is to study the complexation of f-elements in solution by ligands incorporating N-heterocyclic donors. These ligands display interesting properties for the selective separation of An(III)/Ln(III) have been studied to obtain a better understanding of the coordination properties with f-elements and to develop more selective extractants. The hepta-dentate ligand tpaam shows an affinity for Ln(III) similar to the tetradentate ligand tpa in water even when the three additional amide groups are bonded to the metal. Even though the complexation with tpa is exothermic, that with tpaam is endothermic with a more positive entropy. The dehydration of the cation disfavours the formation of Ln(III) complexes with ligands containing weak donors. The analysis of the solution paramagnetic relaxation times of the tpaam complexes is in agreement with data in the solid-state. There is little difference between the formation constants of the Ln 3+ complexes with different ligands (tpaam, tpzen, tpa and tpza) as determined by UV-vis spectrophotometry in anhydrous acetonitrile. The limitations encountered during this study are intrinsic to the ligands studied. The preliminary study of two tetrapodal ligands containing acid and pyridine groups (L py )or pyrazine (L pz ) show the formation of 1:1 complexes in water. Analysis of the formation constants of the corresponding Gd(III) complexes shows that replacement of a pyridine group by pyrazine result in a loss of stability of 1.6 logarithmic units. (author) [fr

  5. High-Order Ca(II)-Chloro Complexes in Mixed CaCl2-LiCl Aqueous Solution: Insights from Density Functional Theory and Molecular Dynamics Simulations.

    Science.gov (United States)

    Wang, Yu-Lin; Wang, Ying; Yi, Hai-Bo

    2016-07-21

    In this study, the structural characteristics of high-coordinated Ca-Cl complexes present in mixed CaCl2-LiCl aqueous solution were investigated using density functional theory (DFT) and molecular dynamics (MD) simulations. The DFT results show that [CaClx](2-x) (x = 4-6) clusters are quite unstable in the gas phase, but these clusters become metastable when hydration is considered. The MD simulations show that high-coordinated Ca-chloro complexes are possible transient species that exist for up to nanoseconds in concentrated (11.10 mol·kg(-1)) Cl(-) solution at 273 and 298 K. As the temperature increases to 423 K, these high-coordinated structures tend to disassociate and convert into smaller clusters and single free ions. The presence of high-order Ca-Cl species in concentrated LiCl solution can be attributed to their enhanced hydration shell and the inadequate hydration of ions. The probability of the [CaClx](2-x)aq (x = 4-6) species being present in concentrated LiCl solution decreases greatly with increasing temperature, which also indicates that the formation of the high-coordinated Ca-Cl structure is related to its hydration characteristics.

  6. Tris-amidoximate uranyl complexes via η2 binding mode coordinated in aqueous solution shown by X-ray absorption spectroscopy and density functional theory methods.

    Science.gov (United States)

    Zhang, Linjuan; Qie, Meiying; Su, Jing; Zhang, Shuo; Zhou, Jing; Li, Jiong; Wang, Yu; Yang, Shitong; Wang, Shuao; Li, Jingye; Wu, Guozhong; Wang, Jian Qiang

    2018-03-01

    The present study sheds some light on the long-standing debate concerning the coordination properties between uranyl ions and the amidoxime ligand, which is a key ingredient for achieving efficient extraction of uranium. Using X-ray absorption fine structure combined with theoretical simulation methods, the binding mode and bonding nature of a uranyl-amidoxime complex in aqueous solution were determined for the first time. The results show that in a highly concentrated amidoxime solution the preferred binding mode between UO 2 2+ and the amidoxime ligand is η 2 coordination with tris-amidoximate species. In such a uranyl-amidoximate complex with η 2 binding motif, strong covalent interaction and orbital hybridization between U 5f/6d and (N, O) 2p should be responsible for the excellent binding ability of the amidoximate ligand to uranyl. The study was performed directly in aqueous solution to avoid the possible binding mode differences caused by crystallization of a single-crystal sample. This work also is an example of the simultaneous study of local structure and electronic structure in solution systems using combined diagnostic tools.

  7. Exploiting the Poor

    DEFF Research Database (Denmark)

    Kamp Justesen, Mogens; Bjørnskov, Christian

    2014-01-01

    While extant research has focused on the causes and consequences of corruption at the macro-level, less effort has been devoted to understanding the micro-foundation of corruption. We argue that poor people are more likely to be victims of corrupt behavior by street-level bureaucrats as the poor...... often rely heavily on services provided by governments. We test this proposition using micro-level survey data from the Afrobaromenter. Multilevel regressions across 18 countries show that poor people are much more prone to experience having to pay bribes to government officials....

  8. Accounting for the Poor

    OpenAIRE

    Robert M. Townsend

    2013-01-01

    Economists and other social scientists have long tried to understand the nature of poverty and how poor people make decisions. For example, T.W. Schultz, a Nobel Laureate, former professor of economics at the University of Chicago, and former president of the American Economic Association, spent his career working in development and agricultural economics. In his 1980 Nobel Prize acceptance speech, Schultz suggests that there is some accounting for the behavior of the poor in agriculture. "Fa...

  9. Simple Solutions to Complex Problems: Moral Panic and the Fluid Shift from "Equity" to "Quality" in Education

    Science.gov (United States)

    Mockler, Nicole

    2014-01-01

    Education is increasingly conceptualised by governments and policymakers in western democracies in terms of productivity and human capital, emphasising elements of individualism and competition over concerns around democracy and equity. More and more, solutions to intransigent educational problems related to equity are seen in terms of quality and…

  10. The Effects of Postprocessing on Physical and Solution Deposition of Complex Oxide Thin Films for Tunable Applications

    Science.gov (United States)

    2016-02-01

    BST film capacitor devices were fabricated using physical and chemical solution deposition techniques. The typical dielectric constant of the...electrode loss, and the parallel resistor- capacitor circuit represents the capacitance and the dielectric loss, assuming lead inductance is...Thin barium strontium titanate (BST) films are being developed as dielectric film for use in tunable radio frequency (RF)/microwave applications. Thin

  11. Solute-solvent complex switching dynamics of chloroform between acetone and dimethylsulfoxide-two-dimensional IR chemical exchange spectroscopy.

    Science.gov (United States)

    Kwak, Kyungwon; Rosenfeld, Daniel E; Chung, Jean K; Fayer, Michael D

    2008-11-06

    Hydrogen bonds formed between C-H and various hydrogen bond acceptors play important roles in the structure of proteins and organic crystals, and the mechanisms of C-H bond cleavage reactions. Chloroform, a C-H hydrogen bond donor, can form weak hydrogen-bonded complexes with acetone and with dimethylsulfoxide (DMSO). When chloroform is dissolved in a mixed solvent consisting of acetone and DMSO, both types of hydrogen-bonded complexes exist. The two complexes, chloroform-acetone and chloroform-DMSO, are in equilibrium, and they rapidly interconvert by chloroform exchanging hydrogen bond acceptors. This fast hydrogen bond acceptor substitution reaction is probed using ultrafast two-dimensional infrared (2D-IR) vibrational echo chemical exchange spectroscopy. Deuterated chloroform is used in the experiments, and the 2D-IR spectrum of the C-D stretching mode is measured. The chemical exchange of the chloroform hydrogen bonding partners is tracked by observing the time-dependent growth of off-diagonal peaks in the 2D-IR spectra. The measured substitution rate is 1/30 ps for an acetone molecule to replace a DMSO molecule in a chloroform-DMSO complex and 1/45 ps for a DMSO molecule to replace an acetone molecule in a chloroform-acetone complex. Free chloroform exists in the mixed solvent, and it acts as a reactive intermediate in the substitution reaction, analogous to a SN1 type reaction. From the measured rates and the equilibrium concentrations of acetone and DMSO, the dissociation rates for the chloroform-DMSO and chloroform-acetone complexes are found to be 1/24 ps and 1/5.5 ps, respectively. The difference between the measured rate for the complete substitution reaction and the rate for complex dissociation corresponds to the diffusion limited rate. The estimated diffusion limited rate agrees well with the result from a Smoluchowski treatment of diffusive reactions.

  12. 1,2,4-Triazines in the Synthesis of Bipyridine Bisphenolate ONNO Ligands and Their Highly Luminescent Tetradentate Pt(II) Complexes for Solution-Processable OLEDs.

    Science.gov (United States)

    Pander, Piotr; Bulmer, Rachel; Martinscroft, Ross; Thompson, Stuart; Lewis, Frank W; Penfold, Thomas J; Dias, Fernando B; Kozhevnikov, Valery N

    2018-04-02

    This article describes a convenient method for the synthesis of ONNO-type tetradentate 6,6'-bis(2-phenoxy)-2,2'-bipyridine (bipyridine bisphenolate, BpyBph) ligands and their platinum(II) complexes. The methodology includes the synthesis of 1,2,4-triazine precursors followed by their transformation to functionalized pyridines by the Boger reaction. Two complementary routes employing 3,3'- and 5,5'-bis-triazines allow a modification of the central pyridine rings in different positions, which was exemplified by the introduction of cyclopentene rings. The new ligands were used to prepare highly luminescent ONNO-type Pt(II) complexes. The position of the cyclopentene rings significantly influences the solubility and photophysical properties of these complexes. Derivatives with closely positioned cyclopentene rings are soluble in organic solvents and proved to be the best candidate for solution-processable organic light-emitting devices (OLEDs), showing efficient single-dopant candlelight electroluminescence.

  13. Fast and low-temperature sintering of silver complex using oximes as a potential reducing agent for solution-processible, highly conductive electrodes

    International Nuclear Information System (INIS)

    Yoo, Ji Hoon; Park, Su Bin; Kim, Ji Man; Han, Dae Sang; Chae, Jangwoo; Kwak, Jeonghun

    2014-01-01

    Highly conductive, solution-processed silver thin-films were obtained at a low sintering temperature of 100 °C in a short sintering time of 10 min by introducing oximes as a potential reductant for silver complex. The thermal properties and reducibility of three kinds of oximes, acetone oxime, 2-butanone oxime, and one dimethylglyoxime, were investigated as a reducing agent, and we found that the thermal decomposition product of oximes (ketones) accelerated the conversion of silver complex into highly conductive silver at low sintering temperature in a short time. Using the acetone oxime, the silver thin-film exhibited the lowest surface resistance (0.91 Ω sq −1 ) compared to those sing other oximes. The silver thin-film also showed a high reflectance of 97.8%, which is comparable to evaporated silver films. We also demonstrated inkjet printed silver patterns with the oxime-added silver complex inks. (paper)

  14. Conductance Studies on Complex Formation between c-Methylcalix[4]resorcinarene and Titanium (III in Acetonitrile-H2O Binary Solutions

    Directory of Open Access Journals (Sweden)

    Naghmeh Saadati

    2013-09-01

    Full Text Available Calixresorcinarenes have proved to be unique molecules for molecular recognition via hydrogen bonding, hydrophobic and ionic interactions with suitable substrates such as cations. The study of the interactions involved in the complexation of different cations with calixresorcinarenes in solvent mixtures is important for a better understanding of the mechanism of biological transport, molecular recognition, and other analytical applications. This article summarizes different aspects of the complexes of the Ti3+ metal cation with c-methylcalix[4]resorcinarene (CMCR as studied by conductometry in acetonitrile (AN–water (H2O binary mixtures at different temperatures. Conductance data show that the metal cation/ligand (ML stoichiometry of the complexes in solution is 1:1 in all cases. Non-linear behaviour was observed for the variation of logKf of the complexes vs. the composition of the binary solvent mixtures. Selectivity of CMCR for the Ti3+ cation is sensitive to solvent composition; in some cases and at certain compositions of the mixed solvent systems, the selectivity order is changed. Values of thermodynamic parameters (, for formation of the CMCR–Ti3+ complexes in AN–H2O binary systems were obtained from the temperature dependence of stability constants, and the results show that the thermodynamics of complexation reactions are affected by the nature and composition of the mixed solvents.

  15. Removal combined with reduction of hexavalent chromium from aqueous solution by Fe-ethylene glycol complex microspheres

    Science.gov (United States)

    Zhang, Yong-Xing; Jia, Yong

    2016-12-01

    Three-dimensional Fe-ethylene glycol (Fe-EG) complex microspheres were synthesized by a facile hydrothermal method, and were characterized by field emission scanning electron microscopy and transmission electron microscopy. The adsorption as well as reduction properties of the obtained Fe-EG complex microspheres towards Cr(VI) ions were studied. The experiment data of adsorption kinetic and isotherm were fitted by nonlinear regression approach. In neutral condition, the maximum adsorption capacity was 49.78 mg g-1 at room temperature, and was increased with the increasing of temperature. Thermodynamic parameters including the Gibbs free energy, standard enthalpy and standard entropy revealed that adsorption of Cr(VI) was a feasible, spontaneous and endothermic process. Spectroscopic analysis revealed the adsorption of Cr(VI) was a physical adsorption process. The adsorbed CrO42- ions were partly reduced to Cr(OH)3 by Fe(II) ions and the organic groups in the Fe-EG complex.

  16. Europium, uranyl, and thorium-phenanthroline amide complexes in acetonitrile solution: an ESI-MS and DFT combined investigation.

    Science.gov (United States)

    Xiao, Cheng-Liang; Wang, Cong-Zhi; Mei, Lei; Zhang, Xin-Rui; Wall, Nathalie; Zhao, Yu-Liang; Chai, Zhi-Fang; Shi, Wei-Qun

    2015-08-28

    The tetradentate N,N'-diethyl-N,N'-ditolyl-2,9-diamide-1,10-phenanthroline (Et-Tol-DAPhen) ligand with hard-soft donor atoms has been demonstrated to be promising for the group separation of actinides from highly acidic nuclear wastes. To identify the formed complexes of this ligand with actinides and lanthanides, electrospray ionization mass spectrometry (ESI-MS) combined with density functional theory (DFT) calculations was used to probe the possible complexation processes. The 1 : 2 Eu-L species ([EuL2(NO3)](2+)) can be observed in ESI-MS at low metal-to-ligand ([M]/[L]) ratios, whereas the 1 : 1 Eu-L species ([EuL(NO3)2](+)) can be observed when the [M]/[L] ratio is higher than 1.0. However, ([UO2L(NO3)](+)) is the only detected species for the uranyl complexes. The [ThL2(NO3)2](2+) species can be observed at low [M]/[L] ratios; the 1 : 2 species ([ThL2(NO3)](3+)) and a new 1 : 1 species ([ThL(NO3)3](+)) can be detected at high [M]/[L] ratios. Collision-induced dissociation (CID) results showed that Et-Tol-DAPhen ligands can coordinate strongly with metal ions, and the coordination moieties remain intact under CID conditions. Natural bond orbital (NBO), molecular electrostatic potential (MEP), electron localization function (ELF), atoms in molecules (AIM) and molecular orbital (MO) analyses indicated that the metal-ligand bonds of the actinide complexes exhibited more covalent character than those of the lanthanide complexes. In addition, according to thermodynamic analysis, the stable cationic M-L complexes in acetonitrile are found to be in good agreement with the ESI-MS results.

  17. Study on complexed lead and cadmium ions removal from aqueous solutions by means of ion exchange method

    International Nuclear Information System (INIS)

    Dudzinska, M.

    1992-01-01

    The possibility of simultaneous removal of heavy metal ions and organic chelates from waste water has been studied. The experimental work has been preceded by extensive theoretical considerations and calculations of physico-chemical parameters of the process for model and real waste water systems. The negative influence of the presence of sulfate anions on cadmium and lead complexes removal in ion exchange process has been experimentally proved. In the systems free of sulfate anions or when their concentrations were low, the purification process conducted on Amberlite IRA-68 was very effective for cadmium and lead complexes removal. 112 refs, 78 figs, 15 tabs

  18. Formation of Mixed-Ligand Complexes of Metals(II) with Monoamine Complexones and Amino Acids in Solution

    Science.gov (United States)

    Pyreu, D. F.; Gridchin, S. N.

    2018-05-01

    The formation of mixed-ligand complexes in the M(II)-Nta, Ida-L (M = Cu(II), Ni, Zn, Co(II), L = Ser, Thr, Asp, Arg, Asn) systems, where Ida and Nta are the residues of iminodiacetic and nitrilotriacetic acids, respectively, is studied using pH measurements, calorimetry and spectrophotometry. The thermodynamic parameters (log K, Δr G 0, Δr H, Δr S) of their formation at 298.15 K and ionic strength I = 0.5 (KNO3) are determined. The most likely scenario of amino acid residue coordination in the composition of mixed complexes is discussed.

  19. Solution of environmental protection problems and complex utilization of raw materials during mining and processing of uranium ores

    International Nuclear Information System (INIS)

    Litvinenko, V.G.; Savva, P.P.

    1993-01-01

    Consideration is given to the complex of measures taken in Priargunsky industrial mine-chemical association and directed to environment protection, complex utilization of raw materials during mining and processing of uranium ores. These measures include: 1) reduction of toxic chemical agent effluents into atmosphere due to introduction of new methods and gas cleaning systems; 2) rational use of water resources owing to application of circulating water supply systems, waste waters treatment and effective control of the state of water consumption by industrial enterprises; 3) utilization of gangue and industrial solid wastes

  20. Characterization of Cu–Ni nanostructured alloys obtained by a chemical route. Influence of the complexing agent content in the starting solution

    Energy Technology Data Exchange (ETDEWEB)

    Carreras, Alejo C., E-mail: acarreras@famaf.unc.edu.ar [Instituto de Física Enrique Gaviola (IFEG), Facultad de Matemática, Astronomía y Física, Universidad Nacional de Córdoba—CONICET, Medina Allende s/n, Ciudad Universitaria, 5016 Córdoba (Argentina); Cangiano, María de los A.; Ojeda, Manuel W.; Ruiz, María del C. [Instituto de Investigaciones en Tecnología Qumica (INTEQUI), Facultad de Química, Bioquímica y Farmacia, Universidad Nacional de San Luis—CONICET, Chacabuco y Pedernera, 5700 San Luis (Argentina)

    2015-03-15

    The influence of the amount of complexing agent added to the starting solution on the physicochemical properties of Cu–Ni nanostructured alloys obtained through a chemical route, was studied. For this purpose, three Cu–Ni nanoalloy samples were synthesized by a previously developed procedure, starting from solutions with citric acid to metal molar ratios (C/Me) of 0.73, 1.00 and 1.50. The synthesis technique consisted in preparing a precursor via the citrate-gel method, and carrying out subsequent thermal treatments in controlled atmospheres. Sample characterization was performed by scanning electron microscopy, X-ray microanalysis, X-ray diffraction, transmission electron microscopy, X-ray nanoanalysis and electron diffraction. In the three cases, copper and nickel formed a solid solution with a Cu/Ni atomic ratio close to 50/50, and free of impurities inside the crystal structure. The citric acid content of the starting solution proved to have an important influence on the morphology, size distribution, porosity, and crystallinity of the Cu–Ni alloy microparticles obtained, but a lesser influence on their chemical composition. The molar ratio C/Me = 1.00 resulted in the alloy with the Cu/Ni atomic ratio closest to 50/50. - Highlights: • We synthesize Cu–Ni nanoalloys by a chemical route based on the citrate-gel method. • We study the influence of the complexing agent content of the starting solution. • We characterize the samples by electron microscopy and X-ray techniques. • Citric acid influences the shape, size, porosity and crystallinity of the alloys.

  1. Gold sorption from aqueous solutions by hydroxides and oxides at conditions of complex formation and oxidation-reduction

    International Nuclear Information System (INIS)

    Novikov, A.I.; Shekoturova, E.K.; Ribalko, T.A.

    1986-01-01

    With using of radionuclide 198 Au 3+ at initial form 198 AuCl 4 - the sorption of Au 3+ at its concentrations from 1.27·10 3 till 1.9·10 -9 mol/l from solutions of NaClO 4 (0.1 and 1 mol/l), KHO 3 (0.1 and 1 mol/l), NaNO 3 (1 mol/l), NaCl(0.7-3 mol/l), KCl(0.01; 0.1 and 1 mol/l), NH 4 NO 3 (0.1 and 1 mol/l)NH 4 Cl(10 -3 ; 10 -2 ; 10 -1 and 1 mol/l) in a wide ph range (0+14) by hydroxides of Fe(III), Zr, oxides of Fe(III), Ti(IV), Mn(IV) and Sn(IV) is studied. The dependences of sorption value of Au 3+ on ph of medium, composition and concentrations of electrolytes in solution are defined. Calculations on condition of Au 3+ in aqueous solutions are conducted. Optimal conditions of gold concentration (including 198 Au) and its separation from carrier at sorption process are defined as well.

