WorldWideScience

Sample records for solution complexation mechanism

  1. 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)

  2. 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

  3. Nonextensive statistical mechanics of ionic solutions

    International Nuclear Information System (INIS)

    Varela, L.M.; Carrete, J.; Munoz-Sola, R.; Rodriguez, J.R.; Gallego, J.

    2007-01-01

    Classical mean-field Poisson-Boltzmann theory of ionic solutions is revisited in the theoretical framework of nonextensive Tsallis statistics. The nonextensive equivalent of Poisson-Boltzmann equation is formulated revisiting the statistical mechanics of liquids and the Debye-Hueckel framework is shown to be valid for highly diluted solutions even under circumstances where nonextensive thermostatistics must be applied. The lowest order corrections associated to nonadditive effects are identified for both symmetric and asymmetric electrolytes and the behavior of the average electrostatic potential in a homogeneous system is analytically and numerically analyzed for various values of the complexity measurement nonextensive parameter q

  4. 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)

  5. Pitfall in quantum mechanical/molecular mechanical molecular dynamics simulation of small solutes in solution.

    Science.gov (United States)

    Hu, Hao; Liu, Haiyan

    2013-05-30

    Developments in computing hardware and algorithms have made direct molecular dynamics simulation with the combined quantum mechanical/molecular mechanical methods affordable for small solute molecules in solution, in which much improved accuracy can be obtained via the quantum mechanical treatment of the solute molecule and even sometimes water molecules in the first solvation shell. However, unlike the conventional molecular mechanical simulations of large molecules, e.g., proteins, in solutions, special care must be taken in the technical details of the simulation, including the thermostat of the solute/solvent system, so that the conformational space of the solute molecules can be properly sampled. We show here that the common setup for classical molecular mechanical molecular dynamics simulations, such as the Berendsen or single Nose-Hoover thermostat, and/or rigid water models could lead to pathological sampling of the solutes' conformation. In the extreme example of a methanol molecule in aqueous solution, improper and sluggish setups could generate two peaks in the distribution of the O-H bond length. We discuss the factors responsible for this somewhat unexpected result and evoke a simple and ancient technical fix-up to resolve this problem.

  6. 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

  7. 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.

  8. 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.

  9. Calculating solution redox free energies with ab initio quantum mechanical/molecular mechanical minimum free energy path method

    International Nuclear Information System (INIS)

    Zeng Xiancheng; Hu Hao; Hu Xiangqian; Yang Weitao

    2009-01-01

    A quantum mechanical/molecular mechanical minimum free energy path (QM/MM-MFEP) method was developed to calculate the redox free energies of large systems in solution with greatly enhanced efficiency for conformation sampling. The QM/MM-MFEP method describes the thermodynamics of a system on the potential of mean force surface of the solute degrees of freedom. The molecular dynamics (MD) sampling is only carried out with the QM subsystem fixed. It thus avoids 'on-the-fly' QM calculations and thus overcomes the high computational cost in the direct QM/MM MD sampling. In the applications to two metal complexes in aqueous solution, the new QM/MM-MFEP method yielded redox free energies in good agreement with those calculated from the direct QM/MM MD method. Two larger biologically important redox molecules, lumichrome and riboflavin, were further investigated to demonstrate the efficiency of the method. The enhanced efficiency and uncompromised accuracy are especially significant for biochemical systems. The QM/MM-MFEP method thus provides an efficient approach to free energy simulation of complex electron transfer reactions.

  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. CEC mechanism in electrochemical oxidation of nitrocatechol-boric acid complexes

    International Nuclear Information System (INIS)

    Rafiee, Mohammad; Nematollahi, Davood; Salehzadeh, Hamid

    2011-01-01

    Graphical abstract: Display Omitted Highlights: → Nitrochetechol and its anionic form undergo complex reaction with boric acid. → The electron transfer of complex is coupled with both proceeding and following chemical reactions. → Electrochemical behavior of complex is resolved by diagnostic criteria and digital simulation. - Abstract: The electrochemical behavior of nitrocatechols-boric acid complexes in aqueous solution has been studied using cyclic voltammetry. The results indicate that nitrocatechol-boric acid complex derivatives are involved in the CEC mechanism. In this work, the impact of empirical parameters on the shape of the voltammograms is examined based on a CEC mechanism. In addition, homogeneous rate constants of both the preceding and the following reactions were estimated by comparing the experimental cyclic voltammograms with the digitally simulated results. The calculated dissociation constants for the complexes (K d ) and for ring cleavage of nitroquinone (k f2 ) were found to vary in the following order: 4-nitrocatechol > 3-methylnitrocatechol > 3-metoxynitrocatechol.

  12. Kinetics and mechanism of nitrobenzene hydrogenation to phenylhydroxylamine in rhenium thiocomplexes solutions

    International Nuclear Information System (INIS)

    Korenyako, G.I.; Belousov, V.M.

    1985-01-01

    A study was made on kinetics of nitrobenzene hydrogenation to phenylhydroxylamine in dimethylformamide solutions of rhenium thiocomplexes. The mechanism of hydrogenation was suggested. Formation of hydride catalyst complex represents the first stage of the process. Kinetic equation derived on the basis of suggested mechanism corresponds satisfactorily with experimental results. Thermodynamic parameters of separate process stages calculated on the basis of equilibrium constant values testify as well to the benefit of suggested mechanism

  13. 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.

  14. 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.

  15. 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

  16. Mechanism of host-guest complexation by cucurbituril.

    Science.gov (United States)

    Márquez, César; Hudgins, Robert R; Nau, Werner M

    2004-05-12

    The factors affecting host-guest complexation between the molecular container compound cucurbit[6]uril (CB6) and various guests in aqueous solution are studied, and a detailed complexation mechanism in the presence of cations is derived. The formation of the supramolecular complex is studied in detail for cyclohexylmethylammonium ion as guest. The kinetics and thermodynamics of complexation is monitored by NMR as a function of temperature, salt concentration, and cation size. The binding constants and the ingression rate constants decrease with increasing salt concentration and cation-binding constant, in agreement with a competitive binding of the ammonium site of the guest and the metal cation with the ureido carbonyl portals of CB6. Studies as a function of guest size indicate that the effective container volume of the CB6 cavity is approximately 105 A(3). It is suggested that larger guests are excluded for two reasons: a high activation barrier for ingression imposed by the tight CB6 portals and a destabilization of the complex due to steric repulsion inside. For example, in the case of the nearly spherical azoalkane homologues 2,3-diazabicyclo[2.2.1]hept-2-ene (DBH, volume ca. 96 A(3)) and 2,3-diazabicyclo[2.2.2]oct-2-ene (DBO, volume ca. 110 A(3)), the former forms the CB6 complex promptly with a sizable binding constant (1300 M(-1)), while the latter does not form a complex even after several months at optimized complexation conditions. Molecular mechanics calculations are performed for several CB6/guest complexes. A qualitative agreement is found between experimental and calculated activation energies for ingression as a function of both guest size and state of protonation. The potential role of constrictive binding by CB6 is discussed.

  17. 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

  18. 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

  19. 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

  20. 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.

  1. 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

  2. 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

  3. Exposure to buffer solution alters tendon hydration and mechanics.

    Science.gov (United States)

    Safa, Babak N; Meadows, Kyle D; Szczesny, Spencer E; Elliott, Dawn M

    2017-08-16

    A buffer solution is often used to maintain tissue hydration during mechanical testing. The most commonly used buffer solution is a physiological concentration of phosphate buffered saline (PBS); however, PBS increases the tissue's water content and decreases its tensile stiffness. In addition, solutes from the buffer can diffuse into the tissue and interact with its structure and mechanics. These bathing solution effects can confound the outcome and interpretation of mechanical tests. Potential bathing solution artifacts, including solute diffusion, and their effect on mechanical properties, are not well understood. The objective of this study was to measure the effects of long-term exposure of rat tail tendon fascicles to several concentrations (0.9-25%) of NaCl, sucrose, polyethylene glycol (PEG), and SPEG (NaCl+PEG) solutions on water content, solute diffusion, and mechanical properties. We found that with an increase in solute concentration the apparent water content decreased for all solution types. Solutes diffused into the tissue for NaCl and sucrose, however, no solute diffusion was observed for PEG or SPEG. The mechanical properties changed for both NaCl solutions, in particular after long-term (8h) incubation the modulus and equilibrium stress decreased compared to short-term (15min) for 25% NaCl, and the cross sectional area increased for 0.9% NaCl. However, the mechanical properties were unchanged for both PEG and SPEG except for minor alterations in stress relaxation parameters. This study shows that NaCl and sucrose buffer solutions are not suitable for long-term mechanical tests. We therefore propose using PEG or SPEG as alternative buffer solutions that after long-term incubation can maintain tissue hydration without solute diffusion and produce a consistent mechanical response. Copyright © 2017 Elsevier Ltd. All rights reserved.

  4. 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 ...

  5. Fluid mechanics problems and solutions

    CERN Document Server

    Spurk, Joseph H

    1997-01-01

    his collection of over 200 detailed worked exercises adds to and complements the textbook Fluid Mechanics by the same author, and illustrates the teaching material through examples. In the exercises the fundamental concepts of Fluid Mechanics are applied to obtaining the solution of diverse concrete problems, and in doing this the student's skill in the mathematical modeling of practical problems is developed. In addition, 30 challenging questions without detailed solutions have been included, and while lecturers will find these questions suitable for examinations and tests, the student himself can use them to check his understanding of the subject.

  6. 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.

  7. 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.

  8. 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)

  9. 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.

  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. 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.

  12. 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.

  13. Influence of complexing agents on the mechanical performances of the cement conditioning matrix

    International Nuclear Information System (INIS)

    Nicu, M.; Mihai, F.; Turcanu, C.

    1998-01-01

    The safety of the radioactive waste disposal is a priority demand concerning the protection of the environment and population. For this reason, an engineering multi-barrier system is studied in order to be improved. This study aims to establish the influence of the complexing agents on the mechanical performances of the cement conditioning matrix. Radioactive effluents which contain agents as oxalic and citric acids are generated during the radioactive decontamination operation using chemical methods. The conditioning of these wastes by cementing process imposed the experimental determination of the mechanical performances of the matrix and the upper permissible level of complexing agent concentration. To determine the influence of complexing agents on the mechanical performances of cement conditioning matrix, cubic samples (20 mm x 20 mm x 20 mm) were prepared using commercial Portland cement and solutions of organic complexing acids or salts (citric acid, oxalic acid, tartaric acid, sodium citrate and ammonium oxalate). The complexation concentration varied between 0.25% and 1% in distilled and drinking water, respectively. The selected cement/water ratio was 0.5. The experiments were focused on: - establishing the firmness of the Pa 35 cement pastes and mortars in dependence on the water/cement ratio, by classical methods (Tetmeyer probe for pastes and standard cone for mortars) and by triclinic time through a funnel with 15 mm aperture; - studying the influence of the tartaric, oxalic, citric acids, ammonium oxalate and sodium citrate solution concentrations on water quantities used to obtain pastes with normal firmness and on Pa 35 cement setting; - the influence of oxalic acid, tartaric acid and ammonium oxalate solution concentrations on the strength of compression of the pastes with normal firmness; - for testing, standard test bar cubes with 20 mm sides were used and the strength of compression was tested at 28 days; - establishing the behaviour in time of

  14. 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.

  15. 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.

  16. 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.

  17. 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

  18. Multi-level quantum mechanics theories and molecular mechanics study of the double-inversion mechanism of the F- + CH3I reaction in aqueous solution.

    Science.gov (United States)

    Liu, Peng; Zhang, Jingxue; Wang, Dunyou

    2017-06-07

    A double-inversion mechanism of the F - + CH 3 I reaction was discovered in aqueous solution using combined multi-level quantum mechanics theories and molecular mechanics. The stationary points along the reaction path show very different structures to the ones in the gas phase due to the interactions between the solvent and solute, especially strong hydrogen bonds. An intermediate complex, a minimum on the potential of mean force, was found to serve as a connecting-link between the abstraction-induced inversion transition state and the Walden-inversion transition state. The potentials of mean force were calculated with both the DFT/MM and CCSD(T)/MM levels of theory. Our calculated free energy barrier of the abstraction-induced inversion is 69.5 kcal mol -1 at the CCSD(T)/MM level of theory, which agrees with the one at 72.9 kcal mol -1 calculated using the Born solvation model and gas-phase data; and our calculated free energy barrier of the Walden inversion is 24.2 kcal mol -1 , which agrees very well with the experimental value at 25.2 kcal mol -1 in aqueous solution. The calculations show that the aqueous solution makes significant contributions to the potentials of mean force and exerts a big impact on the molecular-level evolution along the reaction pathway.

  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. 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

  1. 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.

  2. Influence aqueous solutions on the mechanical behavior of argillaceous rocks

    International Nuclear Information System (INIS)

    Wakim, J.

    2005-12-01

    The hydration of the shale with an aqueous solution induces a swelling deformation which plays an important role in the behaviour of the structures excavated in this type of grounds. This deformation is marked by a three-dimensional and anisotropic character and involves several mechanisms like adsorption, osmosis or capillarity. Several researches were dedicated to swelling and were often much debated due to the complexity of the implied phenomena. The goal of this thesis is therefore to contribute to a better understanding of shale swelling when the rock is confined and hydrated with an aqueous solution. The main part of the work accomplished was related to the Lorraine shale and to the Tournemire shale. To characterize swelling and to identify the main governing parameters, it was necessary to start the issue with an experimental approach. Many apparatus were then developed to carry out tests under various conditions of swelling. In order to facilitate the interpretation of the tests and thereafter the modelling of the behaviour, the experimental procedure adopted consisted of studying first the mechanical aspect and then the chemical aspect of swelling. In the mechanical part, swelling was studied by imposing on the sample a mechanical loading while maintaining during the tests the same aqueous solution. The principal parameters which were studied are the effect of the lateral conditions on axial swelling (impeded strain or constant stress) as well as the influence of the axial stress on radial swelling. The anisotropy of swelling was studied by carrying out, for different orientations of the sample, tests of free swelling, impeded swelling and uniaxial swelling. These various mechanical tests allowed to study the three-dimensional anisotropic swelling in all the conditions and to select the most appropriate test to be used in the second phase of the research. The precise analysis performed to explain the mechanisms behind the swelling of an argillaceous rock

  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. 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.

  5. 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.

  6. 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.

  7. 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.

  8. 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.

  9. 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

  10. 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

  11. 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)

  12. 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 .

  13. 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

  14. 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

  15. Whole analogy between Daniel Bernoulli solution and direct kinematics solution

    Directory of Open Access Journals (Sweden)

    Filipović Mirjana

    2010-01-01

    Full Text Available In this paper, the relationship between the original Euler-Bernoulli's rod equation and contemporary knowledge is established. The solution which Daniel Bernoulli defined for the simplest conditions is essentially the solution of 'direct kinematics'. For this reason, special attention is devoted to dynamics and kinematics of elastic mechanisms configuration. The Euler-Bernoulli equation and its solution (used in literature for a long time should be expanded according to the requirements of the mechanisms motion complexity. The elastic deformation is a dynamic value that depends on the total mechanism movements dynamics. Mathematical model of the actuators comprises also elasticity forces.

  16. 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.

  17. [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.

  18. Kinetics and mechanism of sphalerite leaching by sodium nitrate in sulphuric acid solution

    Directory of Open Access Journals (Sweden)

    Sokić M.

    2012-01-01

    Full Text Available Interest for application of hydrometallurgical processes in a processing of complex sulphide ores and concentrates has increased in recent years. Their application provides better metal recoveries and reduced emission of gaseous and toxic ageneses in the environment. The kinetics and mechanism of sphalerite leaching from complex sulphide concentrate with sulphuric acid and sodium nitrate solution at standard conditions was presented in this paper. The influences of temperature and time on the leaching degree of zinc were investigated and kinetic analysis of the process was accomplished. With temperature increasing from 60 to 90°C, the zinc leaching increased from 25.23% to 71.66% after 2 hours, i.e. from 59.40% to 99.83% after 4 hours. The selected kinetic model indicated that the diffusion through the product layer was the rate-controlling step during the sphalerite leaching. The activation energy was determined to be 55 kJ/mol in the temperature range 60-90°C. XRD, light microscopy and SEM/EDX analyses of the complex concentrate and leach residue confirmed formation of elemental sulphur and diffusion-controlled leaching mechanism.

  19. 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.

  20. 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...

  1. 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)

  2. 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.

  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. Ductile fracture mechanics methodology for complex cracks in nuclear piping

    Energy Technology Data Exchange (ETDEWEB)

    Zahoor, A.