  2. Charge inversion of dendrimers in complexes with linear polyelectrolytes in the solutions with low pH

    NARCIS (Netherlands)

    Larin, S.V.; Lyulin, S.V.; Lyulin, A.V.; Darinskii, A.A.

    2009-01-01

    Complexes of fully ionized third-generation dendrimers with oppositely charged linear polyelectrolyte chains are studied by the Brownian dynamics method. A freely jointed model of a dendrimer and a linear chain is used. Electrostatic interactions are considered within the Debye-Hückel approximation

  3. Removal combined with reduction of hexavalent chromium from aqueous solution by Fe-ethylene glycol complex microspheres

    Energy Technology Data Exchange (ETDEWEB)

    Zhang, Yong-Xing [School of Physics and Electronic Information, Huaibei Normal University, Huaibei 235000 (China); Jia, Yong, E-mail: yjiaahedu@163.com [School of Pharmacy, Anhui University of Chinese Medicine, Hefei 230012 (China)

    2016-12-15

    Highlights: • Fe-EG complex microspheres were synthesized by a hydrothermal method. • The removal properties towards Cr(VI) ions were investigated. • The adsorption and reduction mechanism was revealed by FTIR and XPS. - Abstract: Three-dimensional Fe-ethylene glycol (Fe-EG) complex microspheres were synthesized by a facile hydrothermal method, and were characterized by field emission scanning electron microscopy and transmission electron microscopy. The adsorption as well as reduction properties of the obtained Fe-EG complex microspheres towards Cr(VI) ions were studied. The experiment data of adsorption kinetic and isotherm were fitted by nonlinear regression approach. In neutral condition, the maximum adsorption capacity was 49.78 mg g{sup −1} at room temperature, and was increased with the increasing of temperature. Thermodynamic parameters including the Gibbs free energy, standard enthalpy and standard entropy revealed that adsorption of Cr(VI) was a feasible, spontaneous and endothermic process. Spectroscopic analysis revealed the adsorption of Cr(VI) was a physical adsorption process. The adsorbed CrO{sub 4}{sup 2−} ions were partly reduced to Cr(OH){sub 3} by Fe(II) ions and the organic groups in the Fe-EG complex.

  4. Structure, Dynamics, and Kinetics of Weak Protein-Protein Complexes from NMR Spin Relaxation Measurements of Titrated Solutions

    International Nuclear Information System (INIS)

    Salmon, L.; Licinio, A.; Jensen, M.R.; Blackledge, M.; Ortega Roldan, J.L.; Van Nuland, N.; Lescop, E.

    2011-01-01

    We have recently presented a titration approach for the determination of residual dipolar couplings (RDCs) from experimentally inaccessible complexes. Here, we extend this approach to the measurement of 15 N spin relaxation rates and demonstrate that this can provide long-range structural, dynamic, and kinetic information about these elusive systems. (authors)

  5. Generalist solutions to complex problems: generating practice-based evidence - the example of managing multi-morbidity

    NARCIS (Netherlands)

    Reeve, J.; Blakeman, T.; Freeman, G.K.; Green, L.A.; James, P.A.; Lucassen, P.L.; Martin, C.M.; Sturmberg, J.P.; Weel, C. van

    2013-01-01

    BACKGROUND: A growing proportion of people are living with long term conditions. The majority have more than one. Dealing with multi-morbidity is a complex problem for health systems: for those designing and implementing healthcare as well as for those providing the evidence informing practice. Yet

  6. Alkali Metal Ion Complexes with Phosphates, Nucleotides, Amino Acids, and Related Ligands of Biological Relevance. Their Properties in Solution.

    Science.gov (United States)

    Crea, Francesco; De Stefano, Concetta; Foti, Claudia; Lando, Gabriele; Milea, Demetrio; Sammartano, Silvio

    2016-01-01

    Alkali metal ions play very important roles in all biological systems, some of them are essential for life. Their concentration depends on several physiological factors and is very variable. For example, sodium concentrations in human fluids vary from quite low (e.g., 8.2 mmol dm(-3) in mature maternal milk) to high values (0.14 mol dm(-3) in blood plasma). While many data on the concentration of Na(+) and K(+) in various fluids are available, the information on other alkali metal cations is scarce. Since many vital functions depend on the network of interactions occurring in various biofluids, this chapter reviews their complex formation with phosphates, nucleotides, amino acids, and related ligands of biological relevance. Literature data on this topic are quite rare if compared to other cations. Generally, the stability of alkali metal ion complexes of organic and inorganic ligands is rather low (usually log K  Na(+) > K(+) > Rb(+) > Cs(+). For example, for citrate it is: log K ML = 0.88, 0.80, 0.48, 0.38, and 0.13 at 25 °C and infinite dilution. Some considerations are made on the main aspects related to the difficulties in the determination of weak complexes. The importance of the alkali metal ion complexes was also studied in the light of modelling natural fluids and in the use of these cations as probes for different processes. Some empirical relationships are proposed for the dependence of the stability constants of Na(+) complexes on the ligand charge, as well as for correlations among log K values of NaL, KL or LiL species (L = generic ligand).

  7. pH Sensing Properties of Flexible, Bias-Free Graphene Microelectrodes in Complex Fluids: From Phosphate Buffer Solution to Human Serum.

    Science.gov (United States)

    Ping, Jinglei; Blum, Jacquelyn E; Vishnubhotla, Ramya; Vrudhula, Amey; Naylor, Carl H; Gao, Zhaoli; Saven, Jeffery G; Johnson, Alan T Charlie

    2017-08-01

    Advances in techniques for monitoring pH in complex fluids can have a significant impact on analytical and biomedical applications. This study develops flexible graphene microelectrodes (GEs) for rapid (pH of complex biofluids by measuring real-time Faradaic charge transfer between the GE and a solution at zero electrical bias. For an idealized sample of phosphate buffer solution (PBS), the Faradaic current is varied monotonically and systematically with the pH, with a resolution of ≈0.2 pH unit. The current-pH dependence is well described by a hybrid analytical-computational model, where the electric double layer derives from an intrinsic, pH-independent (positive) charge associated with the graphene-water interface and ionizable (negative) charged groups. For ferritin solution, the relative Faradaic current, defined as the difference between the measured current response and a baseline response due to PBS, shows a strong signal associated with ferritin disassembly and the release of ferric ions at pH ≈2.0. For samples of human serum, the Faradaic current shows a reproducible rapid (pH. By combining the Faradaic current and real-time current variation, the methodology is potentially suitable for use to detect tumor-induced changes in extracellular pH. © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  8. Phosphole complexes of Gold(I) halides: Comparison of solution and solid-state structures by a combination of solution and CP/MAS 31P NMR spectroscopy and x-ray crystallography

    International Nuclear Information System (INIS)

    Attar, S.; Nelson, J.H.; Bearden, W.H.; Alcock, N.W.; Alyea, E.C.

    1990-01-01

    A series of complexes of 1-phenyldibenzophosphole (DBP), 1-phenyl-3,4,-dimethylphosphole (DMPP), and triphenylphosphine of the type L n AuX (n = 1, L = DBP, DMPP, Ph 3 P, X = Cl, Br, I; n = 3, L = DBP, X = Cl, Br, I; n = 3, L = Ph 3 P, X = Cl; n = 4, L = DBP, DMPP, X = PF 6 ) have been prepared and characterized. The structures of (DBP)AuCl (1), (DBP) 3 AuCl (2), and (DMPP)AuCl (3) have been determined from three-dimensional x-ray data collected by counter methods. Crystal structure of the complexes is reported. The CP/MAS 31 P( 1 H) NMR spectrum of complex 1 shows two resonances in a 1:1 intensity ratio, and the CP/MAS 31 P( 1 H) NMR spectrum of complex 3 shows three resonances in a 1:1:1 intensity ratio for reasons that are not yet understood. Though the three phospholes are crystallographically inequivalent (d(AuP) = 2.359 (1), 2.382 (1), and 2.374 (2) angstrom) the molecule has effective C s symmetry as evidenced by the observation of two 31 P resonances in a 2:1 intensity ratio in its CP/MAS 31 P( 1 H) NMR spectrum. Variable-temperature 31 P( 1 H) NMR spectra obtained on solutions of LAuCl + L in various ratios were analyzed to determine the nature of the species present in solution and to gain information regarding their relative stabilities as a function of the nature of the phosphine. 79 refs., 8 figs., 9 tabs

  9. Physical and chemical transformations of μ-oxo dimers and alkoxy complexes of Fe-octaethylporphyrins in solids and in solutions

    Science.gov (United States)

    Ivashin, N. V.; Shulga, A. M.; Terekhov, S. N.; Dzilinski, K.

    1996-11-01

    It has been found that relatively small changes in conditions of crystallization in the synthesis process of μ-oxo dimers can lead to quite different products with dimeric or monomeric structures. Molecular structures of these products, discussed on the basis of Fe-octaethylporphyrin (FeOEP) complexes, have been studied using IR, NMR, EPR, resonance Raman (RR), mass and Mössbauer spectroscopies. The use of chloroform with admixture of alcohols (methanol, deuteromethanol and ethanol) in place of pure chloroform for crystallization of the eluate obtained during synthesis of μ-oxo dimers leads to the formation of alkoxy complexes instead of the μ-oxo dimers. It has been also established that dissolution of the μ-oxo dimers in chloroform-ethanol or chloroform-methanol mixtures leads to conversion of the μ-oxo dimers into the alkoxy complexes after evaporation of the solvents. Methoxy and ethoxy ligands in Fe(OEP)OCH 3 and Fe(OEP)OC 2H 5 complexes can exchange the positions during addition of ethanol to the former and methanol to the latter complex in solution. The possibility of generation of doubly bridged structures of the type: OEP Fe< RRFe OEP where R is OCH 3 or OC 2H 5 is discussed.

  10. Quantum chemical calculations and spectroscopic measurements of spectroscopic and thermodynamic properties of given uranyl complexes in aqueous solutions with possible environmental and industrial applications

    Directory of Open Access Journals (Sweden)

    Višňak Jakub

    2016-01-01

    Full Text Available A brief introduction into computational methodology and preliminary results for spectroscopic (excitation energies, vibrational frequencies in ground and excited electronic states and thermodynamic (stability constants, standard enthalpies and entropies of complexation reactions properties of some 1:1, 1:2 and 1:3 uranyl sulphato- and selenato- complexes in aqueos solutions will be given. The relativistic effects are included via Effective Core Potential (ECP, electron correlation via (TDDFT/B3LYP (dispersion interaction corrected and solvation is described via explicit inclusion of one hydration sphere beyond the coordinated water molecules. We acknowledge limits of this approximate description – more accurate calculations (ranging from semi-phenomenological two-component spin-orbit coupling up to four-component Dirac-Coulomb-Breit hamiltonian and Molecular Dynamics simulations are in preparation. The computational results are compared with the experimental results from Time-resolved Laser-induced Fluorescence Spectroscopy (TRLFS and UV-VIS spectroscopic studies (including our original experimental research on this topic. In case of the TRLFS and UV-VIS speciation studies, the problem of complex solution spectra decomposition into individual components is ill-conditioned and hints from theoretical chemistry could be very important. Qualitative agreement between our quantum chemical calculations of the spectroscopic properties and experimental data was achieved. Possible applications for geochemical modelling (e.g. safety studies of nuclear waste repositories, modelling of a future mining site and analytical chemical studies (including natural samples are discussed.

  11. XI International conference Problems of solvation and complex formation in solutions, and VI Conference of young scientists Theoretical and experimental chemistry of liquid-phase systems (Krestovsky readings). Summary of reports

    International Nuclear Information System (INIS)

    2011-01-01

    The collection contains materials of plenary, sectional and poster sessions, presented at the XI International conference Problems of solvation and complex formation in solutions, and VI Conference of young scientists Theoretical and experimental chemistry of liquid-phase systems (Krestovsky readings). Theoretical questions and new experimental methods of chemistry of solutions, structure and dynamics of molecular and ion-molecular systems in solution and at the phase boundary; modern aspects of applied chemistry of solutions are discussed [ru

  12. Complex solution of problem of all-season construction of roads and pipelines on universal composite pontoon units

    Science.gov (United States)

    Ryabkov, A. V.; Stafeeva, N. A.; Ivanov, V. A.; Zakuraev, A. F.

    2018-05-01

    A complex construction consisting of a universal floating pontoon road for laying pipelines in automatic mode on its body all year round and in any weather for Siberia and the Far North has been designed. A new method is proposed for the construction of pipelines on pontoon modules, which are made of composite materials. Pontoons made of composite materials for bedding pipelines with track-forming guides for automated wheeled transport, pipelayer, are designed. The proposed system eliminates the construction of a road along the route, ensures the buoyancy and smoothness of the self-propelled automated stacker in the form of a "centipede", which has a number of significant advantages in the construction and operation of the entire complex in the swamp and watered areas without overburden.

  13. Application of UV-ozonization to treat complex cyanide and hydroponic solution. Ozone shigaisen heiyo mizushori hoho no oyorei

    Energy Technology Data Exchange (ETDEWEB)

    Wakou, H; Yasuda, M [Industrial Research Institute of Kanagawa Prefecture, Kanagawa (Japan)

    1993-04-15

    Water oxidizing treatment which simultaneously uses both ozone and ultraviolet rays is not widely used because of its large electric power consumption and inappropriate high concentration treatment. However, it is characterized by its small sludge production and non-residual oxidant after the treatment. Its existing examples of application comprise production of drinking water to be urgently used, superpure water to be used for the semiconductor production and water to be used in the cosmic space, disinfection of fish-breeding ponds, and deodorization of chemical factories. As a new purpose of use, it is applied to disinfection of nutrient liquid for the fertilizer. It is necessary to prohibit the discharge of unabsorbed and untreated nutrient liquid for the fertilizer. For the recycling utilization, it is further necessary to disinfect the pathogenic bacteria and prevent the accumulation of organic secretion from the roots. Disinfection could be made by applying the present treatment method to a cultivation of tomatoes with water. The sedimentation of ferrous rust could be prevented by using an appropriate ferrous complex in the nutrient liquid. The decomposition loss of complex was compensated with a quantitative equivalence. When cyanic plating waste water is made innocuous by chlorine or sodium hypophosphite, a large quantity of sludge is produced. However by applying the present treatment method to it, the cyanic complex could be decomposed, and separated and recovered as an insoluble matter. 11 refs., 3 figs.

  14. 9. Poor medication

    African Journals Online (AJOL)

    Sitwala

    Majority (60%) of the patients were reviewed at least twice in the last 6 months at the time of the interview. 195 (83%) patients reported that drugs prescribed were not available at the hospital pharmacy, but 186 (79%) of. Factors Associated With Poor Medication Adherence. In Hypertensive Patients In Lusaka, Zambia. 1,4. 1.

  15. AdS solutions in gauge supergravities and the global anomaly for the product of complex two-cycles

    Energy Technology Data Exchange (ETDEWEB)

    Bytsenko, A.A. [Universidade Estadual de Londrina, Departamento de Fisica, Caixa Postal 6001, Londrina-Parana (Brazil); Elizalde, E. [Universitat Autonoma de Barcelona, Consejo Superior de Investigaciones Cientificas (ICE/CSIC) and Institut d' Estudis Espacials de Catalunya (IEEC), Facultat de Ciencies, Bellaterra (Barcelona) (Spain)

    2011-03-15

    Cohomological methods are applied for the special set of solutions corresponding to rotating branes in arbitrary dimensions, AdS black holes (which can be embedded in ten or eleven dimensions), and gauge supergravities. A new class of solutions is proposed, the Hilbert modular varieties, which consist of the 2n-fold product of the two-spaces H{sup n} /{gamma} (where H{sup n} denotes the product of n upper half-planes, H {sup 2}, equipped with the co-compact action of {gamma} is contained in SL(2, R){sup n}) and (H {sup n}){sup *}/{gamma} (where (H {sup 2}){sup *}=H {sup 2}{gamma} and {gamma} is a congruence subgroup of SL(2, R) {sup n}). The cohomology groups of the Hilbert variety, which inherit a Hodge structure (in the sense of Deligne), are analyzed, as well as bifiltered sequences, weight and Hodge filtrations, and it is argued that the torsion part of the cuspidal cohomology is involved in the global anomaly condition. Indeed, in the presence of the cuspidal part, all cohomology classes can be mapped to the boundary of the space and the cuspidal contribution can be involved in the global anomaly condition. (orig.)

  16. Isolation of an oxomanganese(V) porphyrin intermediate in the reaction of a manganese(III) porphyrin complex and H2O2 in aqueous solution.

    Science.gov (United States)

    Nam, Wonwoo; Kim, Inwoo; Lim, Mi Hee; Choi, Hye Jin; Lee, Je Seung; Jang, Ho G

    2002-05-03

    The reaction of [Mn(TF(4)TMAP)](CF(3)SO(3))(5) (TF(4)TMAP=meso-tetrakis(2,3,5,6-tetrafluoro-N,N,N-trimethyl-4-aniliniumyl)porphinato dianion) with H(2)O(2) (2 equiv) at pH 10.5 and 0 degrees C yielded an oxomanganese(V) porphyrin complex 1 in aqueous solution, whereas an oxomanganese(IV) porphyrin complex 2 was generated in the reactions of tert-alkyl hydroperoxides such as tert-butyl hydroperoxide and 2-methyl-1-phenyl-2-propyl hydroperoxide. Complex 1 was capable of epoxidizing olefins and exchanging its oxygen with H(2) (18)O, whereas 2 did not epoxidize olefins. From the reactions of [Mn(TF(4)TMAP)](5+) with various oxidants in the pH range 3-11, the O-O bond cleavage of hydroperoxides was found to be sensitive to the hydroperoxide substituent and the pH of the reaction solution. Whereas the O-O bond of hydroperoxides containing an electron-donating tert-alkyl group is cleaved homolytically, an electron-withdrawing substituent such as an acyl group in m-chloroperoxybenzoic acid (m-CPBA) facilitates O-O bond heterolysis. The mechanism of the O-O bond cleavage of H(2)O(2) depends on the pH of the reaction solution: O-O bond homolysis prevails at low pH and O-O bond heterolysis becomes a predominant pathway at high pH. The effect of pH on (18)O incorporation from H(2) (18)O into oxygenated products was examined over a wide pH range, by carrying out the epoxidation of carbamazepine (CBZ) with [Mn(TF(4)TMAP)](5+) and KHSO(5) in buffered H(2) (18)O solutions. A high proportion of (18)O was incorporated into the CBZ-10,11-oxide product at all pH values but this proportion was not affected significantly by the pH of the reaction solution.

  17. Coordination and structure of Ca(II)-acetate complexes in aqueous solution studied by a combination of Raman and XAFS spectroscopies

    Science.gov (United States)

    Muñoz Noval, Álvaro; Nishio, Daisuke; Kuruma, Takuya; Hayakawa, Shinjiro

    2018-06-01

    The determination of the structure of Ca(II)-acetate in aqueous solution has been addressed by combining Raman and X-ray absorption fine structure spectroscopies. The pH-dependent speciation of the acetate/Ca(II) system has been studied observing modifications in specific Raman bands of the carboxyl group. The current results evidence the Ca(II)-acetate above acetate pKa forms a bidentate complex and presents a coordination 6, in which the Ca-O shell radius decrease of about 0.1 Å with respect the hydrated Ca2+ with coordination 8. The experimental results show the OCO angle of the carboxyl in the complex is close to 124°, being the OCaO angle about 60°.

  18. Reactive oxygen species generation in aqueous solutions containing GdVO4:Eu3+ nanoparticles and their complexes with methylene blue

    Science.gov (United States)

    Hubenko, Kateryna; Yefimova, Svetlana; Tkacheva, Tatyana; Maksimchuk, Pavel; Borovoy, Igor; Klochkov, Vladimir; Kavok, Nataliya; Opolonin, Oleksander; Malyukin, Yuri

    2018-04-01

    It this letter, we report the study of free radicals and reactive oxygen species (ROS) generation in water solutions containing gadolinium orthovanadate GdVO4:Eu3+ nanoparticles (VNPs) and their complexes with methylene blue (MB) photosensitizer. The catalytic activity was studied under UV-Vis and X-ray irradiation by three methods (conjugated dienes test, OH· radical, and singlet oxygen detection). It has been shown that the VNPs-MB complexes reveal high efficiency of ROS generation under UV-Vis irradiation associated with both high efficiency of OH· radicals generation by VNPs and singlet oxygen generation by MB due to nonradiative excitation energy transfer from VNPs to MB molecules. Contrary to that under X-ray irradiation, the strong OH . radicals scavenging by VNPs has been observed.

  19. Photoluminescence and Coordination Behaviour of Lanthanide Complexes of Tris (Aminomethyl)Ethane-5-Oxine in Aqueous Solution.

    Science.gov (United States)

    Akbar, Rifat; Baral, Minati; Kanungo, B K

    2017-01-01

    Photophysical properties of a multidentate tripodal ligand, 5,5'-(2-(((8-hydroxyquinolin-5-yl) methylamino)methyl)-2-methylpropane-1,3-diyl) bis (azanediyl)bis (methylene)diquinolin-8-ol, (TAME5OX), with La 3+ and Er 3+ ions have been examined for photonics applications. The change in behavior in electronic spectra of these complexes reveals the use of TAME5OX as a sensitive optical pH based sensor to detect Ln 3+ ions whereas indication of strong green fluorescence allows simultaneous sensing within the visible region in competitive medium. The intense fluorescence intermittently gets quenched under acidic and basic conditions due to photoinduced intramolecular electron transfer from the excited 8-hydroxyquinoline (8-HQ) moiety to the metal ion. This renders these compounds the OFF-ON-OFF type of pH-dependent fluorescent sensor. The thermodynamic stability and coordination behaviour of the chelator with the said lanthanide ions have also been probed by potentiometric, UV - visible and fluorescence spectrophotometric method. TAME5OX forms protonated complex [Ln (H 4 L)] 4+ below pH ~4.0 which sequentially deprotonates through one proton process with increase of pH. The stability constants of neutral complexes have been determined to be in the range log β 110  = 32-34 and pLn in the range of 14-20, indicating TAME5OX is a good synthetic lanthanide chelator. Theoretical spectra were also calculated by ZINDO/s methodology at single excitations (CIS) level on PM7 as sparkle energy-minimized geometries.

  20. Density functional theory-based prediction of the formation constants of complexes of ammonia in aqueous solution: indications of the role of relativistic effects in the solution chemistry of gold(I).

    Science.gov (United States)

    Hancock, Robert D; Bartolotti, Libero J

    2005-10-03

    A prediction of the formation constants (log K1) for complexes of metal ions with a single NH3 ligand in aqueous solution, using quantum mechanical calculations, is reported. DeltaG values at 298 K in the gas phase for eq 1 (DeltaG(DFT)) were calculated for 34 metal ions using density functional theory (DFT), with the expectation that these would correlate with the free energy of complex formation in aqueous solution (DeltaG(aq)). [M(H2O)6]n+(g) + NH(3)(g) = [M(H2O)5NH3]n+(g) + H2O(g) (eq 1). The DeltaG(aq) values include the effects of complex changes in solvation on complex formation, which are not included in eq 1. It was anticipated that such changes in solvation would be constant or vary systematically with changes in the log K(1) value for different metal ions; therefore, simple correlations between DeltaG(DFT) and DeltaG(aq) were sought. The bulk of the log K1(NH3) values used to calculate DeltaG(aq) were not experimental, but estimated previously (Hancock 1978, 1980) from a variety of empirical correlations. Separate linear correlations between DeltaG(DFT) and DeltaG(aq) for metal ions of different charges (M2+, M3+, and M4+) were found. In plots of DeltaG(DFT) versus DeltaG(aq), the slopes ranged from 2.201 for M2+ ions down to 1.076 for M4+ ions, with intercepts increasing from M2+ to M4+ ions. Two separate correlations occurred for the M3+ ions, which appeared to correspond to small metal ions with a coordination number (CN) of 6 and to large metal ions with a higher CN in the vicinity of 7-9. The good correlation coefficients (R) in the range of 0.97-0.99 for all these separate correlations suggest that the approach used here may be the basis for future predictions of aqueous phase chemistry that would otherwise be experimentally inaccessible. Thus, the log K1(NH3) value for the transuranic Lr3+, which has a half-life of 3.6 h in its most stable isotope, is predicted to be 1.46. These calculations should also lead to a greater insight into the factors

  1. A surface complexation model of YREE sorption on Ulva lactuca in 0.05-5.0 M NaCl solutions

    Science.gov (United States)

    Zoll, Alison M.; Schijf, Johan

    2012-11-01

    We present distribution coefficients, log iKS, for the sorption of yttrium and the rare earth elements (YREEs) on BCR-279, a dehydrated tissue homogenate of a marine macroalga, Ulva lactuca, resembling materials featured in chemical engineering studies aimed at designing renewable biosorbents. Sorption experiments were conducted in NaCl solutions of different ionic strength (0.05, 0.5, and 5.0 M) at T = 25 °C over the pH range 2.7-8.5. Distribution coefficients based on separation of the dissolved and particulate phase by conventional filtration (3 kDa) using an existing pH-dependent model. Colloid-corrected values were renormalized to free-cation concentrations by accounting for YREE hydrolysis and chloride complexation. At each ionic strength, the pH dependence of the renormalized values is accurately described with a non-electrostatic surface complexation model (SCM) that incorporates YREE binding to three monoprotic functional groups, previously characterized by alkalimetric titration, as well as binding of YREE-hydroxide complexes (MOH2+) to the least acidic one (pKa ∼ 9.5). In non-linear regressions of the distribution coefficients as a function of pH, each pKa was fixed at its reported value, while stability constants of the four YREE surface complexes were used as adjustable parameters. Data for a single fresh U. lactuca specimen in 0.5 M NaCl show generally the same pH-dependent behavior but a lower degree of sorption and were excluded from the regressions. Good linear free-energy relations (LFERs) between stability constants of the YREE-acetate and YREE-hydroxide solution complex and surface complexes with the first and third functional group, respectively, support their prior tentative identifications as carboxyl and phenol. A similar confirmation for the second group is precluded by insufficient knowledge of the stability of YREE-phosphate complexes and a perceived lack of YREE binding in 0.05 M NaCl; this issue awaits further study. The results

  2. Multi-disciplinary engineering for cyber-physical production systems data models and software solutions for handling complex engineering projects

    CERN Document Server

    Lüder, Arndt; Gerhard, Detlef

    2017-01-01

    This book discusses challenges and solutions for the required information processing and management within the context of multi-disciplinary engineering of production systems. The authors consider methods, architectures, and technologies applicable in use cases according to the viewpoints of product engineering and production system engineering, and regarding the triangle of (1) product to be produced by a (2) production process executed on (3) a production system resource. With this book industrial production systems engineering researchers will get a better understanding of the challenges and requirements of multi-disciplinary engineering that will guide them in future research and development activities. Engineers and managers from engineering domains will be able to get a better understanding of the benefits and limitations of applicable methods, architectures, and technologies for selected use cases. IT researchers will be enabled to identify research issues related to the development of new methods, arc...

  3. Direct and indirect photodegradation of estriol in the presence of humic acid, nitrate and iron complexes in water solutions

    Energy Technology Data Exchange (ETDEWEB)

    Chen, Yong [Department of Chemistry and Biochemistry, University of Massachusetts Dartmouth, North Dartmouth, MA 02747 (United States); School of Environmental Science and Engineering, Huazhong University of Science and Technology, Wuhan 430074 (China); Zhang, Kai [Department of Chemistry and Biochemistry, University of Massachusetts Dartmouth, North Dartmouth, MA 02747 (United States); Zuo, Yuegang, E-mail: yzuo@umassd.edu [Department of Chemistry and Biochemistry, University of Massachusetts Dartmouth, North Dartmouth, MA 02747 (United States)

    2013-10-01

    The photochemical behavior of a natural estrogen estriol (E3) was investigated in the presence of the natural photoreactive constituents including nitrate, iron(III), and humic acid (HA). The direct photodegradation of E3 increased with increasing incident light intensity, decreasing initial concentration of E3 and increasing pH in the range of 6.0 to 10.0. The direct photodegradation of the deprotonated speciation of E3 was much faster than that of its protonated form. The presence of NO{sub 3}{sup −} and iron(III) promoted the photochemical loss of E3 in the aqueous solutions. The quenching experiments verified that hydroxyl radicals were predominantly responsible for the indirect photodegradation of E3. HA could act as photosensitizer, light screening agent and free radical quencher. For the first time, the enhancement or inhibition effect of HA on photodegradation was found to depend on the irradiation light intensity. HA enhanced the photodegradation of E3 under sunlight or weak irradiation of simulated sunlight. In contrast, under high irradiation light intensity, HA inhibited the photodegradation. The hydroxylation photoproducts were identified using GC-MS and the photodegradation pathway of E3 was proposed. - Highlights: • Direct and indirect photodegradation of estriol (E3) were first investigated. • The direct photodegradation of E3 increased with increasing pH of the solutions. • The light intensity affected the photosensitization effect of humic acid. • Nitrate and iron(III) promoted the photodecomposition of estriol in water. • The ·OH oxidation products of E3 was first determined.

  4. Complexes of Escherichia coli adenylate kinase and nucleotides: 1H NMR studies of the nucleotide sites in solution

    International Nuclear Information System (INIS)

    Vetter, I.R.; Reinstein, J.; Roesch, P.

    1990-01-01

    One- and two-dimensional nuclear magnetic resonance (NMR) studies, in particular substrate-protein nuclear Overhauser effect (NOESY) measurements, as well as nucleotide and P 1 ,P 5 -bis-(5'-adenosyl) pentaphosphate (AP 5 A) titrations and studies of the temperature-dependent unfolding of the tertiary structure of Escherichia coli adenylate kinase (AK EC ) were performed. These experiments and comparison with the same type of experiments performed with the porcine enzyme led them to the following conclusions: (1) at pH 8 and concentrations of approximately 2.5-3 mM, AK EC is partially unfolded at 318 K; (2) ATP·Mg 2+ binds to the ATP site with a dissociation constant of approximately 40 μM under the assumption that ATP binds to one nucleotide site only; (3) AP 5 A·Mg 2+ binds to both nucleotide sites and thus simulates the active complex; (4) the ATP·Mg 2+ adenine in the AK EC ·AP 5 A·Mg 2+ complex is located close to His 134 and Phe 19 ; (5) the AK EC G-loop with bound ATP·Mg 2+ is structurally highly homologous to the loop region in the oncogene product p21 with bound GTP·Mg 2+

  5. Use of frontal analysis in ion exchange chromatography for the study of reactions of formation of complexes in solution. Application to hydrochloric complexes of nickel (II), cobalt (II) and copper (II)

    International Nuclear Information System (INIS)

    Tremillon, Bernard

    1959-01-01

    The ion exchanger column frontal analysis method provides a convenient way to study complex formation reactions when they are very unstable. It has the advantage of being much more sensitive and precise than the method (already used by other authors) of simple equilibrium between a solution and an ion exchanger. As an illustration of this method, the hydrochloric acid complexes NiCl + , CoCl + and CuCl + , have been studied, and their dissociation constants were determined (respectively 4.6 ± 0.1; 4.0 ± 0.1 and 2.5 ± 0.1, at an ionic strength substantially equal to 1.5). Reprint of a paper published in Bulletin de la Societe Chimique de France, 1958, p. 1483-1487 [fr

  6. Exploration of spectroscopic properties of solvated tris(thenoyltrifluoroacetonate)(2,2′-bipyridine)europium(III)red hybrid organic complex for solution processed OLEDs and displays

    Energy Technology Data Exchange (ETDEWEB)

    Chitnis, Dipti [Department of Physics, RTM Nagpur University, Nagpur 440033 (India); Thejokalyani, N., E-mail: thejokalyani@rediffmail.com [Department of Applied Physics, Laxminarayan Institute of Technology, Nagpur 440033 (India); Dhoble, S.J. [Department of Physics, RTM Nagpur University, Nagpur 440033 (India)

    2017-05-15

    In order to explore the spectroscopic properties of a novel europium activated hybrid organic tris(thenoyltrifluoroacetonate)(2,2′-bipyridine)europium(III), Eu(TTA){sub 3}bipy phosphor in various solvents at different pH and molar concentrations, UV–vis optical absorption and photoluminescence spectra were carried out. With a variation in the solvent from basic (chloroform, toluene, tetrahydrofuran) to acidic (acetic acid, formic acid) media, staggering differences in optical absorptions and optical densities were noticed with hypsochromic shift in the absorption peaks. The optical density was found to be maximum for the complex with pH= 7.0 and the intensity as well as optical density gradually decreased when pH is lowered to 6.0 or raised to 8.0 (at an interval of 0.5), proving that the complex is pH sensitive. It's optical energy gap and stokes shift values in various organic solvents were also calculated on the basis of Lippert-Mataga plot. The exploration of spectroscopic properties of solvated Eu(TTA){sub 3}bipy complex demonstrates its prospective for solution processed OLEDs and display devices. - Graphical abstract: Pictorial depiction of photoluminescence in solvated Eu(TTA){sub 3}bipy complex under UV light.

  7. The formation of amino acid and dipeptide complexes with α-cyclodextrin and cucurbit[6]uril in aqueous solutions studied by titration calorimetry

    International Nuclear Information System (INIS)

    Buschmann, H.-J.; Schollmeyer, E.; Mutihac, L.

    2003-01-01

    The complex stabilities and the thermodynamic data for the complexation of α-cyclodextrin and cucurbit[6]uril with some amino acids (glycine, L-alanine, L-valine, L-phenylalanine, 6-amino hexanoic acid, 8-amino octanoic acid, 11-amino undecanoic acid) and dipeptides (glycyl-glycine, glycyl-L-valine, glycyl-L-leucine and glycyl-L-phenylalanine) have been determined in aqueous solution by calorimetric titrations. The complex formation with α-cyclodextrin is mainly favoured by entropic contributions due to the release of water molecules from the cavity of the ligand. The values of the reaction enthalpies are small with the exception of 11-amino undecanoic acid. In case of the ligand cucurbit[6]uril, ion-dipole interactions between the protonated amino groups of the amino acids and the carbonyl groups take place. By steric reasons these interactions are lowered for native amino acids because the polar carboxylic groups are always located outside the hydrophobic cavity of cucurbit[6]uril. The complexes of both ligands with dipeptides in water are characterised by hydrophobic interactions and in case of cucurbit[6]uril by additional ion-dipole interactions

  8. Exploration of spectroscopic properties of solvated tris(thenoyltrifluoroacetonate)(2,2′-bipyridine)europium(III)red hybrid organic complex for solution processed OLEDs and displays

    International Nuclear Information System (INIS)

    Chitnis, Dipti; Thejokalyani, N.; Dhoble, S.J.

    2017-01-01

    In order to explore the spectroscopic properties of a novel europium activated hybrid organic tris(thenoyltrifluoroacetonate)(2,2′-bipyridine)europium(III), Eu(TTA) 3 bipy phosphor in various solvents at different pH and molar concentrations, UV–vis optical absorption and photoluminescence spectra were carried out. With a variation in the solvent from basic (chloroform, toluene, tetrahydrofuran) to acidic (acetic acid, formic acid) media, staggering differences in optical absorptions and optical densities were noticed with hypsochromic shift in the absorption peaks. The optical density was found to be maximum for the complex with pH= 7.0 and the intensity as well as optical density gradually decreased when pH is lowered to 6.0 or raised to 8.0 (at an interval of 0.5), proving that the complex is pH sensitive. It's optical energy gap and stokes shift values in various organic solvents were also calculated on the basis of Lippert-Mataga plot. The exploration of spectroscopic properties of solvated Eu(TTA) 3 bipy complex demonstrates its prospective for solution processed OLEDs and display devices. - Graphical abstract: Pictorial depiction of photoluminescence in solvated Eu(TTA) 3 bipy complex under UV light.

  9. Effective As(III) Removal by A Multi-Charged Hydroacid Complex Draw Solute Facilitated Forward Osmosis-Membrane Distillation (FO-MD) Processes

    KAUST Repository

    Ge, Qingchun; Han, Gang; Chung, Neal Tai-Shung

    2016-01-01

    © 2016 American Chemical Society. Effective removal of As(III) from water by an oxalic acid complex with the formula of Na3[Cr(C2O4)3] (Na-Cr-OA) is demonstrated via an forward osmosis-membrane distillation (FO-MD) hybrid system in this study. Na-Cr-OA first proved its superiority as a draw solute with high water fluxes and negligible reverse fluxes in FO, then a systematic investigation of the Na-Cr-OA promoted FO process was conducted to ascertain the factors in As(III) removal. Relatively high water fluxes of 28 LMH under the FO mode and 74 LMH under the pressure retarded osmosis (PRO) mode were achieved when using a 1000 ppm As(III) solution as the feed and 1.0 M Na-Cr-OA as the draw solution at 60 °C. As(III) removal with a water recovery up to 21.6% (FO mode) and 48.3% (PRO mode) were also achieved in 2 h. An outstanding As(III) rejection with 30-3000 μg/L As(III) in the permeate was accomplished when As(III) feed solutions varied from 5 × 104 to 1 × 106 μg/L, superior to the best FO performance reported for As(III) removal. Incorporating MD into FO not only makes As(III) removal sustainable by reconcentrating the Na-Cr-OA solution simultaneously, but also reduces the As(III) concentration below 10 μg/L in the product water, meeting the WHO standard.

  10. Effective As(III) Removal by A Multi-Charged Hydroacid Complex Draw Solute Facilitated Forward Osmosis-Membrane Distillation (FO-MD) Processes.

    Science.gov (United States)

    Ge, Qingchun; Han, Gang; Chung, Tai-Shung

    2016-03-01

    Effective removal of As(III) from water by an oxalic acid complex with the formula of Na3[Cr(C2O4)3] (Na-Cr-OA) is demonstrated via an forward osmosis-membrane distillation (FO-MD) hybrid system in this study. Na-Cr-OA first proved its superiority as a draw solute with high water fluxes and negligible reverse fluxes in FO, then a systematic investigation of the Na-Cr-OA promoted FO process was conducted to ascertain the factors in As(III) removal. Relatively high water fluxes of 28 LMH under the FO mode and 74 LMH under the pressure retarded osmosis (PRO) mode were achieved when using a 1000 ppm As(III) solution as the feed and 1.0 M Na-Cr-OA as the draw solution at 60 °C. As(III) removal with a water recovery up to 21.6% (FO mode) and 48.3% (PRO mode) were also achieved in 2 h. An outstanding As(III) rejection with 30-3000 μg/L As(III) in the permeate was accomplished when As(III) feed solutions varied from 5 × 10(4) to 1 × 10(6) μg/L, superior to the best FO performance reported for As(III) removal. Incorporating MD into FO not only makes As(III) removal sustainable by reconcentrating the Na-Cr-OA solution simultaneously, but also reduces the As(III) concentration below 10 μg/L in the product water, meeting the WHO standard.