    1988-02-01

    Limit load and J-integral estimation solutions are developed for circumferentially complex-cracked pipes in bending. The limit load solution is developed using thick-walled cylinder analysis which included the effects of flaw depth accurately. J-integral estimation solutions are developed that are suitable for a wide range of loading from linear elastic, elastic-plastic to net-section yielding of the flawed section. Mode I stress intensity factor solution is developed from experimental compliance data. Two types of J solutions are developed. First, J solutions for determining the J-resistance curve from single load-displacement record are presented. Next, elastic-plastic J solution in the format of EPRI J estimation scheme is presented. The latter solution was used to predict the load carrying capacity of complex-cracked pipes made of Type-304 stainless steel, Inconel 600, and A106 GrB materials. Predictions were compared against pipe tests to demonstrate the accuracy of the limit load and J estimation solutions.

  5. Ductile fracture mechanics methodology for complex cracks in nuclear piping

    International Nuclear Information System (INIS)

    Zahoor, A.

    1988-01-01

    Limit load and J-integral estimation solutions are developed for circumferentially complex-cracked pipes in bending. The limit load solution is developed using thick-walled cylinder analysis which included the effects of flaw depth accurately. J-integral estimation solutions are developed that are suitable for a wide range of loading from linear elastic, elastic-plastic to net-section yielding of the flawed section. Mode I stress intensity factor solution is developed from experimental compliance data. Two types of J solutions are developed. First, J solutions for determining the J-resistance curve from single load-displacement record are presented. Next, elastic-plastic J solution in the format of EPRI J estimation scheme is presented. The latter solution was used to predict the load carrying capacity of complex-cracked pipes made of Type-304 stainless steel, Inconel 600, and A106 GrB materials. Predictions were compared against pipe tests to demonstrate the accuracy of the limit load and J estimation solutions. (orig.)

  6. Numerical Solutions of Mechanical Turbulent Filtration Equation Used in Mechatronics and Micro Mechanic

    OpenAIRE

    Hassan Fathabadi

    2013-01-01

    In this study, several novel numerical solutions are presented to solve the turbulent filtration equation and its special case called “Non-Newtonian mechanical filtration equation”. The turbulent filtration equation in porous media is a very important equation which has many applications to solve the problems appearing especially in mechatronics, micro mechanic and fluid mechanic. Many applied mechanical problems can be solved using this equation. For example, non-Newtonian mechanical filtrat...

  7. Complex numbers, quantum mechanics and the beginning of time

    International Nuclear Information System (INIS)

    Gibbons, G.W.; Pohle, H.J.

    1993-01-01

    A basic problem in quantizing a field in curved space is the decomposition of the classical modes in positive and negative frequency. The decomposition is equivalent to a choice of a complex structure in the space of classical solutions. In our construction the real tunneling geometries provide the link between this complex structure and analytic properties of the classical solutions in a riemannian section of space. This is related to the Osterwalder-Schrader approach to euclidean field theory. (orig.)

  8. 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.

  9. 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.

  10. 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)

  11. 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.

  12. Statistical mechanics of complex networks

    CERN Document Server

    Rubi, Miguel; Diaz-Guilera, Albert

    2003-01-01

    Networks can provide a useful model and graphic image useful for the description of a wide variety of web-like structures in the physical and man-made realms, e.g. protein networks, food webs and the Internet. The contributions gathered in the present volume provide both an introduction to, and an overview of, the multifaceted phenomenology of complex networks. Statistical Mechanics of Complex Networks also provides a state-of-the-art picture of current theoretical methods and approaches.

  13. 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

  14. 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

  15. 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

  16. 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

  17. 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.

  18. Influence aqueous solutions on the mechanical behavior of argillaceous rocks; Influence des solutions aqueuses sur le comportement mecanique des roches argileuses

    Energy Technology Data Exchange (ETDEWEB)

    Wakim, J

    2005-12-15

    The hydration of the shale with an aqueous solution induces a swelling deformation which plays an important role in the behaviour of the structures excavated in this type of grounds. This deformation is marked by a three-dimensional and anisotropic character and involves several mechanisms like adsorption, osmosis or capillarity. Several researches were dedicated to swelling and were often much debated due to the complexity of the implied phenomena. The goal of this thesis is therefore to contribute to a better understanding of shale swelling when the rock is confined and hydrated with an aqueous solution. The main part of the work accomplished was related to the Lorraine shale and to the Tournemire shale. To characterize swelling and to identify the main governing parameters, it was necessary to start the issue with an experimental approach. Many apparatus were then developed to carry out tests under various conditions of swelling. In order to facilitate the interpretation of the tests and thereafter the modelling of the behaviour, the experimental procedure adopted consisted of studying first the mechanical aspect and then the chemical aspect of swelling. In the mechanical part, swelling was studied by imposing on the sample a mechanical loading while maintaining during the tests the same aqueous solution. The principal parameters which were studied are the effect of the lateral conditions on axial swelling (impeded strain or constant stress) as well as the influence of the axial stress on radial swelling. The anisotropy of swelling was studied by carrying out, for different orientations of the sample, tests of free swelling, impeded swelling and uniaxial swelling. These various mechanical tests allowed to study the three-dimensional anisotropic swelling in all the conditions and to select the most appropriate test to be used in the second phase of the research. The precise analysis performed to explain the mechanisms behind the swelling of an argillaceous rock

  19. 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.

  20. Bohmian mechanics with complex action: A new trajectory-based formulation of quantum mechanics

    International Nuclear Information System (INIS)

    Goldfarb, Yair; Degani, Ilan; Tannor, David J.

    2006-01-01

    In recent years there has been a resurgence of interest in Bohmian mechanics as a numerical tool because of its local dynamics, which suggest the possibility of significant computational advantages for the simulation of large quantum systems. However, closer inspection of the Bohmian formulation reveals that the nonlocality of quantum mechanics has not disappeared--it has simply been swept under the rug into the quantum force. In this paper we present a new formulation of Bohmian mechanics in which the quantum action, S, is taken to be complex. This leads to a single equation for complex S, and ultimately complex x and p but there is a reward for this complexification - a significantly higher degree of localization. The quantum force in the new approach vanishes for Gaussian wave packet dynamics, and its effect on barrier tunneling processes is orders of magnitude lower than that of the classical force. In fact, the current method is shown to be a rigorous extension of generalized Gaussian wave packet dynamics to give exact quantum mechanics. We demonstrate tunneling probabilities that are in virtually perfect agreement with the exact quantum mechanics down to 10 -7 calculated from strictly localized quantum trajectories that do not communicate with their neighbors. The new formulation may have significant implications for fundamental quantum mechanics, ranging from the interpretation of non-locality to measures of quantum complexity

  1. 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.

  2. 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

  3. 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.

  4. 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

  5. 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

  6. Sampling Molecular Conformers in Solution with Quantum Mechanical Accuracy at a Nearly Molecular-Mechanics Cost.

    Science.gov (United States)

    Rosa, Marta; Micciarelli, Marco; Laio, Alessandro; Baroni, Stefano

    2016-09-13

    We introduce a method to evaluate the relative populations of different conformers of molecular species in solution, aiming at quantum mechanical accuracy, while keeping the computational cost at a nearly molecular-mechanics level. This goal is achieved by combining long classical molecular-dynamics simulations to sample the free-energy landscape of the system, advanced clustering techniques to identify the most relevant conformers, and thermodynamic perturbation theory to correct the resulting populations, using quantum-mechanical energies from density functional theory. A quantitative criterion for assessing the accuracy thus achieved is proposed. The resulting methodology is demonstrated in the specific case of cyanin (cyanidin-3-glucoside) in water solution.

  7. 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)

  8. 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

  9. 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)

  10. 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.

  11. Direct methods of solution for problems in mechanics from invariance principles

    International Nuclear Information System (INIS)

    Rajan, M.

    1986-01-01

    Direct solutions to problems in mechanics are developed from variational statements derived from the principle of invariance of the action integral under a one-parameter family of infinitesimal transformations. Exact, direct solution procedures for linear systems are developed by a careful choice of the arbitrary functions used to generate the infinitesimal transformations. It is demonstrated that the well-known methods for the solution of differential equations can be directly adapted to the required variational statements. Examples in particle and continuum mechanics are presented

  12. 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.

  13. 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

  14. 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.

  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. Fracture mechanics and residual fatigue life analysis for complex stress fields. Technical report

    International Nuclear Information System (INIS)

    Besuner, P.M.

    1975-07-01

    This report reviews the development and application of an influence function method for calculating stress intensity factors and residual fatigue life for two- and three-dimensional structures with complex stress fields and geometries. Through elastic superposition, the method properly accounts for redistribution of stress as the crack grows through the structure. The analytical methods used and the computer programs necessary for computation and application of load independent influence functions are presented. A new exact solution is obtained for the buried elliptical crack, under an arbitrary Mode I stress field, for stress intensity factors at four positions around the crack front. The IF method is then applied to two fracture mechanics problems with complex stress fields and geometries. These problems are of current interest to the electric power generating industry and include (1) the fatigue analysis of a crack in a pipe weld under nominal and residual stresses and (2) fatigue analysis of a reactor pressure vessel nozzle corner crack under a complex bivariate stress field

  17. 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.