  11. Effective As(III) Removal by A Multi-Charged Hydroacid Complex Draw Solute Facilitated Forward Osmosis-Membrane Distillation (FO-MD) Processes

    KAUST Repository

    Ge, Qingchun

    2016-01-29

    © 2016 American Chemical Society. Effective removal of As(III) from water by an oxalic acid complex with the formula of Na3[Cr(C2O4)3] (Na-Cr-OA) is demonstrated via an forward osmosis-membrane distillation (FO-MD) hybrid system in this study. Na-Cr-OA first proved its superiority as a draw solute with high water fluxes and negligible reverse fluxes in FO, then a systematic investigation of the Na-Cr-OA promoted FO process was conducted to ascertain the factors in As(III) removal. Relatively high water fluxes of 28 LMH under the FO mode and 74 LMH under the pressure retarded osmosis (PRO) mode were achieved when using a 1000 ppm As(III) solution as the feed and 1.0 M Na-Cr-OA as the draw solution at 60 °C. As(III) removal with a water recovery up to 21.6% (FO mode) and 48.3% (PRO mode) were also achieved in 2 h. An outstanding As(III) rejection with 30-3000 μg/L As(III) in the permeate was accomplished when As(III) feed solutions varied from 5 × 104 to 1 × 106 μg/L, superior to the best FO performance reported for As(III) removal. Incorporating MD into FO not only makes As(III) removal sustainable by reconcentrating the Na-Cr-OA solution simultaneously, but also reduces the As(III) concentration below 10 μg/L in the product water, meeting the WHO standard.

  12. Design of future municipal wastewater treatment plants: A mathematical approach to manage complexity and identify optimal solutions

    DEFF Research Database (Denmark)

    Bozkurt, Hande; Quaglia, Alberto; Gernaey, Krist

    The increasing number of alternative wastewater treatment (WWT) technologies and stricter effluent requirements imposed by regulations make the early stage decision making for WWTP layout design, which is currently based on expert decisions and previous experiences, much harder. This paper...... therefore proposes a new approach based on mathematical programming to manage the complexity of the problem and generate/identify novel and optimal WWTP layouts for municipal/domestic wastewater treatment. Towards this end, after developing a database consisting of primary, secondary and tertiary WWT...... solved to obtain the optimal WWT network and the optimal wastewater and sludge flow through the network. The tool is evaluated on a case study, which was chosen as the Benchmark Simulation Model no.1 (BSM1) and many retrofitting options for obtaining a cost-effective treatment were investigated...

  13. Thermodynamics of complexes formation by ITC in methanol/water = 9/1 (v/v) solution: A case study

    Energy Technology Data Exchange (ETDEWEB)

    Fisicaro, Emilia, E-mail: emilia.fisicaro@unipr.it [University of Parma, Department of Pharmacy, Parco Area delle Scienze, 27/A, 43124 Parma (Italy); Compari, Carlotta; Bacciottini, Franco; Contardi, Laura [University of Parma, Department of Pharmacy, Parco Area delle Scienze, 27/A, 43124 Parma (Italy); Carcelli, Mauro; Rispoli, Gabriele; Rogolino, Dominga [University of Parma, Department of Chemistry, Parco Area delle Scienze, 17/A, 43124 Parma (Italy)

    2014-06-01

    Graphical abstract: Integrase strand transfert inhibitors chelate the metal ions in the active site of HIV integrase. - Highlights: • Development of inhibitors acting against those viral enzymes operating via a cooperative two-metal ion mechanism, such as HIV integrase (IN), requires optimizing the binding affinity to the target. • We have defined an experimental procedure for obtaining reliable thermodynamic data by ITC in methanol/water = 9/1 (v/v) as solvent. • Formation heats in mixed solvent of the complexes formed by a ligand, model of Raltegravir, with Mg(II), Mn(II), Co(II) and Zn(II) are here reported. - Abstract: Most enzymes that participate in the biochemistry of nucleic acids require divalent metal ion cofactors to promote activity. Development of potent inhibitors, acting against those viral enzymes operating via a cooperative two-metal ion mechanism, such as HIV integrase (IN) and RNase H, hepatitis C virus polymerase and influenza endonuclease, requires optimizing the binding affinity to the target, which is dictated by the binding free energy composed of both enthalpic and entropic contributions. They can be obtained by using isothermal titration microcalorimetry. We have defined an experimental procedure for obtaining reliable thermodynamic data in methanol/water = 9/1 0.1 M KCl as solvent, used to overcome solubility problems. In this way we have measured the heats of formation of the complexes formed by N-(4-fluorobenzyl)-5-hydroxy-2-isopropyl-1-methyl-6-oxo-1, 6-dihydroxypyrimidine-4-carboxylate (HL, a model of Raltegravir, the antiretroviral drug produced by Merck and Co.), and a series of divalent metal ions of biological interest (Mg(II), Mn(II), Co(II) and Zn(II)), whose speciation was previously determined by potentiometry.

  14. Thermodynamics of inclusion complexes of natural and modified cyclodextrins with acetylsalicylic acid and ibuprofen in aqueous solution at 298 K

    Energy Technology Data Exchange (ETDEWEB)

    Castronuovo, Giuseppina, E-mail: giuseppina.castronuovo@unina.it [Department of Chemistry, University Federico II of Naples, Complesso Universitario a Monte S. Angelo, via Cintia, 80126 Naples (Italy); Niccoli, Marcella [Department of Chemistry, University Federico II of Naples, Complesso Universitario a Monte S. Angelo, via Cintia, 80126 Naples (Italy)

    2013-04-10

    Graphical abstract: Complexation forces acting in the association between natural and modified α- and β-cyclodextrins and acetylsalicylic acid (aspirin) or ibuprofen are examined through the analysis of the thermodynamic parameters obtained by isothermal calorimetry. Highlights: ► A calorimetric method is reported to study the association of natural and substituted cyclodextrins with acetylsalicylic acid and ibuprofen. ► The study aims to propose a hypothesis about the forces involved in the interaction. That can be useful for designing new cyclodextrins having suitable characteristics to include specific drugs. ► Enthalpic and entropic contributions on the association are discussed. The differences in the cavity dimensions of the cyclodextrins determine the values of the thermodynamic properties to be very different. - Abstract: Thermodynamic parameters for the association of natural and substituted α-, β-, and γ-cyclodextrins with acetylsalicylic acid, salicylic acid and ibuprofen have been determined by isothermal titration calorimetry. Analysis of the data shows that complexes form, all having 1:1 stoichiometry. The shape-matching between the host and guest is the factor determining the values of the thermodynamic quantities. In the case of the smallest cyclodextrin interacting with acetylsalicylic acid and salicylic acid, the parameters indicate that hydrophobic interactions play the major role. Association occurs through the shallow inclusion of the benzene ring into the cavity. In the case of substituted β-cyclodextrins, instead, inclusion of the benzene ring is deeper and the tight fitting of the guest molecule to the cavity makes the enthalpy and entropy to be both negative. Ibuprofen interacts through its isobutyl group: the values of the association constants are very high for β-cyclodextrins as determined by the large and positive entropies due to the relaxation of water molecules from the cavity and the hydration spheres of the interacting

  15. Thermodynamics of inclusion complexes of natural and modified cyclodextrins with acetylsalicylic acid and ibuprofen in aqueous solution at 298 K

    International Nuclear Information System (INIS)

    Castronuovo, Giuseppina; Niccoli, Marcella

    2013-01-01

    Graphical abstract: Complexation forces acting in the association between natural and modified α- and β-cyclodextrins and acetylsalicylic acid (aspirin) or ibuprofen are examined through the analysis of the thermodynamic parameters obtained by isothermal calorimetry. Highlights: ► A calorimetric method is reported to study the association of natural and substituted cyclodextrins with acetylsalicylic acid and ibuprofen. ► The study aims to propose a hypothesis about the forces involved in the interaction. That can be useful for designing new cyclodextrins having suitable characteristics to include specific drugs. ► Enthalpic and entropic contributions on the association are discussed. The differences in the cavity dimensions of the cyclodextrins determine the values of the thermodynamic properties to be very different. - Abstract: Thermodynamic parameters for the association of natural and substituted α-, β-, and γ-cyclodextrins with acetylsalicylic acid, salicylic acid and ibuprofen have been determined by isothermal titration calorimetry. Analysis of the data shows that complexes form, all having 1:1 stoichiometry. The shape-matching between the host and guest is the factor determining the values of the thermodynamic quantities. In the case of the smallest cyclodextrin interacting with acetylsalicylic acid and salicylic acid, the parameters indicate that hydrophobic interactions play the major role. Association occurs through the shallow inclusion of the benzene ring into the cavity. In the case of substituted β-cyclodextrins, instead, inclusion of the benzene ring is deeper and the tight fitting of the guest molecule to the cavity makes the enthalpy and entropy to be both negative. Ibuprofen interacts through its isobutyl group: the values of the association constants are very high for β-cyclodextrins as determined by the large and positive entropies due to the relaxation of water molecules from the cavity and the hydration spheres of the interacting

  16. Engineering Education as a Complex System

    Science.gov (United States)

    Gattie, David K.; Kellam, Nadia N.; Schramski, John R.; Walther, Joachim

    2011-01-01

    This paper presents a theoretical basis for cultivating engineering education as a complex system that will prepare students to think critically and make decisions with regard to poorly understood, ill-structured issues. Integral to this theoretical basis is a solution space construct developed and presented as a benchmark for evaluating…

  17. Semi-mechanistic partial buffer approach to modeling pH, the buffer properties, and the distribution of ionic species in complex solutions.

    Science.gov (United States)

    Dougherty, Daniel P; Da Conceicao Neta, Edith Ramos; McFeeters, Roger F; Lubkin, Sharon R; Breidt, Frederick

    2006-08-09

    In many biological science and food processing applications, it is very important to control or modify pH. However, the complex, unknown composition of biological media and foods often limits the utility of purely theoretical approaches to modeling pH and calculating the distributions of ionizable species. This paper provides general formulas and efficient algorithms for predicting the pH, titration, ionic species concentrations, buffer capacity, and ionic strength of buffer solutions containing both defined and undefined components. A flexible, semi-mechanistic, partial buffering (SMPB) approach is presented that uses local polynomial regression to model the buffering influence of complex or undefined components in a solution, while identified components of known concentration are modeled using expressions based on extensions of the standard acid-base theory. The SMPB method is implemented in a freeware package, (pH)Tools, for use with Matlab. We validated the predictive accuracy of these methods by using strong acid titrations of cucumber slurries to predict the amount of a weak acid required to adjust pH to selected target values.

  18. Aluminium-27 n.m.r. studies of aluminium fluoro complexes in dichloromethane solution: evidence for tetrafluoroaluminate anion

    International Nuclear Information System (INIS)

    Colton, R.; Eller, P.G.

    1989-01-01

    Mixed aluminium chloro/fluoro anions are formed in dichloromethane solution by the interaction of AlCl 3 and [Ph 3 PhCH 2 P] [H 2 F 3 ]. Aluminium-27 n.m.r. studies are restricted to the stoichiometric ranges F/Al from 1:1 to 3:1 and F/Al>8:1. Between these limits rapid precipitation reactions occur. In the fluoride-rich stoichiometric range there is rapid exchange on the n.m.r. time scale between the aluminium fluoro anion and free fluoride, so that a direct identification of the species by the multiplicity of the resonance is not possible. Indirect evidence strongly suggests that the aluminium species is [AlF 4 ] - . In the F/Al stoichiometry range from 1:1 to 3:1 aluminium-27 resonances were observed for all the other possible [AlCl χ F 4-χ ] - species. Studies on the aluminium iodo/fluoro system support the identification of [AlF 4 ] - , but the system is labile and the mixed iodo/fluoro species undergo rapid disproportionation. 12 refs., 1 fig

  19. Adsorption of Rh(III) complexes from chloride solutions obtained by leaching chlorinated spent automotive catalysts on ion-exchange resin Diaion WA21J

    International Nuclear Information System (INIS)

    Shen Shaobo; Pan Tonglin; Liu Xinqiang; Yuan Lei; Wang Jinchao; Zhang Yongjian; Guo Zhanchen

    2010-01-01

    It was found that Rh, Pd and Pt contained in the spent ceramic automotive catalysts could be effectively extracted by dry chlorination with chlorine. In order to concentrate Rh(III) ions contained in the chloride solutions obtained, thermodynamic and kinetics studies for adsorption of Rh(III) complexes from the chloride solutions on an anionic exchange resin Diaion WA21J were carried out. Rh, Pd, Pt, Al, Fe, Si, Zn and Pb from the chloride solution could be adsorbed on the resin. The distribution coefficients (K d ) of Rh(III) decreased with the increase in initial Rh(III) concentration or in adsorption temperature. The isothermal adsorption of Rh(III) was found to fit Langmuir, Freundlich and Dubinin-Kaganer-Radushkevich models under the adsorption conditions. The maximum monolayer adsorption capacities Q max based on Langmuir adsorption isotherms were 6.39, 6.61 and 5.81 mg/g for temperatures 18, 28 and 40 deg. C, respectively. The apparent adsorption energy of Rh was about -7.6 kJ/mol and thus Rh(III) adsorption was a physical type. The experimental data obtained could be better simulated by pseudo-first-order kinetic model and the activation energy obtained was 6.54 J/mol. The adsorption rate of Rh(III) was controlled by intraparticle diffusion in most of time of adsorption process.

  20. Solution NMR characterization of magnetic/electronic properties of azide and cyanide-inhibited substrate complexes of human heme oxygenase: implications for steric ligand tilt.

    Science.gov (United States)

    Peng, Dungeng; Ogura, Hiroshi; Ma, Li-Hua; Evans, John P; de Montellano, Paul R Ortiz; La Mar, Gerd N

    2013-04-01

    Solution 2D (1)H NMR was carried out on the azide-ligated substrate complex of human heme oxygenase, hHO, to provide information on the active site molecular structure, chromophore electronic/magnetic properties, and the distal H-bond network linked to the exogenous ligand by catalytically relevant oriented water molecules. While 2D NMR exhibited very similar patterns of two-dimensional nuclear Overhauser spectroscopy cross peaks of residues with substrate and among residues as the previously characterized cyanide complex, significant, broadly distributed chemical shift differences were observed for both labile and non-labile protons. The anisotropy and orientation of the paramagnetic susceptibility tensor, χ, were determined for both the azide and cyanide complexes. The most significant difference observed is the tilt of the major magnetic axes from the heme normal, which is only half as large for the azide than cyanide ligand, with each ligand tilted toward the catalytically cleaved α-meso position. The difference in chemical shifts is quantitatively correlated with differences in dipolar shifts in the respective complexes for all but the distal helix. The necessity of considering dipolar shifts, and hence determination of the orientation/anisotropy of χ, in comparing chemical shifts involving paramagnetic complexes, is emphasized. The analysis shows that the H-bond network cannot detect significant differences in H-bond acceptor properties of cyanide versus azide ligands. Lastly, significant retardation of distal helix labile proton exchange upon replacing cyanide with azide indicates that the dynamic stability of the distal helix is increased upon decreasing the steric interaction of the ligand with the distal helix. Copyright © 2013. Published by Elsevier Inc.

  1. Stability constants of the fluoride complexes of actinides in aqueous solution and their correlation with fundamental properties

    International Nuclear Information System (INIS)

    Chaudhuri, N.K.; Sawant, R.M.

    1997-09-01

    Stability constants of the fluoride complexes of the actinides in different oxidation states measured by potentiometric method using fluoride ion selective electrode have been presented. Procedure and precautions required to overcome certain difficulties particular to actinide ions have been discussed. Literature data from various sources have been compiled. In order to have a reasonable comparison the stability constant (β 1 ) values obtained in diverse ionic strength media are converted to thermodynamic stability constant, β 1 0 , using Davies equation (a modification of Debye-Huckel equation). A correlation of the β 1 0 values with the fundamental properties of the actinide ions using various models available in the literature has been attempted. A semiempirical relation recently developed by Brown, Sylva and Ellis (BSE equation) appears to be most suitable. Using the values of ionic radii and best available values of the stability constants of a large number of metal ions from recent compilations a comparative study of the various models or relations available in the literature has been tried. For metal ions in general, the best correlation is obtained with the BSE equation. In an attempt to accommodate the unusual trend in the stability constants of the tetravalent actinides a modification in a parameter of the BSE equation has been proposed. Good agreement between the theoretically calculated and experimentally determined values for actinides in different oxidation states is then obtained in most of the cases. (author)

  2. Attention-deficit hyperactivity disorder (ADHD), substance use disorders, and criminality: a difficult problem with complex solutions.

    Science.gov (United States)

    Knecht, Carlos; de Alvaro, Raquel; Martinez-Raga, Jose; Balanza-Martinez, Vicent

    2015-05-01

    The association between attention-deficit hyperactivity disorder (ADHD) and criminality has been increasingly recognized as an important societal concern. Studies conducted in different settings have revealed high rates of ADHD among adolescent offenders. The risk for criminal behavior among individuals with ADHD is increased when there is psychiatric comorbidity, particularly conduct disorder and substance use disorder. In the present report, it is aimed to systematically review the literature on the epidemiological, neurobiological, and other risk factors contributing to this association, as well as the key aspects of the assessment, diagnosis, and treatment of ADHD among offenders. A systematic literature search of electronic databases (PubMed, EMBASE, and PsycINFO) was conducted to identify potentially relevant studies published in English, in peer-reviewed journals. Studies conducted in various settings within the judicial system and in many different countries suggest that the rate of adolescent and adult inmates with ADHD far exceeds that reported in the general population; however, underdiagnosis is common. Similarly, follow-up studies of children with ADHD have revealed high rates of criminal behaviors, arrests, convictions, and imprisonment in adolescence and adulthood. Assessment of ADHD and comorbid condition requires an ongoing and careful process. When treating offenders or inmates with ADHD, who commonly present other comorbid psychiatric disorder complex, comprehensive and tailored interventions, combining pharmacological and psychosocial strategies are likely to be needed.

  3. Crystal and solution structures of an odorant-binding protein from the southern house mosquito complexed with an oviposition pheromone

    Energy Technology Data Exchange (ETDEWEB)

    Mao, Yang; Xu, Xianzhong; Xu, Wei; Ishida, Yuko; Leal, Walter S.; Ames, James B.; Clardy, Jon (Harvard-Med); (UCD)

    2010-11-15

    Culex mosquitoes introduce the pathogens responsible for filariasis, West Nile virus, St. Louis encephalitis, and other diseases into humans. Currently, traps baited with oviposition semiochemicals play an important role in detection efforts and could provide an environmentally friendly approach to controlling their populations. The odorant binding proteins (OBPs) in the female's antenna play a crucial, if yet imperfectly understood, role in sensing oviposition cues. Here, we report the X-ray crystallography and NMR 3D structures of OBP1 for Culex quinquefasciatus (CquiOBP1) bound to an oviposition pheromone (5R,6S)-6-acetoxy-5-hexadecanolide (MOP). In both studies, CquiOBP1 had the same overall six-helix structure seen in other insect OBPs, but a detailed analysis revealed an important previously undescribed feature. There are two models for OBP-mediated signal transduction: (i) direct release of the pheromone from an internal binding pocket in a pH-dependent fashion and (ii) detection of a pheromone-induced conformational change in the OBP {center_dot} pheromone complex. Although CquiOBP1 binds MOP in a pH-dependent fashion, it lacks the C terminus required for the pH-dependent release model. This study shows that CquiOBP binds MOP in an unprecedented fashion using both a small central cavity for the lactone head group and a long hydrophobic channel for its tail.

  4. A Solution to Modeling Multilevel Confirmatory Factor Analysis with Data Obtained from Complex Survey Sampling to Avoid Conflated Parameter Estimates

    Directory of Open Access Journals (Sweden)

    Jiun-Yu Wu

    2017-09-01

    Full Text Available The issue of equality in the between-and within-level structures in Multilevel Confirmatory Factor Analysis (MCFA models has been influential for obtaining unbiased parameter estimates and statistical inferences. A commonly seen condition is the inequality of factor loadings under equal level-varying structures. With mathematical investigation and Monte Carlo simulation, this study compared the robustness of five statistical models including two model-based (a true and a mis-specified models, one design-based, and two maximum models (two models where the full rank of variance-covariance matrix is estimated in between level and within level, respectively in analyzing complex survey measurement data with level-varying factor loadings. The empirical data of 120 3rd graders' (from 40 classrooms perceived Harter competence scale were modeled using MCFA and the parameter estimates were used as true parameters to perform the Monte Carlo simulation study. Results showed maximum models was robust to unequal factor loadings while the design-based and the miss-specified model-based approaches produced conflated results and spurious statistical inferences. We recommend the use of maximum models if researchers have limited information about the pattern of factor loadings and measurement structures. Measurement models are key components of Structural Equation Modeling (SEM; therefore, the findings can be generalized to multilevel SEM and CFA models. Mplus codes are provided for maximum models and other analytical models.