  18. Classical and quantum mechanics of complex Hamiltonian systems ...

    Indian Academy of Sciences (India)

    Vol. 73, No. 2. — journal of. August 2009 physics pp. 287–297. Classical and quantum mechanics of complex. Hamiltonian systems: An extended complex phase space ... 1Department of Physics, Ramjas College (University Enclave), University of Delhi,. Delhi 110 ... 1.1 Motivation behind the study of complex Hamiltonians.

  19. 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.

  20. 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

  1. Electrochemical studies of Copper, Tantalum and Tantalum Nitride surfaces in aqueous solutions for applications in chemical-mechanical and electrochemical-mechanical planarization

    Science.gov (United States)

    Sulyma, Christopher Michael

    This report will investigate fundamental properties of materials involved in integrated circuit (IC) manufacturing. Individual materials (one at a time) are studied in different electrochemical environmental solutions to better understand the kinetics associated with the polishing process. Each system tries to simulate a real CMP environment in order to compare our findings with what is currently used in industry. To accomplish this, a variety of techniques are used. The voltage pulse modulation technique is useful for electrochemical processing of metal and alloy surfaces by utilizing faradaic reactions like electrodeposition and electrodissolution. A theoretical framework is presented in chapter 4 to facilitate quantitative analysis of experimental data (current transients) obtained in this approach. A typical application of this analysis is demonstrated for an experimental system involving electrochemical removal of copper surface layers, a relatively new process for abrasive-free electrochemical mechanical planarization of copper lines used in the fabrication of integrated circuits. Voltage pulse modulated electrodissolution of Cu in the absence of mechanical polishing is activated in an acidic solution of oxalic acid and hydrogen peroxide. The current generated by each applied voltage step shows a sharp spike, followed by a double-exponential decay, and eventually attains the rectangular shape of the potential pulses. For the second system in chapter 5, open-circuit potential measurements, cyclic voltammetry and Fourier transform impedance spectroscopy have been used to study pH dependent surface reactions of Cu and Ta rotating disc electrodes (RDEs) in aqueous solutions of succinic acid (SA, a complexing agent), hydrogen peroxide (an oxidizer), and ammonium dodecyl sulfate (ADS, a corrosion inhibitor for Cu). The surface chemistries of these systems are relevant for the development of a single-slurry approach to chemical mechanical planarization (CMP) of Cu

  2. 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

  3. Flotation separation of hafnium(IV) from aqueous solutions

    International Nuclear Information System (INIS)

    Downey, D.M.; Narick, C.N.; Cohen, T.A.

    1985-01-01

    A simple, rapid method for the separation of hafnium from aqueous solutions was investigated using sup(175+181)Hf tracer. Cationic hafnium complex ions were floated from dilute acid solutions with sodium lauryl sulfate (SLS) and anionic hafnium complexes were floated from basic and oxalic acid solutions with hexadecyltrimethyl ammonium bromide (HTMAB). The conditions necessary for quantitative recovery of the metal and mechanisms of flotation are described. (author)

  4. 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

  5. SOLUTION TREATMENT EFFECT ON MICROSTRUCTURE AND MECHANICAL PROPERTIES OF AUTOMOTIVE CAST ALLOY

    Directory of Open Access Journals (Sweden)

    Eva Tillová

    2012-02-01

    Full Text Available The contribution describes influence of the heat treatment (solution treatment at temperature 545°C and 565°C with different holding time 2, 4, 8, 16 and 32 hours; than water quenching at 40°C and natural aging at room temperature during 24 hours on mechanical properties (tensile strength and Brinell hardness and microstructure of the secondary AlSi12Cu1Fe automotive cast alloy. Mechanical properties were measured in line with EN ISO. A combination of different analytical techniques (light microscopy, scanning electron microscopy (SEM were therefore been used for study of microstructure. Solution treatment led to changes in microstructure includes the spheroidization and coarsening of eutectic silicon. The dissolution of precipitates and the precipitation of finer hardening phase further increase the hardness and tensile strength of the alloy. Optimal solution treatment (545°C/4 hours most improves mechanical properties and there mechanical properties are comparable with mechanical properties of primary AlSi12Cu1Fe alloy. Solution treatment at 565 °C caused testing samples distortion, local melting process and is not applicable for this secondary alloy with 12.5 % Si.

  6. 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.

  7. 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.

  8. Flotation separation of hafnium(IV) from aqueous solutions

    Energy Technology Data Exchange (ETDEWEB)

    Downey, D.M.; Narick, C.N.; Cohen, T.A.

    1985-09-01

    A simple, rapid method for the separation of hafnium from aqueous solutions was investigated using sup(175 + 181)Hf tracer. Cationic hafnium complex ions were floated from dilute acid solutions with sodium lauryl sulfate (SLS) and anionic hafnium complexes were floated from basic and oxalic acid solutions with hexadecyltrimethyl ammonium bromide (HTMAB). The conditions necessary for quantitative recovery of the metal and mechanisms of flotation are described. (author). 21 refs.; 5 figs.

  9. The activation mechanism of Ru-indenylidene complexes in olefin metathesis

    KAUST Repository

    Urbina-Blanco, Cé sar A.; Poater, Albert; Lé bl, Tomá š; Manzini, Simone; Slawin, Alexandra M. Z.; Cavallo, Luigi; Nolan, Steven P.

    2013-01-01

    Olefin metathesis is a powerful tool for the formation of carbon-carbon double bonds. Several families of well-defined ruthenium (Ru) catalysts have been developed during the past 20 years; however, the reaction mechanism for all such complexes was assumed to be the same. In the present study, the initiation mechanism of Ru-indenylidene complexes was examined and compared with that of benzylidene counterparts. It was discovered that not all indenylidene complexes followed the same mechanism, highlighting the importance of steric and electronic properties of so-called spectator ligands, and that there is no single mechanism for the Ru-based olefin metathesis reaction. The experimental findings are supported quantitatively by DFT calculations. © 2013 American Chemical Society.

  10. The activation mechanism of Ru-indenylidene complexes in olefin metathesis

    KAUST Repository

    Urbina-Blanco, César A.

    2013-05-08

    Olefin metathesis is a powerful tool for the formation of carbon-carbon double bonds. Several families of well-defined ruthenium (Ru) catalysts have been developed during the past 20 years; however, the reaction mechanism for all such complexes was assumed to be the same. In the present study, the initiation mechanism of Ru-indenylidene complexes was examined and compared with that of benzylidene counterparts. It was discovered that not all indenylidene complexes followed the same mechanism, highlighting the importance of steric and electronic properties of so-called spectator ligands, and that there is no single mechanism for the Ru-based olefin metathesis reaction. The experimental findings are supported quantitatively by DFT calculations. © 2013 American Chemical Society.

  11. Game Theoretic Problems in Network Economics and Mechanism Design Solutions

    CERN Document Server

    Narahari, Y; Narayanam, Ramasuri; Prakash, Hastagiri

    2009-01-01

    Explores game theoretic modeling and mechanism design for problem solving in Internet and network economics. This monograph contains an exposition of representative game theoretic problems in three different network economics situations and a systematic exploration of mechanism design solutions to these problems.

  12. 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)

  13. Classical and quantum mechanics of complex Hamiltonian systems

    Indian Academy of Sciences (India)

    Certain aspects of classical and quantum mechanics of complex Hamiltonian systems in one dimension investigated within the framework of an extended complex phase space approach, characterized by the transformation = 1 + 2, = 1 + 2, are revisited. It is argued that Carl Bender inducted P T symmetry in ...

  14. 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

  15. 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

  16. 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(-)).

  17. 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…

  18. 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.