  5. Aggregation and metal-complexation behaviour of THPP porphyrin in ethanol/water solutions as function of pH

    Science.gov (United States)

    Zannotti, Marco; Giovannetti, Rita; Minofar, Babak; Řeha, David; Plačková, Lydie; D'Amato, Chiara A.; Rommozzi, Elena; Dudko, Hanna V.; Kari, Nuerguli; Minicucci, Marco

    2018-03-01

    The effect of pH change on 5,10,15,20-Tetrakis(4-hydroxyphenyl)-21H,23H-porphine (THPP) with its aggregation as function of water-ethanol mixture was studied with UV-vis, fluorescence, Raman and computational analysis. In neutral pH, THPP was present as free-base and, increasing the water amount, aggregation occurred with the formation of H- and J-aggregates. The aggregation constant and the concentration of dimers were calculated, other information about the dimer aggregation were evaluated by computational study. In acidic pH, by the insertions of two hydrogens in the porphyrin rings, the porphyrin changed its geometry with a ring deformation confirmed by red-shifted spectrum and quenching in fluorescence; at this low pH, increasing the water amount, the acidic form (THPPH2)2 + resulted more stable due to a polar environment with stronger interaction by hydrogen bonding. In basic pH, reached by NH4OH, THPP porphyrin was able to react with alkali metals in order to form sitting-atop complex (M2THPP) confirmed by the typical absorption spectrum of metallo-porphyrin, Raman spectroscopy and by computational analysis.

  6. Savings for the Poor

    OpenAIRE

    Ignacio Mas

    2010-01-01

    This paper reviews the relevance of formal financial services – in particular, savings – to poor people, the economic factors that have hindered the mass-scale delivery of such services in developing countries, and the technology-based opportunities that exist today to make massive gains in financial inclusion. It also highlights the benefits to government from universal financial access, as well as the key policy enablers that would need to be put in place to allow the necessary innovati...

  7. Poorly Differentiated Thyroid Carcinoma.

    Science.gov (United States)

    Setia, Namrata; Barletta, Justine A

    2014-12-01

    Poorly differentiated thyroid carcinoma (PDTC) has been recognized for the past 30 years as an entity showing intermediate differentiation and clinical behavior between well-differentiated thyroid carcinomas (ie, papillary thyroid carcinoma and follicular thyroid carcinoma) and anaplastic thyroid carcinoma; however, there has been considerable controversy around the definition of PDTC. In this review, the evolution in the definition of PDTC, current diagnostic criteria, differential diagnoses, potentially helpful immunohistochemical studies, and molecular alterations are discussed with the aim of highlighting where the diagnosis of PDTC currently stands. Published by Elsevier Inc.

  8. Electron Transfer Mediator Effects in Water Oxidation Catalysis by Solution and Surface-Bound Ruthenium Bpy-Dicarboxylate Complexes

    Energy Technology Data Exchange (ETDEWEB)

    Sheridan, Matthew V.; Sherman, Benjamin D.; Marquard, Seth L.; Fang, Zhen; Ashford, Dennis L.; Wee, Kyung-Ryang; Gold, Alexander S.; Alibabaei, Leila; Rudd, Jennifer A.; Coggins, Michael K.; Meyer, Thomas J.

    2015-11-12

    Electrocatalytic water oxidation by the catalyst, ruthenium 2,2'-bipyridine-6,6'-dicarboxylate (bda) bis-isoquinoline (isoq), [Ru(bda)(isoq)2], 1, was investigated at metal oxide electrodes surface-derivatized with electron transfer (ET) mediators. At indium-doped tin oxide (ITO) in pH 7.2 in H2PO4–/HPO42– buffers in 0.5 M NaClO4 with added acetonitrile (MeCN), the catalytic activity of 1 is enhanced by the surface-bound redox mediators [Ru (4,4'-PO3H2-bpy)(4,4'-R-bpy)2]2+ (RuPbpyR22+, R = Br, H, Me, or OMe, bpy = 2,2'-bipyridine). Rate-limiting ET between the Ru3+ form of the mediator and the RuIV(O) form in the [RuV/IV(O)]+/0 couple of 1 is observed at relatively high concentrations of HPO42– buffer base under conditions where O···O bond formation is facilitated by atom-proton transfer (APT). For the solution [Ru(bpy)3]3+/2+ mediator couple and 1 as the catalyst, catalytic currents vary systematically with the concentration of mediator and the HPO42– buffer base concentration. Electron transfer mediation of water oxidation catalysis was also investigated on nanoparticle TiO2 electrodes co-loaded with catalyst [Ru(bda)(py-4-O(CH2)3-PO3H2)2], 2, (py = pyridine) and RuPbpyR22+ (R = H, Me, or OMe) with an interplay between rate-limiting catalyst oxidation and rate-limiting O···O bond formation by APT. Lastly, the co-loaded assembly RuPbpyR22+ + 2 has been investigated in a dye-sensitized photoelectrosynthesis cell for water splitting.

  9. Small-angle X-ray Solution Scattering Study of the Multi-aminoacyl-tRNA Synthetase Complex Reveals an Elongated and Multi-armed particle*

    Science.gov (United States)

    Dias, José; Renault, Louis; Pérez, Javier; Mirande, Marc

    2013-01-01

    In animal cells, nine aminoacyl-tRNA synthetases are associated with the three auxiliary proteins p18, p38, and p43 to form a stable and conserved large multi-aminoacyl-tRNA synthetase complex (MARS), whose molecular mass has been proposed to be between 1.0 and 1.5 MDa. The complex acts as a molecular hub for coordinating protein synthesis and diverse regulatory signal pathways. Electron microscopy studies defined its low resolution molecular envelope as an overall rather compact, asymmetric triangular shape. Here, we have analyzed the composition and homogeneity of the native mammalian MARS isolated from rabbit liver and characterized its overall internal structure, size, and shape at low resolution by hydrodynamic methods and small-angle x-ray scattering in solution. Our data reveal that the MARS exhibits a much more elongated and multi-armed shape than expected from previous reports. The hydrodynamic and structural features of the MARS are large compared with other supramolecular assemblies involved in translation, including ribosome. The large dimensions and non-compact structural organization of MARS favor a large protein surface accessibility for all its components. This may be essential to allow structural rearrangements between the catalytic and cis-acting tRNA binding domains of the synthetases required for binding the bulky tRNA substrates. This non-compact architecture may also contribute to the spatiotemporal controlled release of some of its components, which participate in non-canonical functions after dissociation from the complex. PMID:23836901

  10. Use of Electro-spray Ionization Mass Spectrometry (ESI-MS) for the characterization of complexes 'ligand - metallic cations' in solution

    Energy Technology Data Exchange (ETDEWEB)

    Berthon, Laurence; Zorz, Nicole; Lagrave, Stephanie; Gannaz, Benoit; Hill, Clement [CEA-Marcoule DEN-DRCP-SCPS-LCSE, BP 17171, 30207 Bagnols sur Ceze cedex (France)

    2008-07-01

    In the framework of nuclear waste reprocessing, separation processes of minor actinides from fission products are developed by Cea. In order to understand the mechanisms involved in the extraction processes, the 'ligand/metallic cation' complexes, formed in the organic phases are characterized by electro-spray-mass-spectrometry (ESI-MS). This paper deals with the extraction of lanthanides (III) and americium (III) cations by an organic phase composed of a malonamide or / and a dialkyl phosphoric acid, diluted in an aliphatic diluent. For the dialkyl phosphoric acid, Ln(DEHP){sub 3}(HDEHP){sub 3} complexes are observed and in the presence of a large excess of Ln(NO{sub 3}){sub 3}, dinuclear species are also observed. For the malonamide extractant, it appears that the complexes formed in the organic phase are of the Nd(NO{sub 3}){sub 3}D{sub x} type, with 2 {<=} x {<=} 4: their distributions depend on the ratio [Ln]/[DMDOHEMA]. When the two extractants are present in the organic phase, mixed 'Ln-malonamide-dialkyl phosphoric acid' species are observed. The influence of several parameters, such as extractant concentration, solute concentration, aqueous acidity and the nature of the cations (lanthanides or americium) are studied. (authors)

  11. Investigation of the luminescent properties of terbium-anthranilate complexes and application to the determination of anthranilic acid derivatives in aqueous solutions

    Energy Technology Data Exchange (ETDEWEB)

    Arnaud, N.; Georges, J

    2003-01-10

    The luminescent properties of terbium complexes with furosemide (FR), flufenamic (FF) acid, tolfenamic (TF) acid and mefenamic (MF) acid have been investigated in aqueous solutions. For all four compounds, complexation occurs when the carboxylic acid of the aminobenzoic group is dissociated and is greatly favoured in the presence of trioctylphosphine oxide as co-ligand and Triton X-100 as surfactant. Under optimum conditions, luminescence of the lanthanide ion is efficiently sensitised and the lifetime of the {sup 5}D{sub 4} resonance level of terbium in the complex is ranging between 1 and 1.9 ms, against 0.4 ms for the aqua ion. The sensitivity of the method for the determination of anthranilic acid derivatives is improved by one to two orders of magnitude with respect to that achieved using native fluorescence or terbium-sensitised luminescence in methanol. The limits of detection are 2x10{sup -10}, 5x10{sup -10} and 2x10{sup -9} mol l{sup -1} for flufenamic acid, furosemide and tolfenamic acid, and mefenamic acid, respectively, with within-run RSD values of less than 1%. The method has been applied to the determination of flufenamic acid in spiked calf sera with and without sample pretreatment. Depending on the method and the analyte concentration, the recovery was ranging between 83 and 113% and the lowest concentration attainable in serum samples was close to 1x10{sup -7} mol l{sup -1}.

  12. Comparative solution equilibrium studies on pentamethylcyclopentadienyl rhodium complexes of 2,2'-bipyridine and ethylenediamine and their interaction with human serum albumin.

    Science.gov (United States)

    Enyedy, Éva A; Mészáros, János P; Dömötör, Orsolya; Hackl, Carmen M; Roller, Alexander; Keppler, Bernhard K; Kandioller, Wolfgang

    2015-11-01

    Complex formation equilibrium processes of the (N,N) donor containing 2,2'-bipyridine (bpy) and ethylenediamine (en) with (η(5)-pentamethylcyclopentadienyl)rhodium(III) were investigated in aqueous solution via pH-potentiometry, (1)H NMR spectroscopy, and UV-vis spectrophotometry in the absence and presence of chloride ions. The structure of [RhCp*(en)Cl]ClO4 (Cp*, pentamethylcyclopentadienyl) was also studied by single-crystal X-ray diffraction. pKa values of 8.56 and 9.58 were determined for [RhCp*(bpy)(H2O)](2+) and [RhCp*(en)(H2O)](2+), respectively resulting in the formation of negligible amount of mixed hydroxido complexes at pH 7.4. Stability and the H2O/Cl(-) co-ligand exchange constants of bpy and en complexes considerably exceed those of the bidentate O-donor deferiprone. The strong affinity of the bpy and en complexes to chloride ions most probably contributes to their low antiproliferative effect. Interactions between human serum albumin (HSA) and [RhCp*(H2O)3](2+), its complexes formed with deferiprone, bpy and en were also monitored by (1)H NMR spectroscopy, ultrafiltration/UV-vis and spectrofluorometry. Numerous binding sites (≥ 8) are available for [RhCp*(H2O)3](2+); and the interaction takes place most probably via covalent bonds through the imidazole nitrogen of His. According to the various fluorescence studies [RhCp*(H2O)3](2+) binds on sites I and II, and coordination of surface side chain donor atoms of the protein is also feasible. The binding of the bpy and en complex is weaker and slower compared to that of [RhCp*(H2O)3](2+), and formation of ternary HSA-RhCp*-ligand adducts was proved. In the case of the deferiprone complex, the RhCp* fragment is cleaved off when HSA is loaded with low equivalents of the compound.

  13. Complex chemistry

    International Nuclear Information System (INIS)

    Kim, Bong Gon; Kim, Jae Sang; Kim, Jin Eun; Lee, Boo Yeon

    2006-06-01

    This book introduces complex chemistry with ten chapters, which include development of complex chemistry on history coordination theory and Warner's coordination theory and new development of complex chemistry, nomenclature on complex with conception and define, chemical formula on coordination compound, symbol of stereochemistry, stereo structure and isomerism, electron structure and bond theory on complex, structure of complex like NMR and XAFS, balance and reaction on solution, an organo-metallic chemistry, biology inorganic chemistry, material chemistry of complex, design of complex and calculation chemistry.

  14. [Poor insight and psychosis].

    Science.gov (United States)

    Giotakos, O

    2017-01-01

    A variety of phenomena might be considered as reflecting impaired insight in psychosis, like failure to recognize signs, symptoms or disease, failure to derive appropriate cognitive representations, despite recognition of the disease, and misattribution of the source or cause of the disease. The unawareness of tardive dyskinesia symptoms in schizophrenic patients points that self-awareness deficits in schizophrenia may be domain specific. Poor insight is an independent phenomenological and a prevalent feature in psychotic disorders in general, and in schizophrenia in particular, but we don't know yet if delusions in schizophrenia are the result of an entirely normal attempt to account for abnormal perceptual experiences or a product of abnormal experience but of normal reasoning. The theoretical approaches regarding impaired insight include the disturbed perceptual input, the impaired linkage between thought and emotion and the breakdown of the process of self-monitoring and error checking. The inability to distinguish between internally and externally generated mental events has been described by the metarepresentation theory. This theory includes the awareness of ones' goals, which leads to disorders of willed action, the awareness of intention, which leads to movement disorders, and the awareness of intentions of others, which leads to paranoid delusions. The theory of metarepresentation implies mainly output mechanisms, like the frontal cortex, while the input mechanism implies posterior brain systems, including the parietal lobe. There are many similarities between the disturbances of awareness seen in schizophrenia and those seen as a result of known neurological impairment. Neuropsychological models of impaired insight typically attribute the disturbance to any of a variety of core deficits in the processing of information. In this respect, lack of insight is on conceptual par with alogia, apraxia or aphasia in reflecting disturbed cognitive processing. In

  15. The 'poor man's laryngogram'

    International Nuclear Information System (INIS)

    Bartelt, D.

    1991-01-01

    This paper is reassessment of an old method improved by well-directed application of well-known maneuvers of laryngo-pharyngeal function. Although not as visually attractive as a dedicated laryngogram (now hardly ever requested), it does render similarly reliable diagnostic information, which, supported, as occasionally necessary, by conventional tomography, can even surpass that given by the older technique. Its main advantage lies in providing cheap, quick, noninvasive studies with minimal descomfort for the patient. Should further investigation be necessary, for analysis of deep extension, modern cross-sectional imaging methods (especially MR) far surpass even dedicated laryngography in diagnostic value and can be based adequately on 'poor mans's laryngography'. Ways in which this method may be optimised, especially those involving laryngopharyngeal function, are briefly presented - with emphasis on relevant practical aspects - as are normal and abnormal findings. (orig.) [de

  16. REMO poor man's reanalysis

    Science.gov (United States)

    Ries, H.; Moseley, C.; Haensler, A.

    2012-04-01

    Reanalyses depict the state of the atmosphere as a best fit in space and time of many atmospheric observations in a physically consistent way. By essentially solving the data assimilation problem in a very accurate manner, reanalysis results can be used as reference for model evaluation procedures and as forcing data sets for different model applications. However, the spatial resolution of the most common and accepted reanalysis data sets (e.g. JRA25, ERA-Interim) ranges from approximately 124 km to 80 km. This resolution is too coarse to simulate certain small scale processes often associated with extreme events. In addition, many models need higher resolved forcing data ( e.g. land-surface models, tools for identifying and assessing hydrological extremes). Therefore we downscaled the ERA-Interim reanalysis over the EURO-CORDEX-Domain for the time period 1989 to 2008 to a horizontal resolution of approximately 12 km. The downscaling is performed by nudging REMO-simulations to lower and lateral boundary conditions of the reanalysis, and by re-initializing the model every 24 hours ("REMO in forecast mode"). In this study the three following questions will be addressed: 1.) Does the REMO poor man's reanalysis meet the needs (accuracy, extreme value distribution) in validation and forcing? 2.) What lessons can be learned about the model used for downscaling? As REMO is used as a pure downscaling procedure, any systematic deviations from ERA-Interim result from poor process modelling but not from predictability limitations. 3.) How much small scale information generated by the downscaling model is lost with frequent initializations? A comparison to a simulation that is performed in climate mode will be presented.

  17. Kinetics and Mechanism of the Reaction of a Ruthenium(VI) Nitrido Complex with HSO3 (-) and SO3 (2-) in Aqueous Solution.

    Science.gov (United States)

    Wang, Qian; Zhao, Hong Yan; Man, Wai-Lun; Lam, William W Y; Lau, Kai-Chung; Lau, Tai-Chu

    2016-07-25

    The kinetics and mechanism of the reaction of S(IV) (SO3 (2-) +HSO3 (-) ) with a ruthenium(VI) nitrido complex, [(L)Ru(VI) (N)(OH2 )](+) (Ru(VI) N, L=N,N'-bis(salicylidene)-o-cyclohexyldiamine dianion), in aqueous acidic solutions are reported. The kinetic results are consistent with parallel pathways involving oxidation of HSO3 (-) and SO3 (2-) by Ru(VI) N. A deuterium isotope effect of 4.7 is observed in the HSO3 (-) pathway. Based on experimental results and DFT calculations the proposed mechanism involves concerted N-S bond formation (partial N-atom transfer) between Ru(VI) N and HSO3 (-) and H(+) transfer from HSO3 (-) to a H2 O molecule. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  18. Butterfly Deformation Modes in a Photoexcited Pyrazolate-Bridged Pt Complex Measured by Time-Resolved X-Ray Scattering in Solution

    DEFF Research Database (Denmark)

    Haldrup, Kristoffer; Dohn, Asmus Ougaard; Shelby, Megan L.

    2016-01-01

    the monochromatic X-ray pulses at Beamline 11IDD of the Advanced Photon Source. The excited-state structural analysis of 1 was performed based on the results from both transient WAXS measurements and density functional theory calculations to shed light on the primary structural changes in its triplet metal-metal...... excited state has remained scarce. Using time-resolved wide-angle X-ray scattering (WAXS), the excited triplet state molecular structure of [Pt(ppy)(μ-t-Bu2pz)]2 (ppy = 2-phenylpyridine; t-Bu2pz = 3,5-di-tert-butylpyrazolate), complex 1, was obtained in a dilute (0.5 mM) toluene solution utilizing...

  19. Potentiometric and spectrophotometric characterization of the UO{sub 2}{sup 2+}-citrate complexes in aqueous solution, at different concentrations, ionic strengths and supporting electrolytes

    Energy Technology Data Exchange (ETDEWEB)

    Berto, S.; Daniele, P.G.; Prenesti, E. [Torino Univ. (Italy). Dipt. di Chimica Analitica; Crea, F.; De Stefano, C.; Sammartano, S. [Messina Univ. (Italy). Dipt. di Chimica Inorganica, Chimica Analitica e Chimica Fisica

    2012-07-01

    In this paper we report an investigation on the interactions between dioxouranium(VI) and citrate using potentiometry (H{sup +}-glass electrode) and UV-spectrophotometry. Potentiometric measurements were carried out in NaCl and KNO{sub 3} aqueous solutions at t = 25 C in a wide range of experimental conditions (concentrations, ligand/metal molar ratio, pH, titrants). Measurements in NaCl were carried out at different ionic strength values (0.1 {<=} I/mol L{sup -1} {<=} 1.0); different procedures were employed for the acquisition of experimental data and careful analysis of these data performed. In all cases the speciation model that best fits experimental data takes into account the formation of the following species: UO{sub 2}(Cit){sup -}, (UO{sub 2}){sub 2}(Cit){sub 2}{sup 2-}, (UO{sub 2}){sub 2}(Cit){sub 2}(OH){sub 2}{sup 4-}, (UO{sub 2}){sub 2}(Cit){sub 2}(OH){sup 3-}, (UO{sub 2}){sub 2}(Cit)(OH){sub 2}{sup -}, (UO{sub 2}){sub 2}(Cit)(OH){sup 0}, (UO{sub 2}){sub 3}(Cit){sub 2}(OH){sub 5}{sup 5-}. The dependence on ionic strength of formation constants was taken into account by using both a simple Debye-Hueckel type equation and the SIT (specific ion interaction theory) approach. Moreover, a visible absorption spectrum for each complex reaching a significant percentage of formation in solution (KNO{sub 3} medium) has been calculated to characterise the compounds found by pH-metric refinement. Recommended values for the uranyl-citrate species were proposed for each ionic strength values in NaCl aqueous solution. Comparison with literature stability constants is reported too. (orig.)