  19. PHENOMENOLOGY AND MECHANISMS OF THE SOLUTION OF EXISTENTIAL INTRAPERSONAL CONFLICTS

    Directory of Open Access Journals (Sweden)

    Krasilnikov Igor Aleksandrovich

    2013-05-01

    Full Text Available In the article sights of founders of existential psychology at phenomenology and psychological mechanisms of intrapersonal conflicts are considered. It is underlined, that the basic internal conflict is connected with existential anxiety, human life-death. Experience of the existence in the modern social world often has tragical character for the person. The solution of existential intrapersonal conflicts is defined by how the person could realize in itself deep «Me» connected with feeling of finding of internal and external freedom, creative and spontaneity. It is emphasized, that freedom is the main quality of social human life, but the way to it demands from the person of the responsibility, courage and honesty. The authorship of own destiny, personal identity are a source of the solution of existential intrapersonal conflicts. Not each person is capable to keep authenticity in the life. Integrity «Me» cannot be restored, ignoring cultural mental-moral values. Purpose. To study phenomenology and psychological mechanisms of the solution of existential intrapersonal conflicts. Methodology. The qualitative theoretical analysis and synthesis of literary data. Results. In the article general concepts of leading scientists-psychologists of existential orientation to phenomenology and mechanisms of the solution of intrapersonal conflicts are presented. The significant attention is given R. Meya's to sights, as one of the main representatives of existential psychotherapy. Practical implications. Preparation of psychologists in the field of psychotherapeutic consultation.

  20. 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.)

  1. Polycomb complexes and silencing mechanisms

    DEFF Research Database (Denmark)

    Lund, Anders H; van Lohuizen, Maarten

    2004-01-01

    Advances in the past couple of years have brought important new knowledge on the mechanisms by which Polycomb-group proteins regulate gene expression and on the consequences of their actions. The discovery of histone methylation imprints specific for Polycomb and Trithorax complexes has provided...... mechanistic insight on how this ancient epigenetic memory system acts to repress and indicates that it may share mechanistic aspects with other silencing and genome-protective processes, such as RNA interference....

  2. 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

  3. 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.

  4. Single-molecule exploration of photoprotective mechanisms in light-harvesting complexes

    Science.gov (United States)

    Yang, Hsiang-Yu; Schlau-Cohen, Gabriela S.; Gwizdala, Michal; Krüger, Tjaart; Xu, Pengqi; Croce, Roberta; van Grondelle, Rienk; Moerner, W. E.

    2015-03-01

    Plants harvest sunlight by converting light energy to electron flow through the primary events in photosynthesis. One important question is how the light harvesting machinery adapts to fluctuating sunlight intensity. As a result of various regulatory processes, efficient light harvesting and photoprotection are balanced. Some of the biological steps in the photoprotective processes have been extensively studied and physiological regulatory factors have been identified. For example, the effect of lumen pH in changing carotenoid composition has been explored. However, the importance of photophysical dynamics in the initial light-harvesting steps and its relation to photoprotection remain poorly understood. Conformational and excited-state dynamics of multi-chromophore pigment-protein complexes are often difficult to study and limited information can be extracted from ensemble-averaged measurements. To address the problem, we use the Anti-Brownian ELectrokinetic (ABEL) trap to investigate the fluorescence from individual copies of light-harvesting complex II (LHCII), the primary antenna protein in higher plants, in a solution-phase environment. Perturbative surface immobilization or encapsulation schemes are avoided, and therefore the intrinsic dynamics and heterogeneity in the fluorescence of individual proteins are revealed. We perform simultaneous measurements of fluorescence intensity (brightness), excited-state lifetime, and emission spectrum of single trapped proteins. By analyzing the correlated changes between these observables, we identify forms of LHCII with different fluorescence intensities and excited-state lifetimes. The distinct forms may be associated with different energy dissipation mechanisms in the energy transfer chain. Changes of relative populations in response to pH and carotenoid composition are observed, which may extend our understanding of the molecular mechanisms of photoprotection.

  5. 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.)

  6. Electronic structure tautomerism, and mechanism of H-D exchange in imidazole aqueous solutions

    International Nuclear Information System (INIS)

    Borisov, Yu.A.; Vorob'eva, N.P.; Abronin, I.A.; Kolomiets, A.F.

    1988-01-01

    The imidazole electronic structure in a gaseous phase is studied taking into account the influence of solvation effects in aqueous solutions. Possible mechanisms of tautomeric transformations and H-D exchange reactions with water molecules are discussed. Using the quantum chemistry methods, it is shown that the intramolecular mechanism of imidazole isomerization in the gaseous phase and the aqueous solution is unprofitable, and the intermolecular mechanism can proceed through the stage of protonated and carbene form formation

  7. 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.

  8. 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.

  9. 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

  10. Multi-level Quantum Mechanics and Molecular Mechanics Study of Ring Opening Process of Guanine Damage by Hydroxyl Radical in Aqueous Solution.

    Science.gov (United States)

    Liu, Peng; Wang, Qiong; Niu, Meixing; Wang, Dunyou

    2017-08-10

    Combining multi-level quantum mechanics theories and molecular mechanics with an explicit water model, we investigated the ring opening process of guanine damage by hydroxyl radical in aqueous solution. The detailed, atomic-level ring-opening mechanism along the reaction pathway was revealed in aqueous solution at the CCSD(T)/MM levels of theory. The potentials of mean force in aqueous solution were calculated at both the DFT/MM and CCSD(T)/MM levels of the theory. Our study found that the aqueous solution has a significant effect on this reaction in solution. In particular, by comparing the geometries of the stationary points between in gas phase and in aqueous solution, we found that the aqueous solution has a tremendous impact on the torsion angles much more than on the bond lengths and bending angles. Our calculated free-energy barrier height 31.6 kcal/mol at the CCSD(T)/MM level of theory agrees well with the one obtained based on gas-phase reaction profile and free energies of solvation. In addition, the reaction path in gas phase was also mapped using multi-level quantum mechanics theories, which shows a reaction barrier at 19.2 kcal/mol at the CCSD(T) level of theory, agreeing very well with a recent ab initio calculation result at 20.8 kcal/mol.

  11. Complexity: a new paradigm for fracture mechanics

    Directory of Open Access Journals (Sweden)

    S. Puzzi

    2009-10-01

    Full Text Available The so-called Complexity Sciences are a topic of fast growing interest inside the scientific community. Actually, researchers did not come to a definition of complexity, since it manifests itself in so many different ways [1]. This field itself is not a single discipline, but rather a heterogeneous amalgam of different techniques of mathematics and science. In fact, under the label of Complexity Sciences we comprehend a large variety of approaches: nonlinear dynamics, deterministic chaos theory, nonequilibrium thermodynamics, fractal geometry, intermediate asymptotics, complete and incomplete similarity, renormalization group theory, catastrophe theory, self-organized criticality, neural networks, cellular automata, fuzzy logic, etc. Aim of this paper is at providing insight into the role of complexity in the field of Materials Science and Fracture Mechanics [2-3]. The presented examples will be concerned with the snap-back instabilities in the structural behaviour of composite structures (Carpinteri [4-6], the occurrence of fractal patterns and selfsimilarity in material damage and deformation of heterogeneous materials, and the apparent scaling on the nominal mechanical properties of disordered materials (Carpinteri [7,8]. Further examples will deal with criticality in the acoustic emissions of damaged structures and with scaling in the time-to-failure (Carpinteri et al. [9]. Eventually, results on the transition towards chaos in the dynamics of cracked beams will be reported (Carpinteri and Pugno [10,11].

  12. 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.

  13. 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

  14. Fluorescent copper(II complexes: The electron transfer mechanism, interaction with bovine serum albumin (BSA and antibacterial activity

    Directory of Open Access Journals (Sweden)

    Madhumita Hazra

    2017-01-01

    Full Text Available Dinuclear copper(II complexes with formula [Cu2(L2(N32] (1 and [Cu2(L2(NCS2] (2 HL = (1-[(3-methyl-pyridine-2-ylimino-methyl]-naphthalen-2-ol were synthesized by controlling the molar ratio of Cu(OAC2·6H2O, HL, sodium azide (1 and ammonium thiocyanate (2. The end on bridges appear exclusively in azide and thiocyanate to copper complexes. The electron transfer mechanism of copper(II complexes is examined by cyclic voltammetry indicating copper(II complexes are Cu(II/Cu(I couple. The interactions of copper(II complexes towards bovine serum albumin (BSA were examined with the help of absorption and fluorescence spectroscopic tools. We report a superficial solution-based route for the synthesis of micro crystals of copper complexes with BSA. The antibacterial activity of the Schiff base and its copper complexes were investigated by the agar disc diffusion method against some species of pathogenic bacteria (Escherichia coli, Vibrio cholerae, Streptococcus pneumonia and Bacillus cereus. It has been observed that the antibacterial activity of all complexes is higher than the ligand.

  15. 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.

  16. 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.)

  17. 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.

  18. Quantum mechanical studies of complex ferroelectric perovskites

    Science.gov (United States)

    Ramer, Nicholas John

    In many electronic device applications, there is a need to interconvert electrical energy and other types of energy. Ferroelectric materials, which possess a voltage-dependent polarization, can enable this energy conversion process. Because of the broad interest in ferroelectric materials for these devices, there is a critical research effort, both experimental and theoretical, to understand these materials and aid in the development of materials with improved properties. This thesis presents detailed quantum mechanical investigations of the behavior of a complex ferroelectric perovskite under applied stress. In particular, we have chosen to study the solid solution PbZr1-xTix O3 (PZT). Since the study of ferroelectricity involves understanding both its structural and electronic signatures in materials, it has necessitated the development of a novel theoretical technique which improves the accuracy of the pseudopotentials used in our density functional theory calculations as well as a new method for constructing three-dimensional atomistic responses to small amounts of external stress. To examine the material's behavior under larger amounts of stress, we have studied the behavior of a composition of PZT lying near a structural phase boundary. On either side of the phase boundary, the material is characterized by a different polarization direction and may easily be switched between phases by applying external stress. In addition to stress-induced phase transitions, most ferroelectric materials also have composition dependent phase boundaries. Since different compositions of PZT would require increased computational effort, we have formulated an improved virtual crystal approach that makes tractable the study of the entire composition range. Using this method, we have been able to show for the first time via first-principles calculations, a composition dependent phase transition in a ferroelectric material. This thesis has accomplished three important goals: new

  19. 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.

  20. 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.

  1. Quantum mechanics: why complex Hilbert space?

    Science.gov (United States)

    Cassinelli, G.; Lahti, P.

    2017-10-01

    We outline a programme for an axiomatic reconstruction of quantum mechanics based on the statistical duality of states and effects that combines the use of a theorem of Solér with the idea of symmetry. We also discuss arguments favouring the choice of the complex field. This article is part of the themed issue `Second quantum revolution: foundational questions'.

  2. 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

  3. Elucidation of the electronic spectrum changes of KA-Al3+ complex by potentiometric titration, FTIR, 13C NMR and quantum mechanics

    International Nuclear Information System (INIS)

    Piantavini, Mário S.; Gonçalves, Alan G.; Trindade, Ângela C.L.B.; Noseda, Miguel D.; Mercê, Ana L.R.; Pontarolo, Roberto; Machado, Antonio E.H.

    2017-01-01

    Kojic acid (KA) is an organic acid widely used in pharmaceutical industry, mainly as a skin lightening agent. Based on the ability of KA to form complexes with ions, we found the most possible kind of complex formed with cation aluminum. KA-Al 3+ complex structures were studied using potentiometric and spectrophotometric (UV) titrations, FTIR and 13 C NMR. The electronic spectroscopy showed that the KA-Al 3+ complexes absorb at higher wavelengths (λ max = 305 nm) than do the non-complexed KA (λ max = 269 nm), confirming complexation. The IR spectra of KA complexed and not complexed allowed to correlate the changes in the absorption of enol and carbonyl groups in absence and presence of Al 3+ in aqueous solutions. The complexation suggested by the potentiometric titration and FTIR spectroscopy are in accordance with the data obtained from NMR results. Calculations based on quantum mechanics were utilized to understand the differences found in the non complexed and complexed KAH electronic spectra. (author)

  4. Exact solution for stresses/displacements in a multilayered hollow cylinder under thermo-mechanical loading

    International Nuclear Information System (INIS)

    Yeo, W.H.; Purbolaksono, J.; Aliabadi, M.H.; Ramesh, S.; Liew, H.L.

    2017-01-01

    In this study, a new analytical solution by the recursive method for evaluating stresses/displacements in multilayered hollow cylinder under thermo-mechanical loading was developed. The results for temperature distribution, displacements and stresses obtained by using the proposed solution were shown to be in good agreement with the FEM results. The proposed analytical solution was also found to produce more accurate results than those by the analytical solution reported in literature. - Highlights: • A new analytical solution for evaluating stresses in multilayered hollow cylinder under thermo-mechanical loading. • A simple computational procedure using a recursive method. • A promising technique for evaluating the operating axial and hoop stresses in pressurized composite vessels.

  5. 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.

  6. 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

  7. Solved problems in classical mechanics analytical and numerical solutions with comments

    CERN Document Server

    de Lange, O L

    2010-01-01

    Apart from an introductory chapter giving a brief summary of Newtonian and Lagrangian mechanics, this book consists entirely of questions and solutions on topics in classical mechanics that will be encountered in undergraduate and graduate courses. These include one-, two-, and three- dimensional motion; linear and nonlinear oscillations; energy, potentials, momentum, and angular momentum; spherically symmetric potentials; multi-particle systems; rigid bodies; translation androtation of the reference frame; the relativity principle and some of its consequences. The solutions are followed by a set of comments intended to stimulate inductive reasoning and provide additional information of interest. Both analytical and numerical (computer) techniques are used to obtain andanalyze solutions. The computer calculations use Mathematica (version 7), and the relevant code is given in the text. It includes use of the interactive Manipulate function which enables one to observe simulated motion on a computer screen, and...

  8. Quantum mechanics: why complex Hilbert space?

    Science.gov (United States)

    Cassinelli, G; Lahti, P

    2017-11-13

    We outline a programme for an axiomatic reconstruction of quantum mechanics based on the statistical duality of states and effects that combines the use of a theorem of Solér with the idea of symmetry. We also discuss arguments favouring the choice of the complex field.This article is part of the themed issue 'Second quantum revolution: foundational questions'. © 2017 The Author(s).

  9. Human Error Mechanisms in Complex Work Environments

    DEFF Research Database (Denmark)

    Rasmussen, Jens

    1988-01-01

    will account for most of the action errors observed. In addition, error mechanisms appear to be intimately related to the development of high skill and know-how in a complex work context. This relationship between errors and human adaptation is discussed in detail for individuals and organisations...

  10. 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

  11. 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.

  12. 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.

  13. 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...

  14. Reaction mechanisms of metal complexes

    CERN Document Server

    Hay, R W

    2000-01-01

    This text provides a general background as a course module in the area of inorganic reaction mechanisms, suitable for advanced undergraduate and postgraduate study and/or research. The topic has important research applications in the metallurgical industry and is of interest in the science of biochemistry, biology, organic, inorganic and bioinorganic chemistry. In addition to coverage of substitution reactions in four-, five- and six-coordinate complexes, the book contains further chapters devoted to isomerization and racemization reactions, to the general field of redox reactions, and to the reactions of coordinated ligands. It is relevant in other fields such as organic, bioinorganic and biological chemistry, providing a bridge to organic reaction mechanisms. The book also contains a chapter on the kinetic background to the subject with many illustrative examples which should prove useful to those beginning research. Provides a general background as a course module in the area of inorganic reaction mechanis...

  15. 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.

  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. 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

  18. 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.

  19. 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

  20. 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.

  1. 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.

  2. Effects of solution treatment on the microstructure and mechanical properties of Al-Cu-Mg-Ag alloy

    International Nuclear Information System (INIS)

    Liu, Xiao Yan; Pan, Qing Lin; Lu, Zhi Lun; Cao, Su Fang; He, Yun Bin; Li, Wen Bin

    2010-01-01

    The effects of solution treatment on the microstructure and mechanical properties of Al-Cu-Mg-Ag alloy were studied by optical microscopy (OM), scanning electron microscopy (SEM), energy dispersive X-ray (EDX), differential scanning calorimeter (DSC), transmission electron microscopy (TEM) and tensile test, respectively. The results show that the mechanical property increases and then decreases with increasing the solution temperature. And the residual phases are dissolved into the matrix gradually, the number fraction of the precipitation and the size of recrystallized grains increase. Compared to the solution temperature, the solution holding time has less effect on the microstructure and the mechanical properties of Al-Cu-Mg-Ag alloy. The overburnt temperature of Al-Cu-Mg-Ag alloy is 525 o C. The yield strength and the elongation get the best when the alloy is solution treated at 515 o C for 1.5 h, is 504 MPa and 12.2% respectively. The fracture mechanism of the samples is ductile fracture.

  3. 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.