  20. Inhibition of precipitation of carbonate apatite by trisodium citrate analysed in base of the formation of chemical complexes in growth solution

    Energy Technology Data Exchange (ETDEWEB)

    Prywer, Jolanta, E-mail: jolanta.prywer@p.lodz.pl [Institute of Physics, Lodz University of Technology, ul. Wólczańska 219, 93-005 Łódź (Poland); Olszynski, Marcin [Institute of Physics, Lodz University of Technology, ul. Wólczańska 219, 93-005 Łódź (Poland); Mielniczek-Brzóska, Ewa [Institute of Chemistry, Environment Protection and Biotechnology, Jan Długosz University of Częstochowa, ul. Armii Krajowej 13/15, 42-200 Częstochowa (Poland)

    2015-11-15

    Effect of trisodium citrate on the precipitation of carbonate apatite is studied. The experimental series are performed in the solution of artificial urine. The investigations are related to infectious urinary stones formation as carbonate apatite is one of the main components of this kind of stones. To mimic a real infection in urinary tract the aqueous ammonia solution was added to the solution of artificial urine. The spectrophotometric results demonstrate that trisodium citrate increases induction time with respect to carbonate apatite formation and decreases the efficiency of carbonate apatite precipitation. The inhibitory effect of trisodium citrate on the precipitation of carbonate apatite is explained in base of chemical speciation analysis. Such an analysis demonstrates that the inhibitory effect is mainly related with the fact that trisodium citrate binds Ca{sup 2+} ions and causes the formation of CaCit{sup −} and Ca{sub 10}(PO{sub 4}){sub 6}CO{sub 3} complexes. Trisodium citrate binds Ca{sup 2+} ions in the range of pH from 6 to 9.5 for which carbonate apatite is favored to be formed. - Highlights: • Trisodium citrate (TC) increases induction time of carbonate apatite (CA) formation. • TC decreases the efficiency of CA precipitation. • The inhibitory effect of TC is explained in base of chemical speciation analysis. • The inhibitory effect is mainly related with the fact that TC binds Ca{sup 2+} ions. • TC binds Ca{sup 2+} ions in the range of pH from 6 to 9.5 for which CA is formed.

  1. Solution structure of the human Grb7-SH2 domain/erbB2 peptide complex and structural basis for Grb7 binding to ErbB2

    International Nuclear Information System (INIS)

    Ivancic, Monika; Daly, Roger J.; Lyons, Barbara A.

    2003-01-01

    The solution structure of the hGrb7-SH2 domain in complex with a ten amino acid phosphorylated peptide ligand representative of the erbB2 receptor tyrosine kinase (pY1139) is presented as determined by nuclear magnetic resonance methods. The hGrb7-SH2 domain structure reveals the Src homology 2 domain topology consisting of a central β-sheet capped at each end by an α-helix. The presence of a four residue insertion in the region between β-strand E and the EF loop and resulting influences on the SH2 domain/peptide complex structure are discussed. The binding conformation of the erbB2 peptide is in a β-turn similar to that found in phosphorylated tyrosine peptides bound to the Grb2-SH2 domain. To our knowledge this is only the second example of an SH2 domain binding its naturally occurring ligands in a turn, instead of extended, conformation. Close contacts between residues responsible for binding specificity in hGrb7-SH2 and the erbB2 peptide are characterized and the potential effect of mutation of these residues on the hGrb7-SH2 domain structure is discussed

  2. Tackling Complex Emergency Response Solutions Evaluation Problems in Sustainable Development by Fuzzy Group Decision Making Approaches with Considering Decision Hesitancy and Prioritization among Assessing Criteria.

    Science.gov (United States)

    Qi, Xiao-Wen; Zhang, Jun-Ling; Zhao, Shu-Ping; Liang, Chang-Yong

    2017-10-02

    In order to be prepared against potential balance-breaking risks affecting economic development, more and more countries have recognized emergency response solutions evaluation (ERSE) as an indispensable activity in their governance of sustainable development. Traditional multiple criteria group decision making (MCGDM) approaches to ERSE have been facing simultaneous challenging characteristics of decision hesitancy and prioritization relations among assessing criteria, due to the complexity in practical ERSE problems. Therefore, aiming at the special type of ERSE problems that hold the two characteristics, we investigate effective MCGDM approaches by hiring interval-valued dual hesitant fuzzy set (IVDHFS) to comprehensively depict decision hesitancy. To exploit decision information embedded in prioritization relations among criteria, we firstly define an fuzzy entropy measure for IVDHFS so that its derivative decision models can avoid potential information distortion in models based on classic IVDHFS distance measures with subjective supplementing mechanism; further, based on defined entropy measure, we develop two fundamental prioritized operators for IVDHFS by extending Yager's prioritized operators. Furthermore, on the strength of above methods, we construct two hesitant fuzzy MCGDM approaches to tackle complex scenarios with or without known weights for decision makers, respectively. Finally, case studies have been conducted to show effectiveness and practicality of our proposed approaches.

  3. Dynamic studies of H-Ras•GTPγS interactions with nucleotide exchange factor Sos reveal a transient ternary complex formation in solution.

    Science.gov (United States)

    Vo, Uybach; Vajpai, Navratna; Embrey, Kevin J; Golovanov, Alexander P

    2016-07-14

    The cycling between GDP- and GTP- bound forms of the Ras protein is partly regulated by the binding of Sos. The structural/dynamic behavior of the complex formed between activated Sos and Ras at the point of the functional cycle where the nucleotide exchange is completed has not been described to date. Here we show that solution NMR spectra of H-Ras∙GTPγS mixed with a functional fragment of Sos (Sos(Cat)) at a 2:1 ratio are consistent with the formation of a rather dynamic assembly. H-Ras∙GTPγS binding was in fast exchange on the NMR timescale and retained a significant degree of molecular tumbling independent of Sos(Cat), while Sos(Cat) also tumbled largely independently of H-Ras. Estimates of apparent molecular weight from both NMR data and SEC-MALS revealed that, at most, only one H-Ras∙GTPγS molecule appears stably bound to Sos. The weak transient interaction between Sos and the second H-Ras∙GTPγS may provide a necessary mechanism for complex dissociation upon the completion of the native GDP → GTP exchange reaction, but also explains measurable GTP → GTP exchange activity of Sos routinely observed in in vitro assays that use fluorescently-labelled analogs of GTP. Overall, the data presents the first dynamic snapshot of Ras functional cycle as controlled by Sos.

  4. On the accuracy of DFT methods in reproducing ligand substitution energies for transition metal complexes in solution: The role of dispersive interactions

    KAUST Repository

    Jacobsen, Heiko

    2011-12-23

    The performance of a series of density functionals when tested on the prediction of the phosphane substitution energy of transition metal complexes is evaluated. The complexes Fe-BDA and Ru-COD (BDA=benzylideneacetone, COD=cyclooctadiene) serve as reference systems, and calculated values are compared with the experimental values in THF as obtained from calorimetry. Results clearly indicate that functionals specifically developed to include dispersion interactions usually outperform other functionals when BDA or COD substitution is considered. However, when phosphanes of different sizes are compared, functionals including dispersion interactions, at odd with experimental evidence, predict that larger phosphanes bind more strongly than smaller phosphanes, while functionals not including dispersion interaction reproduce the experimental trends with reasonable accuracy. In case of the DFT-D functionals, inclusion of a cut-off distance on the dispersive term resolves this issue, and results in a rather robust behavior whatever ligand substitution reaction is considered. Ne quid nimis: Describing chemical reactions in solution by computational techniques developed for gas-phase scenarios might produce erroneous results (see histogram). Copyright © 2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  5. Tackling Complex Emergency Response Solutions Evaluation Problems in Sustainable Development by Fuzzy Group Decision Making Approaches with Considering Decision Hesitancy and Prioritization among Assessing Criteria

    Directory of Open Access Journals (Sweden)

    Xiao-Wen Qi

    2017-10-01

    Full Text Available In order to be prepared against potential balance-breaking risks affecting economic development, more and more countries have recognized emergency response solutions evaluation (ERSE as an indispensable activity in their governance of sustainable development. Traditional multiple criteria group decision making (MCGDM approaches to ERSE have been facing simultaneous challenging characteristics of decision hesitancy and prioritization relations among assessing criteria, due to the complexity in practical ERSE problems. Therefore, aiming at the special type of ERSE problems that hold the two characteristics, we investigate effective MCGDM approaches by hiring interval-valued dual hesitant fuzzy set (IVDHFS to comprehensively depict decision hesitancy. To exploit decision information embedded in prioritization relations among criteria, we firstly define an fuzzy entropy measure for IVDHFS so that its derivative decision models can avoid potential information distortion in models based on classic IVDHFS distance measures with subjective supplementing mechanism; further, based on defined entropy measure, we develop two fundamental prioritized operators for IVDHFS by extending Yager’s prioritized operators. Furthermore, on the strength of above methods, we construct two hesitant fuzzy MCGDM approaches to tackle complex scenarios with or without known weights for decision makers, respectively. Finally, case studies have been conducted to show effectiveness and practicality of our proposed approaches.

  6. Static and dynamic investigations of poly(aspartic acid) and Pluronic F127 complex prepared by self-assembling in aqueous solution

    Science.gov (United States)

    Nita, Loredana E.; Chiriac, Aurica P.; Bercea, Maria; Nistor, Manuela T.

    2015-12-01

    The present investigation is focused on evaluation of self-assembling ability in aqueous solutions of two water soluble polymers: poly(aspartic acid) (PAS) and Pluronic F127 (PL). The intermolecular complexes, realized between polyacid and neutral copolymer surfactant in different ratios, have been studied by combining various characterization techniques as rheology, DLS, spectroscopy, microscopy, chemical imaging, and zeta potential determination, measurements performed in static and/or dynamic conditions. In static conditions, when the equilibrium state between PAS/PL polymeric pair was reached, and depending on the polymers mixture composition, and of experimental rheological conditions, positive or negative deviations from the additive rule are registered. Conformational changes of the macromolecular chains and correspondingly physical interactions are generated between PL and PAS for self-assembly and the formation of interpolymer complex as suprastructure with micellar configuration. The phenomenon was better evidenced in case of 1/1 wt ratio between the two polymers. In dynamic conditions of determination, during ;in situ; evaluation of the hydrodynamic diameter, zeta potential and conductivity, when the equilibrium state is not reached and as result either the intermolecular bonds are not achieved, the self-assembling process is not so obvious evidenced.

  7. Structure of the Hydrated Platinum(II) Ion And the Cis-Diammine-Platinum(II) Complex in Acidic Aqueous Solution: An EXAFS Study

    Energy Technology Data Exchange (ETDEWEB)

    Jalilehvand, F.; Laffin, L.J.

    2009-05-18

    Careful analysis of Pt L{sub 3}-edge extended X-ray absorption fine structure (EXAFS) spectra shows that the hydrated platinum(II) ion in acidic (HClO{sub 4}) aqueous solution binds four water molecules with the Pt-O bond distance 2.01(2) {angstrom} and one (or two) in the axial position at 2.39(2) {angstrom}. The weak axial water coordination is in accordance with the unexpectedly small activation volume previously reported for water exchange in an interchange mechanism with associative character. The hydrated cis-diammineplatinum(II) complex has a similar coordination environment with two ammine and two aqua ligands strongly bound with Pt-O/N bond distances of 2.01(2) {angstrom} and, in addition, one (or two) axial water molecule at 2.37(2) {angstrom}. This result provides a new basis for theoretical computational studies aiming to connect the function of the anticancer drug cis-platin to its ligand exchange reactions, where usually four-coordinated square planar platinum(II) species are considered as the reactant and product. {sup 195}Pt NMR spectroscopy has been used to characterize the Pt(II) complexes.

  8. Robust binding between carbon nitride nanosheets and a binuclear ruthenium(II) complex enabling durable, selective CO{sub 2} reduction under visible light in aqueous solution

    Energy Technology Data Exchange (ETDEWEB)

    Kuriki, Ryo; Ishitani, Osamu; Maeda, Kazuhiko [Department of Chemistry, School of Science, Tokyo Institute of Technology (Japan); Yamamoto, Muneaki; Yoshida, Tomoko [Advanced Research Institute for Natural Science and Technology, Osaka City University (Japan); Higuchi, Kimitaka; Yamamoto, Yuta; Akatsuka, Masato; Yagi, Shinya [Institute of Materials and Systems for Sustainability, Nagoya University (Japan); Lu, Daling [Suzukakedai Materials Analysis Division, Technical Department, Tokyo Institute of Technology, Yokohama (Japan)

    2017-04-18

    Carbon nitride nanosheets (NS-C{sub 3}N{sub 4}) were found to undergo robust binding with a binuclear ruthenium(II) complex (RuRu') even in basic aqueous solution. A hybrid material consisting of NS-C{sub 3}N{sub 4} (further modified with nanoparticulate Ag) and RuRu' promoted the photocatalytic reduction of CO{sub 2} to formate in aqueous media, in conjunction with high selectivity (approximately 98 %) and a good turnover number (>2000 with respect to the loaded Ru complex). These represent the highest values yet reported for a powder-based photocatalytic system during CO{sub 2} reduction under visible light in an aqueous environment. We also assessed the desorption of RuRu' from the Ag/C{sub 3}N{sub 4} surface, a factor that can contribute to a loss of activity. It was determined that desorption is not induced by salt additives, pH changes, or photoirradiation, which partly explains the high photocatalytic performance of this material. (copyright 2017 Wiley-VCH Verlag GmbH and Co. KGaA, Weinheim)

  9. Binuclear Pt-Tl bonded complex with square pyramidal coordination around Pt: a combined multinuclear NMR, EXAFS, UV-Vis, and DFT/TDDFT study in dimethylsulfoxide solution.

    Science.gov (United States)

    Purgel, Mihály; Maliarik, Mikhail; Glaser, Julius; Platas-Iglesias, Carlos; Persson, Ingmar; Tóth, Imre

    2011-07-04

    The structure and bonding of a new Pt-Tl bonded complex formed in dimethylsulfoxide (dmso), (CN)(4)Pt-Tl(dmso)(5)(+), have been studied by multinuclear NMR and UV-vis spectroscopies, and EXAFS measurements in combination with density functional theory (DFT) and time dependent density functional theory (TDDFT) calculations. This complex is formed following the equilibrium reaction Pt(CN)(4)(2-) + Tl(dmso)(6)(3+) ⇆ (CN)(4)Pt-Tl(dmso)(5)(+) + dmso. The stability constant of the Pt-Tl bonded species, as determined using (13)C NMR spectroscopy, amounts to log K = 2.9 ± 0.2. The (NC)(4)Pt-Tl(dmso)(5)(+) species constitutes the first example of a Pt-Tl bonded cyanide complex in which the sixth coordination position around Pt (in trans with respect to the Tl atom) is not occupied. The spectral parameters confirm the formation of the metal-metal bond, but differ substantially from those measured earlier in aqueous solution for complexes (CN)(5)Pt-Tl(CN)(n)(H(2)O)(x)(n-) (n = 0-3). The (205) Tl NMR chemical shift, δ = 75 ppm, is at extraordinary high field, while spin-spin coupling constant, (1)J(Pt-Tl) = 93 kHz, is the largest measured to date for a Pt-Tl bond in the absence of supporting bridging ligands. The absorption spectrum is dominated by two strong absorption bands in the UV region that are assigned to MMCT (Pt → Tl) and LMCT (dmso → Tl) bands, respectively, on the basis of MO and TDDFT calculations. The solution of the complex has a bright yellow color as a result of a shoulder present on the low energy side of the band at 355 nm. The geometry of the (CN)(4)Pt-Tl core can be elucidated from NMR data, but the particular stoichiometry and structure involving the dmso ligands are established by using Tl and Pt L(III)-edge EXAFS measurements. The Pt-Tl bond distance is 2.67(1) Å, the Tl-O bond distance is 2.282(6) Å, and the Pt-C-N entity is linear with Pt-C and Pt···N distances amounting to 1.969(6) and 3.096(6) Å, respectively. Geometry optimizations on

  10. ⁹⁹mTc pyrene derivative complex causes double-strand breaks in dsDNA mainly through cluster-mediated indirect effect in aqueous solution.

    Directory of Open Access Journals (Sweden)

    Wei-Ju Chung

    Full Text Available Radiation therapy for cancer patients works by ionizing damage to nuclear DNA, primarily by creating double-strand breaks (DSB. A major shortcoming of traditional radiation therapy is the set of side effect associated with its long-range interaction with nearby tissues. Low-energy Auger electrons have the advantage of an extremely short effective range, minimizing damage to healthy tissue. Consequently, the isotope ⁹⁹mTc, an Auger electron source, is currently being studied for its beneficial potential in cancer treatment. We examined the dose effect of a pyrene derivative ⁹⁹mTc complex on plasmid DNA by using gel electrophoresis in both aqueous and methanol solutions. In aqueous solutions, the average yield per decay for double-strand breaks is 0.011±0.005 at low dose range, decreasing to 0.0005±0.0003 in the presence of 1 M dimethyl sulfoxide (DMSO. The apparent yield per decay for single-strand breaks (SSB is 0.04±0.02, decreasing to approximately a fifth with 1 M DMSO. In methanol, the average yield per decay of DSB is 0.54±0.06 and drops to undetectable levels in 2 M DMSO. The SSB yield per decay is 7.2±0.2, changing to 0.4±0.2 in the presence of 2 M DMSO. The 95% decrease in the yield of DSB in DMSO indicates that the main mechanism for DSB formation is through indirect effect, possibly by cooperative binding or clustering of intercalators. In the presence of non-radioactive ligands at a near saturation concentration, where radioactive Tc compounds do not form large clusters, the yield of SSB stays the same while the yield of DSB decreases to the value in DMSO. DSBs generated by ⁹⁹mTc conjugated to intercalators are primarily caused by indirect effects through clustering.

  11. ⁹⁹mTc pyrene derivative complex causes double-strand breaks in dsDNA mainly through cluster-mediated indirect effect in aqueous solution.

    Science.gov (United States)

    Chung, Wei-Ju; Cui, Yujia; Huang, Feng-Yun J; Tu, Tzu-Hui; Yang, Tzu-Sen; Lo, Jem-Mau; Chiang, Chi-Shiun; Hsu, Ian C

    2014-01-01

    Radiation therapy for cancer patients works by ionizing damage to nuclear DNA, primarily by creating double-strand breaks (DSB). A major shortcoming of traditional radiation therapy is the set of side effect associated with its long-range interaction with nearby tissues. Low-energy Auger electrons have the advantage of an extremely short effective range, minimizing damage to healthy tissue. Consequently, the isotope ⁹⁹mTc, an Auger electron source, is currently being studied for its beneficial potential in cancer treatment. We examined the dose effect of a pyrene derivative ⁹⁹mTc complex on plasmid DNA by using gel electrophoresis in both aqueous and methanol solutions. In aqueous solutions, the average yield per decay for double-strand breaks is 0.011±0.005 at low dose range, decreasing to 0.0005±0.0003 in the presence of 1 M dimethyl sulfoxide (DMSO). The apparent yield per decay for single-strand breaks (SSB) is 0.04±0.02, decreasing to approximately a fifth with 1 M DMSO. In methanol, the average yield per decay of DSB is 0.54±0.06 and drops to undetectable levels in 2 M DMSO. The SSB yield per decay is 7.2±0.2, changing to 0.4±0.2 in the presence of 2 M DMSO. The 95% decrease in the yield of DSB in DMSO indicates that the main mechanism for DSB formation is through indirect effect, possibly by cooperative binding or clustering of intercalators. In the presence of non-radioactive ligands at a near saturation concentration, where radioactive Tc compounds do not form large clusters, the yield of SSB stays the same while the yield of DSB decreases to the value in DMSO. DSBs generated by ⁹⁹mTc conjugated to intercalators are primarily caused by indirect effects through clustering.