  4. Skeletal muscle mechanics: questions, problems and possible solutions.

    Science.gov (United States)

    Herzog, Walter

    2017-09-16

    Skeletal muscle mechanics have been studied ever since people have shown an interest in human movement. However, our understanding of muscle contraction and muscle mechanical properties has changed fundamentally with the discovery of the sliding filament theory in 1954 and associated cross-bridge theory in 1957. Nevertheless, experimental evidence suggests that our knowledge of the mechanisms of contraction is far from complete, and muscle properties and muscle function in human movement remain largely unknown.In this manuscript, I am trying to identify some of the crucial challenges we are faced with in muscle mechanics, offer possible solutions to questions, and identify problems that might be worthwhile exploring in the future. Since it is impossible to tackle all (worthwhile) problems in a single manuscript, I identified three problems that are controversial, important, and close to my heart. They may be identified as follows: (i) mechanisms of muscle contraction, (ii) in vivo whole muscle mechanics and properties, and (iii) force-sharing among synergistic muscles. These topics are fundamental to our understanding of human movement and movement control, and they contain a series of unknowns and challenges to be explored in the future.It is my hope that this paper may serve as an inspiration for some, may challenge current beliefs in selected areas, tackle important problems in the area of muscle mechanics, physiology and movement control, and may guide and focus some of the thinking of future muscle mechanics research.

  5. Mechanical properties of calcium phosphate cements obtained by solution combustion synthesis

    Energy Technology Data Exchange (ETDEWEB)

    Volkmer, Tiago M.; Barreiro, Oscar; Souza, Vania Caldas; Santos, Luis Alberto dos, E-mail: tiagovolkmer@gmail.com, E-mail: oscarbafer@hotmail.com, E-mail: vania.souza@ufrgs.br, E-mail: luis.santos@ufrgs.br [Universidade Federal do Rio Grande do Sul (UFRS), Porto Alegre, RS (Brazil). Laboratorio de Biomateriais

    2009-07-01

    Bioceramics based on calcium phosphates, especially hydroxyapatite and tricalcium phosphates (TCP) are the most used biomaterials as bone substitutes. The objective of this work is to evaluate the mechanical properties of α-tricalcium phosphate (α-TCP) synthesized by the solution combustion method. The solution combustion synthesis (SCS) can be considered as faster and simpler as other methods, furthermore it allows the obtainment of high purity α-TCP. In the calcium phosphates (CPC), α-TCP reacts with water forming needle like HA, which restrain the movement of grains, increasing mechanical resistance. In the present paper the influence of particle size on mechanical properties of α-TCP cements were evaluated. The α-TCP powder were characterized by XRD, TEM, BET and laser diffraction to asses particle size while the CPC bodies by SEM, Arquimedes method and compression tests. Increasing the milling time, the particle size decreases, resulting in samples with less porosity and consequently with higher compression resistance. (author)

  6. Investigation of Mechanical Properties and Fracture Simulation of Solution-Treated AA 5754

    Science.gov (United States)

    Kumar, Pankaj; Singh, Akhilendra

    2017-10-01

    In this work, mechanical properties and fracture toughness of as-received and solution-treated aluminum alloy 5754 (AA 5754) are experimentally evaluated. Solution heat treatment of the alloy is performed at 530 °C for 2 h, and then, quenching is done in water. Yield strength, ultimate tensile strength, impact toughness, hardness, fatigue life, brittle fracture toughness (K_{Ic} ) and ductile fracture toughness (J_{Ic} ) are evaluated for as-received and solution-treated alloy. Extended finite element method has been used for the simulation of tensile and fracture behavior of material. Heaviside function and asymptotic crack tip enrichment functions are used for modelling of the crack in the geometry. Ramberg-Osgood material model coupled with fracture energy is used to simulate the crack propagation. Fracture surfaces obtained from various mechanical tests are characterized by scanning electron microscopy.

  7. Solid solution in Al-4.5 wt% Cu produced by mechanical alloying

    International Nuclear Information System (INIS)

    Fogagnolo, J.B.; Amador, D.; Ruiz-Navas, E.M.; Torralba, J.M.

    2006-01-01

    Mechanical alloying has been used to produce oxide dispersion strengthened alloys, intermetallic compounds, aluminium alloys and to obtain nanostructured and amorphous materials, as well as to extend the solid solution limit. In this work, Al and Cu elemental powders were subjected to high-energy milling to produce Al-4.5 wt% Cu powder alloy. The powders obtained were characterized by scanning electron microscopy, X-ray diffraction (XRD) and differential scanning calorimetry (DSC), aiming to explore if the copper is present in solid solution or as small particles after high-energy milling. Related to the formation of a supersaturated solid solution, the results of scanning electron microscopy and X-ray diffraction are non-conclusive: the copper could be dispersed with a very small size, undetectable to both techniques. The Al 2 Cu precipitation at temperatures between 160 and 230 deg. C, verified by DSC and XRD analyses, substantiated that mechanical alloying had produced a supersaturated solid solution of copper in aluminium. The crystallite size as a function of milling time and annealing temperature was also determined by X-ray techniques

  8. Sorption mechanisms of chromate with coprecipitated ferrihydrite in aqueous solution

    Energy Technology Data Exchange (ETDEWEB)

    Mamun, Abdullah Al, E-mail: mamun@toki.waseda.jp [Graduate School of Creative Science and Engineering, Waseda University, 3-4-1 Okubo, Shinjuku-ku, Tokyo 169-8555 (Japan); Morita, Masao, E-mail: masao.swimer@akane.waseda.jp [Graduate School of Creative Science and Engineering, Waseda University, 3-4-1 Okubo, Shinjuku-ku, Tokyo 169-8555 (Japan); Matsuoka, Mitsuaki, E-mail: m-matsuoka@aoni.waseda.jp [Faculty of Science and Engineering, Waseda University, 3-4-1 Okubo, Shinjuku-ku, Tokyo 169-8555 (Japan); Tokoro, Chiharu, E-mail: tokoro@waseda.jp [Faculty of Science and Engineering, Waseda University, 3-4-1 Okubo, Shinjuku-ku, Tokyo 169-8555 (Japan)

    2017-07-15

    Highlights: • Coprecipitation showed twice the sorption density of simple adsorption at pH 5. • Mechanism shift from outer- to inner-sphere surface complexation at high Cr/Fe. • In coprecipitation the mechanism shift occurs at lower Cr/Fe ratios than adsorption. • Higher-molar-ratio bidentate binuclear Cr−Fe bonds; yielded ferrihydrite expansion. - Abstract: Hexavalent chromium (Cr(VI)) attracted researchers’ interest for its toxicity, natural availability and removal difficulty. Nevertheless, its sorption mechanism is not clearly understood yet. In this work, we elucidated the sorption mechanism of the co-precipitation of chromates with ferrihydrite through quantitative analysis. The influence of Cr/Fe molar ratio on sorption was investigated by zeta potential measurements, X-ray diffraction (XRD) and X-ray adsorption fine-structure analysis (XAFS). Coprecipitation at pH 5 showed almost twice the sorption density of adsorption at pH 5. In co-precipitation, a shift of the XRD peak due to inner-sphere sorption of chromate was observed at Cr/Fe molar ratio 0.5. For adsorption, the same peak shift was confirmed at Cr/Fe molar ratio of 1. Zeta potential at pH 5 suggested that the sorption mechanism changed at Cr/Fe molar ratio 0.25 for coprecipitation and at Cr/Fe molar ratio of 1 for adsorption. Fitting of Cr and Fe K-edge extended X-ray adsorption fine-structure suggested that ferrihydrite immobilized Cr(VI) via outer sphere surface complexation for lower Cr/Fe ratios and via inner-sphere surface complexation for higher molar ratios. At higher molar ratios, bidentate binuclear Cr−Fe bonds were well established, thus resulting in the expansion of the ferrihydrite structure.

  9. Visualizing the complex functions and mechanisms of the anaphase promoting complex/cyclosome (APC/C)

    Science.gov (United States)

    Alfieri, Claudio; Zhang, Suyang

    2017-01-01

    The anaphase promoting complex or cyclosome (APC/C) is a large multi-subunit E3 ubiquitin ligase that orchestrates cell cycle progression by mediating the degradation of important cell cycle regulators. During the two decades since its discovery, much has been learnt concerning its role in recognizing and ubiquitinating specific proteins in a cell-cycle-dependent manner, the mechanisms governing substrate specificity, the catalytic process of assembling polyubiquitin chains on its target proteins, and its regulation by phosphorylation and the spindle assembly checkpoint. The past few years have witnessed significant progress in understanding the quantitative mechanisms underlying these varied APC/C functions. This review integrates the overall functions and properties of the APC/C with mechanistic insights gained from recent cryo-electron microscopy (cryo-EM) studies of reconstituted human APC/C complexes. PMID:29167309

  10. Mechanisms of iodine release from iodoapatite in aqueous solution

    Science.gov (United States)

    Zhang, Z.; Wang, J.