  12. Copper(II) 12-metallacrown-4 complexes of alpha-, beta- and gamma-aminohydroxamic acids: a comparative thermodynamic study in aqueous solution.

    Science.gov (United States)

    Tegoni, Matteo; Remelli, Maurizio; Bacco, Dimitri; Marchiò, Luciano; Dallavalle, Francesco

    2008-05-28

    A complete thermodynamic study of the protonation and Cu(II) complex formation equilibria of a series of alpha- and beta-aminohydroxamic acids in aqueous solution was performed. The thermodynamic parameters obtained for the protonation of glycine-, (S)-alpha-alanine-, (R,S)-valine-, (S)-leucine-, beta-alanine- and (R)-aspartic-beta-hydroxamic acids were compared with those previously reported for gamma-amino- and (S)-glutamic-gamma-hydroxamic acids. The enthalpy/entropy parameters calculated for the protonation microequilibria of these three types of ligands are in very good agreement with the literature values for simple amines and hydroxamic acids. The pentanuclear complexes [Cu5L4H(-4)]2+ contain the ligands acting as (NH2,N-)-(O,O-) bridging bis-chelating and correspond to 12-metallacrown-4 (12-MC-4) which are formed by self-assembly between pH 4 and 6 with alpha-aminohydroxamates (HL), while those with beta- and gamma-derivatives exist in a wider pH range (4-11). The stability order of these metallomacrocycles is beta- > alpha- > gamma-aminohydroxamates. The formation of 12-MC-4 with alpha-aminohydroxamates is entropy-driven, and that with beta-derivatives is enthalpy-driven, while with gamma-GABAhydroxamate both effects occur. These results are interpreted on the basis of specific enthalpies or entropy contributions related to chelate ring dimensions, charge neutralization and solvation-desolvation effects. The enthalpy/entropy parameters of 12-MC-4 with alpha-aminohydroxamic acids considered are also dependent on the optical purity of the ligands. Actually, that with (R,S)-valinehydroxamic acid presents an higher entropy and a lower enthalpy value than those of enantiopure ligands, although the corresponding stabilities are almost equivalent. Moreover, DFT calculations are in agreement with a more exothermic enthalpy found for metallacrowns with enantiomerically pure ligands.

  13. Solvation and complexation study by fluorescence spectroscopy of Eu(III) and Cm(III) ions in octanol solution and at the interface with water

    International Nuclear Information System (INIS)

    Vu, T.H.

    2008-01-01

    Polydentate N-donors ligands like bis-triazine-pyridine (BTP) and bis-triazine-bis-pyridine (BTBP) can selectively extract minor actinides (III) from lanthanides (III) ions and therefore have been studied in the field of nuclear waste reprocessing. The aim of the researches carried out during this thesis is a better description of this family in biphasic systems: speciation in the organic phase and around the interfacial area. After an exhaustive description of the solvation of europium(III) cation in mixed solutions n-octanol water with TRLIF spectrometry, the complexation with nitrogen ligands iPr-BTP, C5-BTBP and CyMe4-BTBP has been studied by TRLIF and ESI-MS techniques. For each compound, the inner sphere of europium has been described and the conditional stability constants determined. The composition of the organic medium, and particularly the hydration degree of n-octanol, has an impact on the nature and the ratio of species 'cation - counter ion - ligand - water'. With high water content (representative of extraction systems), the complexes observed with Cm(III) and Eu(III) have the same stoichiometry but the affinity towards the curium cation is higher and consistent to separation factors measured with biphasic systems. The method TIRF (total internal reflection fluorescence) was retained to study the behaviour of europium(III) inside the interfacial area. Fluorescence spectra of europium have been obtained but side signals and the high depth resolution of detection lead to difficulty in obtaining the signal of interfacial europium alone. The selected technique remains promising but some improvements need to be implemented for forthcoming measurement at liquid/liquid interface. (author) [fr

  14. Capitalizing Resolving Power of Density Gradient Ultracentrifugation by Freezing and Precisely Slicing Centrifuged Solution: Enabling Identification of Complex Proteins from Mitochondria by Matrix Assisted Laser Desorption/Ionization Time-of-Flight Mass Spectrometry

    Directory of Open Access Journals (Sweden)

    Haiqing Yu

    2016-01-01

    Full Text Available Density gradient centrifugation is widely utilized for various high purity sample preparations, and density gradient ultracentrifugation (DGU is often used for more resolution-demanding purification of organelles and protein complexes. Accurately locating different isopycnic layers and precisely extracting solutions from these layers play a critical role in achieving high-resolution DGU separations. In this technique note, we develop a DGU procedure by freezing the solution rapidly (but gently after centrifugation to fix the resolved layers and by slicing the frozen solution to fractionate the sample. Because the thickness of each slice can be controlled to be as thin as 10 micrometers, we retain virtually all the resolution produced by DGU. To demonstrate the effectiveness of this method, we fractionate complex V from HeLa mitochondria using a conventional technique and this freezing-slicing (F-S method. The comparison indicates that our F-S method can reduce complex V layer thicknesses by ~40%. After fractionation, we analyze complex V proteins directly on a matrix assisted laser desorption/ionization, time-of-flight mass spectrometer. Twelve out of fifteen subunits of complex V are positively identified. Our method provides a practical protocol to identify proteins from complexes, which is useful to investigate biomolecular complexes and pathways in various conditions and cell types.

  15. Determination of 13C CSA Tensors: Extension of the Model-independent Approach to an RNA Kissing Complex Undergoing Anisotropic Rotational Diffusion in Solution

    International Nuclear Information System (INIS)

    Ravindranathan, Sapna; Kim, Chul-Hyun; Bodenhausen, Geoffrey

    2005-01-01

    Chemical shift anisotropy (CSA) tensor parameters have been determined for the protonated carbons of the purine bases in an RNA kissing complex in solution by extending the model-independent approach [Fushman, D., Cowburn, D. (1998) J. Am. Chem. Soc. 120, 7109-7110]. A strategy for determining CSA tensor parameters of heteronuclei in isolated X-H two-spin systems (X = 13 C or 15 N) in molecules undergoing anisotropic rotational diffusion is presented. The original method relies on the fact that the ratio κ 2 =R 2 auto /R 2 cross of the transverse auto- and cross-correlated relaxation rates involving the X CSA and the X-H dipolar interaction is independent of parameters related to molecular motion, provided rotational diffusion is isotropic. However, if the overall motion is anisotropic κ 2 depends on the anisotropy D parallel /D -perpendicular of rotational diffusion. In this paper, the field dependence of both κ 2 and its longitudinal counterpart κ 1 =R 1 auto /R 1 cross are determined. For anisotropic rotational diffusion, our calculations show that the average κ av = 1/2 (κ 1 +κ 2 ), of the ratios is largely independent of the anisotropy parameter D parallel /D -perpendicular . The field dependence of the average ratio κ av may thus be utilized to determine CSA tensor parameters by a generalized model-independent approach in the case of molecules with an overall motion described by an axially symmetric rotational diffusion tensor

  16. Electrochemical analysis of the corrosion inhibition effect of trypsin complex on the pitting corrosion of 420 martensitic stainless steel in 2M H2SO4 solution.

    Science.gov (United States)

    Loto, Roland Tolulope

    2018-01-01

    Inhibition effect of trypsin complex (TC) on the pitting corrosion of martensitic stainless steel (type 420) in 1M H2SO4 solution was studied with potentiodynamic polarization, open circuit potential measurement and optical microscopy. TC reduced the corrosion rate of the steel with maximum inhibition efficiency of 80.75%. Corrosion potential shifted anodically due to the electrochemical action of TC. The pitting potential increased from 1.088VAg/AgCl (3M) at 0% TC to 1.365VAg/AgCl(3M) at 4% TC. TC shifts the open circuit corrosion potential from -0.270s at 0% TC concentration to -0.255V at 5% TC. The compound completely adsorbed onto the steel according to Langmuir, Frumkin and Temkin isotherms. ATF-FTIR spectroscopy confirmed the inhibition mode to be through surface coverage. Thermodynamic calculations showed physisorption molecular interaction. Corrosion pits are present on the uninhibited 420 morphology in comparison to TC inhibited surface which slightly deteriorated.

  17. Spray drying of poorly soluble drugs from aqueous arginine solution.

    Science.gov (United States)

    Ojarinta, Rami; Lerminiaux, Louise; Laitinen, Riikka

    2017-10-30

    Co-amorphous drug-amino acid mixtures have shown potential for improving the solid-state stability and dissolution behavior of amorphous drugs. In previous studies, however these mixtures have been produced mainly with small-scale preparation methods, or with methods that have required the use of organic solvents or other dissolution enhancers. In the present study, co-amorphous ibuprofen-arginine and indomethacin-arginine mixtures were spray dried from water. The mixtures were prepared at two drug-arginine molar ratios (1:1 and 1:2). The properties of the prepared mixtures were investigated with differential scanning calorimetry, X-ray powder diffractometry, Fourier-transform infrared spectroscopy and a 24h, non-sink, dissolution study. All mixtures exhibited a single glass transition temperature (T g ), evidence of the formation of homogenous single-phase systems. Fourier transform infrared spectroscopy revealed strong interactions (mainly salt formation) that account for the positive deviation between measured and estimated T g values. No crystallization was observed during a 1-year stability study in either 1:1 or 1:2 mixtures, but in the presence of moisture, handling difficulties were encountered. The formation of co-amorphous salts led to improved dissolution characteristics when compared to the corresponding physical mixtures or to pure crystalline drugs. Copyright © 2017 Elsevier B.V. All rights reserved.

  18. Counting the World's Poor : Problems and Possible Solutions

    OpenAIRE

    Deaton, Angus

    2001-01-01

    As recent discussions have made clear, the apparent lack of poverty reduction in the face of historically high rates of economic growth-both in the world as a whole and in specific countries (most notably India)-provides fuel for the argument that economic growth does little to reduce poverty. How confident can we be that the data actually support these inferences? At the international lev...

  19. Sci-Thur AM: Planning - 04: Evaluation of the fluence complexity, solution quality, and run efficiency produced by five fluence parameterizations implemented in PARETO multiobjective radiotherapy treatment planning software.

    Science.gov (United States)

    Champion, H; Fiege, J; McCurdy, B; Potrebko, P; Cull, A

    2012-07-01

    PARETO (Pareto-Aware Radiotherapy Evolutionary Treatment Optimization) is a novel multiobjective treatment planning system that performs beam orientation and fluence optimization simultaneously using an advanced evolutionary algorithm. In order to reduce the number of parameters involved in this enormous search space, we present several methods for modeling the beam fluence. The parameterizations are compared using innovative tools that evaluate fluence complexity, solution quality, and run efficiency. A PARETO run is performed using the basic weight (BW), linear gradient (LG), cosine transform (CT), beam group (BG), and isodose-projection (IP) methods for applying fluence modulation over the projection of the Planning Target Volume in the beam's-eye-view plane. The solutions of each run are non-dominated with respect to other trial solutions encountered during the run. However, to compare the solution quality of independent runs, each run competes against every other run in a round robin fashion. Score is assigned based on the fraction of solutions that survive when a tournament selection operator is applied to the solutions of the two competitors. To compare fluence complexity, a modulation index, fractal dimension, and image gradient entropy are calculated for the fluence maps of each optimal plan. We have found that the LG method results in superior solution quality for a spine phantom, lung patient, and cauda equina patient. The BG method produces solutions with the highest degree of fluence complexity. Most methods result in comparable run times. The LG method produces superior solution quality using a moderate degree of fluence modulation. © 2012 American Association of Physicists in Medicine.

  20. Solute-solute interactions in intermetallic compounds

    Energy Technology Data Exchange (ETDEWEB)

    Banerjee, Debashis; Murray, Ryan; Collins, Gary S., E-mail: collins@wsu.edu [Washington State University, Department of Physics and Astronomy (United States); Zacate, Matthew O. [Northern Kentucky University, Department of Physics and Geology (United States)

    2017-11-15

    Experiments were carried out on highly ordered GdAl{sub 2} samples containing extremely dilute mole fractions of{sup 111}In/Cd probe-atom solutes (about 10{sup −11}), intrinsic antisite atoms Al{sub Gd} having mole fractions of order 0-10{sup −2}, and doped with Ag solutes at mole fractions of order 10{sup −2}. Three types of defect interactions were investigated. (1) Quadrupole interactions caused by Ag-solute atoms neighboring{sup 111}In/Cd solute probe atoms were detected using the method of perturbed angular correlation of gamma rays (PAC). Three complexes of pairs of In-probes and Ag-solutes occupying neighboring positions on Gd- and Al-sublattices were identified by comparing site fractions in Gd-poor and Gd-rich GdAl{sub 2}(Ag) samples and from the symmetry of the quadrupole interactions. Interaction enthalpies between solute-atom pairs were determined from temperature dependences of observed site fractions. Repulsive interactions were observed for close-neighbor complexes In{sub Gd}+Ag{sub Gd} and In{sub Gd}+Ag{sub Al} pairs, whereas a slightly attractive interaction was observed for In{sub Al}+Ag{sub Al}. Interaction enthalpies were all small, in the range ±0.15 eV. (2) Quadrupole interactions caused by intrinsic antisite atoms Al{sub Gd} neighboring In{sub Gd} probes were also detected and site fractions measured as a function of temperature, as in previous work on samples not doped with Ag-solutes [Temperature- and composition-driven changes in site occupation of solutes in Gd{sub 1+3x}Al{sub 2−3x}, Zacate and Collins (Phys. Rev. B69, 174202 (1))]. However, the effective binding enthalpy between In{sub Gd} probe and Al{sub Gd} antisite was found to change sign from -0.12 eV (attractive interaction) in undoped samples to + 0.24 eV (repulsive) in Ag-doped samples. This may be attributed to an attractive interaction between Al{sub Gd} antisite atoms and Ag-dopants that competes with the attractive interaction between In{sub Gd} and Al{sub Gd

  1. Flash and Continuous Photolysis Studies of the Thionitrosyl Complex Cr(CH3CN)5(NS)2+ and the Nitric Oxide Analogs. Reactions of Nitrogen Monosulfide in Solution

    DEFF Research Database (Denmark)

    Dethlefsen, Johannes Wied; Hedegård, Erik; Rimmer, R. Dale

    2009-01-01

    Photolysis of the thionitrosyl complex Cr(CH3CN)5(NS)2+ (1) in acetonitrile solution leads to the dissociation of nitrogen monosulfide (NS).  In deaerated solution, this reaction is reversible, and flash photolysis studies demonstrate that NS reacts with Cr(CH3CN)62+ according to the rate law d[1...... dependent quantum yields of 0.3-1.0 mol/Einstein. Mass spectroscopic studies of the product solutions demonstrate formation of S8, presumably from the decomposition of NS. The quantitative photochemical behaviors of 1 and the nitrosyl analog 2 are compared. Udgivelsesdato: Jan....

  2. Does Lean & Agile Project Management Help Coping with Project Complexity?

    NARCIS (Netherlands)

    Jalali Sohi, A.; Hertogh, M.J.C.M.; Bosch-Rekveldt, M.G.C.; Blom, R.; Serpell, A.; Ferrada, X.

    2016-01-01

    Still, projects in the construction sector are delivered with time delays and cost overruns. One of the reasons for poor performance was assigned to project complexity. A combination of lean construction and agile project management are hypothesized as a possible solution to cope with project

  3. Simultaneous mass transfer of H2S and CO2 with complex chemical reactions in an aqueous di-isopropanolamine solution = Gleichzeitige absorption von H2S und CO2 in Wässriger Di-isopropanolaminlösung

    NARCIS (Netherlands)

    Blauwhoff, P.M.M.; van Swaaij, Willibrordus Petrus Maria

    1985-01-01

    The absorption of H2S and CO2 into an aqueous di-isopropanolamine (DIPA) solution was studied experimentally and theoretically as an example of simultaneous mass transfer with complex reversible reactions. The absorption phenomena were classified into three regimes: (1) negligible mutual interaction

  4. Superconducting properties of GdBa{sub 2}Cu{sub 3}O{sub y} films by metal-organic deposition using new fluorine-free complex solutions

    Energy Technology Data Exchange (ETDEWEB)

    Nakamura, T. [Department of Electrical and Electronic Engineering, Faculty of Engineering, Shizuoka University, Johoku 3-5-1, Hamamatsu, Shizuoka 432-8561 (Japan); Kita, R. [Department of Electrical and Electronic Engineering, Faculty of Engineering, Shizuoka University, Johoku 3-5-1, Hamamatsu, Shizuoka 432-8561 (Japan); CREST-JST, Honcho 4-1-8, Kawaguchi, Saitama 332-0012 (Japan)], E-mail: terkita@ipc.shizuoka.ac.jp; Miura, O. [Tokyo Metropolitan University, Minamiosawa 1-1, Hachioji, Tokyo 192-0364 (Japan); CREST-JST, Honcho 4-1-8, Kawaguchi, Saitama 332-0012 (Japan); Ichinose, A. [CRIEPI, Nagasaka 2-6-1, Yokosuka, Kanagawa 240-0916 (Japan); CREST-JST, Honcho 4-1-8, Kawaguchi, Saitama 332-0012 (Japan); Matsumoto, K. [Kyushu Institute of Techonology, Sensui-cho, Tobata-ku, Kitakyushu, Hukuoka 804-8550 (Japan); CREST-JST, Honcho 4-1-8, Kawaguchi, Saitama 332-0012 (Japan); Yoshida, Y. [Nagoya University, Furo-cho, Chikusa-ku, Nagoya 464-8603 (Japan); CREST-JST, Honcho 4-1-8, Kawaguchi, Saitama 332-0012 (Japan); Mukaida, M. [Kyushu University, Hakozaki 6-10-1, Higashi-ku 4-3-16, Fukuoka 992-8510 (Japan); CREST-JST, Honcho 4-1-8, Kawaguchi, Saitama 332-0012 (Japan); Horii, S. [University of Tokyo, Hongo 7-3-1, Bunkyo-ku, Tokyo 113-8586 (Japan); CREST-JST, Honcho 4-1-8, Kawaguchi, Saitama 332-0012 (Japan)

    2008-09-15

    GdBa{sub 2}Cu{sub 3}O{sub y} (GdBCO) films have been prepared on LaAlO{sub 3} single-crystal substrates by metal-organic deposition (MOD) using new fluorine-free complex solutions consisting of metal 2-ethylhexanates (2-EH) and metal naphthenates. The dispersion of T{sub c} values for GdBCO films improved by using a complex solution, rather than only a solution of metal naphthenates. c-axis oriented GdBCO films with flat surfaces were grown under lower calcining temperatures and higher firing temperatures than in the process using only metal naphthenates. The T{sub c} and J{sub c} of the GdBCO films were 91.2 K and 0.61 MA/cm{sup 2}, respectively, at 77 K at self-field.

  5. Are the energy poor also income poor? Evidence from India

    International Nuclear Information System (INIS)

    Khandker, Shahidur R.; Barnes, Douglas F.; Samad, Hussain A.

    2012-01-01

    The energy poverty line is defined as the threshold point at which energy consumption begins to rise with increases in household income. This approach is applied to cross-sectional data from a comprehensive 2005 household survey representative of both urban and rural India. The objective is to determine if the energy poor are also income poor and whether and how energy policies help reduce energy poverty, independent of income. The findings suggest that in rural areas some 57% of households are energy poor, versus 22% that are income poor. But in urban areas the energy poverty rate is 28% compared to 20% that are income poor. That is, energy policies are expected to play some roles in mitigating energy poverty. We find that reducing energy poverty requires not only support for rural electrification, but also more use of modern cooking fuels such as LPG. While income growth matters, a combination of energy related programs can play an independent and substantial role in reducing energy poverty. - Highlights: ► This paper applies a new approach to measuring energy poverty to rural and urban India. ► It also compares and contrasts income poverty with energy poverty in the context of India. ► Findings suggest that income poverty tracks energy poverty in urban India, but not in rural India. ► Income growth is very important in reducing energy poverty. ► In addition, access to and reliability of modern sources (electricity, LPG) are also helpful.

  6. Isotopic studies on ligand exchange between complex and simple cyanides in water medium and in liquid hydrogen cyanide. Part 2. Radiocyanide ligand exchange study between hydrogen cyanide and octacyanotungstate(4) in water solutions of mineral acids

    International Nuclear Information System (INIS)

    Zielinski, M.

    1979-01-01

    Radiocyanide ligand exchange between potassium octacyanotungstate(4) and hydrogen cyanide in aqueous solutions of sulfuric acid and between octacyanotungstic(4) acid and hydrogen cyanide in aqueous solutions have been investigated experimentally. The observed enhancement of the rate of ligand exchange in acidic medium has been rationalized in terms of the proposed new general reaction scheme taking into account the reversible decomposition of complex cyanide at low pH, and irreversible one at high pH. The discussion on the results obtained has been carried out within the framework of derived formal kinetic equations. (author)

  7. Synthesis and reactivity of TADDOL-based chiral Fe(II) PNP pincer complexes-solution equilibria between κ(2)P,N- and κ(3)P,N,P-bound PNP pincer ligands.

    Science.gov (United States)

    Holzhacker, Christian; Stöger, Berthold; Carvalho, Maria Deus; Ferreira, Liliana P; Pittenauer, Ernst; Allmaier, Günter; Veiros, Luis F; Realista, Sara; Gil, Adrià; Calhorda, Maria José; Müller, Danny; Kirchner, Karl

    2015-08-07

    Treatment of anhydrous FeX2 (X = Cl, Br) with 1 equiv. of the asymmetric chiral PNP pincer ligands PNP-R,TAD (R = iPr, tBu) with an R,R-TADDOL (TAD) moiety afforded complexes of the general formula [Fe(PNP)X2]. In the solid state these complexes adopt a tetrahedral geometry with the PNP ligand coordinated in κ(2)P,N-fashion, as shown by X-ray crystallography and Mössbauer spectroscopy. Magnetization studies led to a magnetic moment very close to 4.9μB reflecting the expected four unpaired d-electrons (quintet ground state). In solution there are equilibria between [Fe(κ(3)P,N,P-PNP-R,TAD)X2] and [Fe(κ(2)P,N-PNP-R,TAD)X2] complexes, i.e., the PNP-R,TAD ligand is hemilabile. At -50 °C these equilibria are slow and signals of the non-coordinated P-TAD arm of the κ(2)P,N-PNP-R,TAD ligand can be detected by (31)P{(1)H} NMR spectroscopy. Addition of BH3 to a solution of [Fe(PNP-iPr,TAD)Cl2] leads to selective boronation of the pendant P-TAD arm shifting the equilibrium towards the four-coordinate complex [Fe(κ(2)P,N-PNP-iPr,TAD(BH3))Cl2]. DFT calculations corroborate the existence of equilibria between four- and five-coordinated complexes. Addition of CO to [Fe(PNP-iPr,TAD)X2] in solution yields the diamagnetic octahedral complexes trans-[Fe(κ(3)P,N,P-PNP-iPr,TAD)(CO)X2], which react further with Ag(+) salts in the presence of CO to give the cationic complexes trans-[Fe(κ(3)P,N,P-PNP-iPr,TAD)(CO)2X](+). CO addition most likely takes place at the five coordinate complex [Fe(κ(3)P,N,P-PNP-iPr,TAD)X2]. The mechanism for the CO addition was also investigated by DFT and the most favorable path obtained corresponds to the rearrangement of the pincer ligand first from a κ(2)P,N- to a κ(3)P,N,P-coordination mode followed by CO coordination to [Fe(κ(3)P,N,P-PNP-iPr,TAD)X2]. Complexes bearing tBu substituents do not react with CO. Moreover, in the solid state none of the tetrahedral complexes are able to bind CO.

  8. Developing or Managing the Poor: The Complexities and ...

    African Journals Online (AJOL)

    The new South African government since 2001 developed what might be called a skeletal welfare system that extends social grants, infrastructure and free services to millions of previously deprived citizens. Extending electricity is held up as a major developmental intervention. A free amount of household electricity has ...

  9. Study of the selectivity of poly-nitrogenous extracting molecules in the complexation of actinides (III) and lanthanides (III) in solution in anhydrous pyridine

    International Nuclear Information System (INIS)

    Riviere, Ch.

    2000-01-01

    The aim of this work is to better understand the factors which contribute to the separation of lanthanides(III) and actinides(III). Polydentate nitrogenous molecules present an interesting selectivity. A thermodynamic study of the complexation in pyridine of lanthanide and uranium by the bipyridine ligand (bipy) has been carried out. The formation constants and the thermodynamic values of the different complexes have been determined. It has been shown that the bipy complexes formation is controlled by the enthalpy and unfavored by the entropy. The conductometry has revealed too a significant difference in the uranium and lanthanides complexation by the bipyridine ligand. The use of the phenanthroline ligand induces a better complexation of the metallic ions but the selectivity is not improved. On the other hand, the decrease of the basicity and the increase of the ligand denticity (for instance in the case of the use of ter-pyridine) favour the selectivity without improving the complexation. The selectivity difference for the complexation of actinides(III) and lanthanides(III) by the different studied ligands (independent systems) has been confirmed by experiments of inter-metals competition. (O.M.)

  10. Spectrophotometric Analysis of the Kinetic of Pd(II Chloride Complex Ions Sorption Process from Diluted Aqua Solutions Using Commercially Available Activated Carbon

    Directory of Open Access Journals (Sweden)

    Wojnicki M.

    2017-12-01

    Full Text Available In this paper, results of adsorption kinetic studies of Pd(II chloride complex ions on activated carbon Organosrob 10 CO are presented. Spectorphotometrical method was applied to investigate the process. Kinetic model was proposed, and fundamental thermodynamic parameters were determined. Proposed kinetic model describes well observed phenomenon in the studied range of concentration of Pd(II chloride complex ions as well, as concentration of activated carbon.

  11. Study of Sr sup 2+ and Eu sup 2+ complexing with 18-crown-6 in aqueous-ethanolic solutions. Izuchenie kompleksoobrazovaniya Sr sup 2+ i Eu sup 2+ s 18-kraun-6 v vodno-ehtanol'nykh rastvorakh

    Energy Technology Data Exchange (ETDEWEB)

    Kulyukhin, S A; Majorov, A V; Kamenskaya, A N; Mikheev, N B

    1989-01-01

    Using cocrystallization and conductometry methods Sr{sup 2+} and Eu{sup 2+} complexing with 18-crown-6 in aqueous-ethanolic solutions at (H{sub 2}O)=10 mol/l is studied. Stability constants of Sr{sup 2+} and Eu{sup 2+} complexes with 18-crown-6 in C{sub 2}H{sub 5}OH, for which lg{beta} is equal to (4.76{plus minus}0.12) and (4.72{plus minus}0.13) respectively, are determined. Comparison of the investigated elements features during complexing with 18-crown-6 in aqueous and aqueous-ethanolic solutions is carried out. It is shown that both in water and in C{sub 2}H{sub 5}OH -10 mol/l H{sub 2}O system under Sr{sup 2+} and Eu{sup 2+} complexing with 18-crown-6 the differences in properties of these elements are not detected.

  12. Effects of Ligands on a Ternary Hydroxo Complex Formation with Eu(III) in a Aqueous Solution: Comparison of a Pyridine-2,6-dicarboxylate with a Phthalate

    International Nuclear Information System (INIS)

    Park, K. K.; Cho, H. R.; Kim, W. H.; Jung, E. C.

    2008-01-01

    The interaction of a radionuclide with ligands in a groundwater influences its migration through a hydrogeological system due to a change in the characteristics of a dissolution and a sorption. Actinide ions are classified as a hard acid and strongly interact with ligands having an oxygen donor atom of a hard base such as a hydroxide, carbonate and carboxylate. These ligands reveal a large ionic bonding character. A number of experimental results on a binary complex formation of actinides have been reported. However, actinides may easily form a ternary complex by interacting simultaneously with two different ligands, since an ionic bonding does not restrict the spatial orientation of a ligand. In previous studies, a ternary hydroxo complex formation was investigated by using pyridine-2,6-dicarboxylate (PDA) or phthalate as an organic ligand and Eu(III) as an analogue of an actinide(III) ion. Although these organic ligands equally contain two carboxylate groups that interact with an Eu(III) ion, their stabilities reveal big differences. PDA is a tridentate ligand forming two 5-membered chelates, while phthalate is a bidentate ligand forming a 7-membered chelate. The latter reveals a lower stability than the former due to an angle strain. This is one of the reasons for the lower stability of the Eu(III)-phthalate than that of the Eu(III)- PDA. The difference in the stabilities of binary complexes, EuL + (L=organic ligand), influences the stabilities of the ternary hydroxo complexes, Eu(OH)L. The coordination of a phenylic or pyridine ligand can greatly enhance the fluorescence of an Eu(III) ion due to the high absorbance of a ligand by a π → π * transition and the transfer of this energy to an Eu(III) ion. These fluorescence characteristics in a binary complex system could be changed in a ternary complex. In this study, the effect of a ligand on the stability of a ternary hydroxo complex is reported by comparing the stabilities of Eu-PDA with Eu-phthalate systems

  13. Solution NMR investigation of the CD95/FADD homotypic death domain complex suggests lack of engagement of the CD95 C terminus.

    Science.gov (United States)

    Esposito, Diego; Sankar, Andrew; Morgner, Nina; Robinson, Carol V; Rittinger, Katrin; Driscoll, Paul C

    2010-10-13

    We have addressed complex formation between the death domain (DD) of the death receptor CD95 (Fas/APO-1) with the DD of immediate adaptor protein FADD using nuclear magnetic resonance (NMR) spectroscopy, mass spectrometry, and size-exclusion chromatography with in-line light scattering. We find complexation to be independent of the C-terminal 12 residues of CD95 and insensitive to mutation of residues that engage in the high-order clustering of CD95-DD molecules in a recently reported crystal structure obtained at pH 4. Differential NMR linewidths indicate that the C-terminal region of the CD95 chains remains in a disordered state and (13)C-methyl TROSY data are consistent with a lack of high degree of symmetry for the complex. The overall molecular mass of the complex is inconsistent with that in the crystal structure, and the complex dissociates at pH 4. We discuss these findings using sequence analysis of CD95 orthologs and the effect of FADD mutations on the interaction with CD95. Copyright © 2010 Elsevier Ltd. All rights reserved.

  14. Effect of solvents on relation of intensities of bands of luminescence spectra of terbium and dysprosium ions in solutions of their complexes with acetoacetic ester

    International Nuclear Information System (INIS)

    Kononenko, L.I.; Bel'tyukova, S.V.; Meshkova, S.B.; Kravchenko, T.B.; Poluehktov, N.S.

    1978-01-01

    An investigation is made of the effect of different solvents on the ratio of the intensity of luminescence spectrum bands of terbium and dysprosium ions, corresponding and not corresponding to ''supersensitive'' transitions in complex compounds with acetoacetic ether. A dependence is established between these values and the dielectric constant of the solvent, and also parallels in their changes, which indicate the similar manifestation of the effect of solvents in both elements. A correlation is observed between ratios of the intensity of luminescence spectrum bands and values of forces of neodymium complex absorption band oscillators in different solvents

  15. Testosterone for Poor Ovarian Responders

    DEFF Research Database (Denmark)

    Polyzos, Nikolaos P; Davis, Susan R; Drakopoulos, Panagiotis

    2016-01-01

    Testosterone, an androgen that directly binds to the androgen receptor, has been shown in previous small randomized controlled trials to increase the reproductive outcomes of poor ovarian responders. In most of these studies, transdermal testosterone in relatively high doses was administered before...... ovarian stimulation with a duration varying from 5 to 21 days. Nevertheless, the key question to be asked is whether, based on ovarian physiology and testosterone pharmacokinetics, a short course of testosterone administration of more than 10 mg could be expected to have any beneficial effect...... stages. In addition, extreme testosterone excess is not only likely to induce adverse events but has also the potential to be ineffective and even detrimental. Thus, evidence from clinical studies is not enough to either "reopen" or "close" the "androgen chapter" in poor responders, mainly because...

  16. Structural and thermodynamic aspects of aqueous solution of trivalent lanthanides complexation by hydrophobic compounds of tartaric acid, by gluconic acid and related molecules. Outlook for liquid-liquid extraction of these cations

    International Nuclear Information System (INIS)

    Giroux, Sebastien

    1999-01-01

    This work deals with the complexation of lanthanide(III) ions by different molecules and with the synthesis of hydrophobic molecules able to extract them of an aqueous solution. Its aim is to describe the systems obtained by the determination of the formation constants of the species and by the description of their structure. The aim of this work is also to obtain a selective complexation of lanthanides(III) towards actinides(III), because this aim presents a great interest in the reprocessing of radioactive wastes. The complexation studies have been followed by potentiometry, NMR, UV-visible spectroscopy and circular dichroism. The first mixtures studied are the couples: lanthanide(III)-gluconic acid (LH). The complexes system they formed has been described and the structures have been specified; a strong complexation has been revealed. The MLH -2 specie induces a selectivity between the lanthanides(III) equivalent to those obtained with EDTA and its uncharged character allows to consider the use of gluconic acid as extractant. The use of ligands as glucosaminic acid or glucamine slows the beginning of the complexation until pH= 6-7. The neutral specie MLH -2 is formed too. In order to use the complexing properties of gluconic acid and its selective character towards lanthanides(III), the synthesis of molecules derived containing a long alkyl chain with a hydrophobic character has been carried out for using them as extracting agents. An original method of the preparation of tartramides is presented. This preparation consists of an amidation of one of the carboxylic functions of the tartaric acid by a fatty amine. These molecules, surface-active, complex the lanthanides(III) and extract them in an organic phase using the tri-n-butyl phosphate as co-extractant. (O.M.)

  17. Determination of formal redox potentials in aqueous solution of copper(II) complexes with ligands having nitrogen and oxygen donor atoms and comparison with their EPR and UV-Vis spectral features.

    Science.gov (United States)

    Tabbì, Giovanni; Giuffrida, Alessandro; Bonomo, Raffaele P

    2013-11-01

    Formal redox potentials in aqueous solution were determined for copper(II) complexes with ligands having oxygen and nitrogen as donor atoms. All the chosen copper(II) complexes have well-known stereochemistries (pseudo-octahedral, square planar, square-based pyramidal, trigonal bipyramidal or tetrahedral) as witnessed by their reported spectroscopic, EPR and UV-visible (UV-Vis) features, so that a rough correlation between the measured redox potential and the typical geometrical arrangement of the copper(II) complex could be established. Negative values have been obtained for copper(II) complexes in tetragonally elongated pseudo-octahedral geometries, when measured against Ag/AgCl reference electrode. Copper(II) complexes in tetrahedral environments (or flattened tetrahedral geometries) show positive redox potential values. There is a region, always in the field of negative redox potentials which groups the copper(II) complexes exhibiting square-based pyramidal arrangements. Therefore, it is suggested that a measurement of the formal redox potential could be of great help, when some ambiguities might appear in the interpretation of spectroscopic (EPR and UV-Vis) data. Unfortunately, when the comparison is made between copper(II) complexes in square-based pyramidal geometries and those in square planar environments (or a pseudo-octahedral) a little perturbed by an equatorial tetrahedral distortion, their redox potentials could fall in the same intermediate region. In this case spectroscopic data have to be handled with great care in order to have an answer about a copper complex geometrical characteristics. © 2013.

  18. Sensitive determination of adenosine disodium triphosphate in soil, milk, and pharmaceutical formulation by enoxacin–europium (III) fluorescence complex in solution

    International Nuclear Information System (INIS)

    Alam, Al-Mahmnur; Kamruzzaman, Mohammad; Hak Lee, Sang; Ho Kim, Young; Jin Jo, Hae; Hong Kim, Sung; Park, Sang-Ryoul

    2012-01-01

    A new spectroflurometric method for the determination of adenosine disodium triphosphate (ATP) is developed. Fluorometric interaction between ATP and enoxacin (ENX)–Eu 3+ complex was studied using UV–vis and fluorescence spectroscopy. Weak luminescence spectra of Eu 3+ were enhanced after complexation with ENX at 589 nm and 614 nm upon excitation at 395 nm due to energy transfer from the ligand to the lanthanide ion. It was observed that luminescence spectrum of Eu 3+ was strongly enhanced further at 614 nm after incorporation of ATP into the ENX–Eu 3+ complex. Under optimal conditions, the enhancement of luminescence at 614 nm was responded linearly with the concentration of ATP. The linearity was maintained in the range of 1.5×10 −10 –1.15×10 −8 M (R=0.9973) with the limit of detection (3σ) of 4.71×10 −11 M. The relative standard deviation (RSD) for 9 repeated measurements of 1×10 −9 M ATP was 1.25%. Successful determinations of ATP in soil, milk, and a pharmaceutical formulation with the proposed method were demonstrated. - Highlights: ► Weak luminescence of Eu 3+ was enhanced at 614 nm after formation of complex with ENX. ► Energy transfer occurs through FRET from ENX to Eu 3+ upon excitation. ► Luminescence signal was further enhanced when ATP conjugates with ENX–Eu 3+ complex. ► Luminescence intensity of Eu 3+ at 614 nm was correlated with concentration of ATP. ► The method was applied to determine ATP in soil, milk, and pharmaceutical samples.

  19. Energy poor or fuel poor: What are the differences?

    International Nuclear Information System (INIS)

    Li, Kang; Lloyd, Bob; Liang, Xiao-Jie; Wei, Yi-Ming

    2014-01-01

    Energy poverty and fuel poverty are descriptors of problems of households' energy consumption, they are both distinct problems and have been addressed by many researchers, organizations and governments. Cross use of the terms of energy poverty and fuel poverty in published papers is common. As an accurate descriptor is the presupposition of research and policy development, especially for those who just started to pay attention to this issue, this paper compares the definitions, research priorities, status quo, and problems of these two concepts, and summarizes the relationship between them. The paper suggests that only when the research targets are households who are living in a cold climate and have difficulty in getting access to electricity or modern cooking facilities, and in supplying indoor heating with appropriate cost, the concepts of energy poverty and fuel poverty have the chance to be broadened and mutually integrated. - Highlights: • Address energy poverty and fuel poverty simultaneously. • Compare energy poverty and fuel poverty from 4 perspectives. • Summarize the relationship between energy poverty and fuel poverty. • Divide energy poor and fuel poor into three categories

  20. One-electron reduction of 1,2-dihydroxy-9,10-anthraquinone and some of its transition metal complexes in aqueous solution and in aqueous isopropanol-acetone-mixed solvent: a steady-state and pulse radiolysis study

    International Nuclear Information System (INIS)

    Das, S.; Bhattacharya, A.; Mandal, P.C.; Rath, M.C.; Mukherjee, T.

    2002-01-01

    One-electron reduction of 1,2-dihydroxy-9,10-anthraquinone (DHA) and its complexes with Cu(II), Ni(II) and Fe(III), by acetone ketyl radical, (CH 3 ) 2 C·OH, was carried out in aqueous solution and in aqueous isopropanol acetone mixed solvent using both steady-state gamma radiolysis and pulse radiolysis techniques. The rate constants for the reduction of DHA at different pH values by the ketyl radical are in the order of ∼10 9 dm 3 mol -1 s -1 , whereas those for the metal complexes are comparatively less. These rate constants are, however, in conformity with the one-electron reduction potentials of the ligand in free DHA and in its metal complexes. Decay kinetics of the one-electron reduced semiquinones of the free ligand and its metal complexes suggest disproportionation of the semiquinone in the case of the free ligand and intermolecular electron transfer from the co-ordinated semiquinone radical to the metal centre in the case of the metal complexes