    2017-12-01

    Immobilization of iodine-129 with waste forms in geological setting is challenging due to its extremely long half-life and high volatility in the environment. To evaluate the long-term performance of waste form, it is imperative to determine the release mechanism of iodine hosted in the waste form materials. This study investigated the iodine released from apatite structured waste form Pb9.85 (VO4)6 I1.7 to understand how diffusion and dissolution control the durability of apatite waste form. A standard semi-dynamic leach test was adopted in this study. Samples were exposed in fresh leachant periodically and the leachant was replaced after each interval. Each experiment was carried out in cap-sealed Teflon vessels under constant temperature (e.g. 90 °C). ICP-MS analysis on the reacted leachates shows that Pb and V were released constantly and congruently with the stoichiometric ratio of Pb/V. However, iodine release is incongruent and time dependent. The iodine release rate starts significantly higher than the corresponding stoichiometric value and gradually decreases, approaching the stoichiometric value. Therefore, a dual-mode mechanism is proposed to account for the iodine release from apatite, which is dominated by short-term diffusion and long-term dissolution processes. Additional tests show that the element release rates depend on a number of test parameters, including sample surface to solution volume ratio (m-1), interval (day), temperature (°C), and solution pH. This study provides a quantitative characterization of iodine release mechanism. The activation energy of iodine leaching 21±1.6 kJ/mol was obtained by varying the test temperature. At the test conditions of to neutral pH and 90 °C, the long-term iodine release rate 3.3 mg/(m2 • day) is projected by normalizing sample surface area to solution volume ratio (S/V) to 1.0 m-1 and interval to 1 day. These findings demonstrate i) the feasibility of our approach to quantify the release mechanism

  11. Fractionalization of the complex-valued Brownian motion of order n using Riemann-Liouville derivative. Applications to mathematical finance and stochastic mechanics

    International Nuclear Information System (INIS)

    Jumarie, Guy

    2006-01-01

    The (complex-valued) Brownian motion of order n is defined as the limit of a random walk on the complex roots of the unity. Real-valued fractional noises are obtained as fractional derivatives of the Gaussian white noise (or order two). Here one combines these two approaches and one considers the new class of fractional noises obtained as fractional derivative of the complex-valued Brownian motion of order n. The key of the approach is the relation between differential and fractional differential provided by the fractional Taylor's series of analytic function f(z+h)=E α (h α D z α ).f(z), where E α is the Mittag-Leffler function on the one hand, and the generalized Maruyama's notation, on the other hand. Some questions are revisited such as the definition of fractional Brownian motion as integral w.r.t. (dt) α , and the exponential growth equation driven by fractional Brownian motion, to which a new solution is proposed. As a first illustrative example of application, in mathematical finance, one proposes a new approach to the optimal management of a stochastic portfolio of fractional order via the Lagrange variational technique applied to the state moment dynamical equations. In the second example, one deals with non-random Lagrangian mechanics of fractional order. The last example proposes a new approach to fractional stochastic mechanics, and the solution so obtained gives rise to the question as to whether physical systems would not have their own internal random times

  12. 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.

  13. Photoelectrochemical etching of gallium nitride surface by complexation dissolution mechanism

    Energy Technology Data Exchange (ETDEWEB)

    Zhang, Miao-Rong [Suzhou Institute of Nano-Tech and Nano-Bionics, Chinese Academy of Sciences, 215123 Suzhou (China); University of Chinese Academy of Sciences, 100049 Beijing (China); Hou, Fei; Wang, Zu-Gang; Zhang, Shao-Hui [Suzhou Institute of Nano-Tech and Nano-Bionics, Chinese Academy of Sciences, 215123 Suzhou (China); Changchun University of Science and Technology, 130022 Changchun (China); Pan, Ge-Bo, E-mail: gbpan2008@sinano.ac.cn [Suzhou Institute of Nano-Tech and Nano-Bionics, Chinese Academy of Sciences, 215123 Suzhou (China)

    2017-07-15

    Graphical abstract: GaN surface was etched by 0.3 M EDTA-2Na. The proposed complexation dissolution mechanism can be applicable to almost all neutral etchants under the prerequisite of strong light and electric field. - Highlights: • GaN surface was etched by EDTA-2Na. • GaN may be dissolved into EDTA-2Na by forming Ga–EDTA complex. • We propose the complexation dissolution mechanism for the first time. - Abstract: Gallium nitride (GaN) surface was etched by 0.3 M ethylenediamine tetraacetic acid disodium (EDTA-2Na) via photoelectrochemical etching technique. SEM images reveal the etched GaN surface becomes rough and irregular. The pore density is up to 1.9 × 10{sup 9} per square centimeter after simple acid post-treatment. The difference of XPS spectra of Ga 3d, N 1s and O 1s between the non-etched and freshly etched GaN surfaces can be attributed to the formation of Ga–EDTA complex at the etching interface between GaN and EDTA-2Na. The proposed complexation dissolution mechanism can be broadly applicable to almost all neutral etchants under the prerequisite of strong light and electric field. From the point of view of environment, safety and energy, EDTA-2Na has obvious advantages over conventionally corrosive etchants. Moreover, as the further and deeper study of such nearly neutral etchants, GaN etching technology has better application prospect in photoelectric micro-device fabrication.

  14. 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.

  15. 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.

  16. Influence of mechanical activation on the leaching of non-ferrous metals from a CuPbZn complex concentrate

    Directory of Open Access Journals (Sweden)

    Godoèíková Erika

    2000-09-01

    Full Text Available The aim of study was to research the procedures of copper, lead and zinc leaching from CuPbZn complex sulphide concentrate during the intervention of mechanical activation.Mechanical activation belongs to innovative procedures, which intensifies technological processes by means of creation of new surfaces and making defective structure of solid phase. Mechanical impact on the solid phase is a suitable procedure to ensure the mobility of its structure elements and to accumulate the mechanical energy that is later used in following processes of leaching.This paper deals with the intensification of the chloride and thiourea leaching of copper, lead and zinc from a CuPbZn complex concentrate of Hodruša-Hámre (Slovak deposit by using the mechanical activation in an attritor. Ferric chloride and thiourea were used as leaching reagents. The leaching of the concentrate with ferric chloride solution afforded 23 % recovery of Cu, 99 % of Pb and 28 % of Zn. 9 % recovery of Cu, 17 % of Pb and 3 % of Zn were achieved by the leaching with thiourea. Thus results showed that the extraction of Cu, Zn and also Pb in the case of thiourea leaching was low. The use of milling in the attritor as an innovation method of pretreatment leads to the structural degradation and increasing the surface area of the investigated concentrate from the original value of 0.18 m2g-1 to the maximum value of 4.67 m2g-1. This fact manifested itself in the subsequent process of extraction of Cu, Pb and Zn into the chloride and thiourea solutions. Our results indicate more effective leaching of pretreated concentrate in the chloride medium with recoveries of 84 % Zn and 100 % Pb. In thiourea, the recoveries for Zn and Pb were low, however 99 % Cu can be recovered. In regard to the economy, the extraction of Cu, Pb and Zn was studied in this work with the aspect of minimal energy consumption during milling. The maximum recoveries of non-ferrous metals in the solutions of ferric chloride

  17. 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.

  18. Human error mechanisms in complex work environments

    International Nuclear Information System (INIS)

    Rasmussen, J.

    1988-01-01

    Human error taxonomies have been developed from analysis of industrial incident reports as well as from psychological experiments. In this paper the results of the two approaches are reviewed and compared. It is found, in both cases, that a fairly small number of basic psychological mechanisms will account for most of the action errors observed. In addition, error mechanisms appear to be intimately related to the development of high skill and know-how in a complex work context. This relationship between errors and human adaptation is discussed in detail for individuals and organisations. The implications for system safety and briefly mentioned, together with the implications for system design. (author)

  19. Human error mechanisms in complex work environments

    International Nuclear Information System (INIS)

    Rasmussen, Jens; Danmarks Tekniske Hoejskole, Copenhagen)

    1988-01-01

    Human error taxonomies have been developed from analysis of industrial incident reports as well as from psychological experiments. In this paper the results of the two approaches are reviewed and compared. It is found, in both cases, that a fairly small number of basic psychological mechanisms will account for most of the action errors observed. In addition, error mechanisms appear to be intimately related to the development of high skill and know-how in a complex work context. This relationship between errors and human adaptation is discussed in detail for individuals and organisations. The implications for system safety are briefly mentioned, together with the implications for system design. (author)

  20. 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.

  1. Influence of solution annealing on microstructure and mechanical properties of Maraging 300 steel

    Energy Technology Data Exchange (ETDEWEB)

    Lima Filho, Venceslau Xavier; Barros, Isabel Ferreira; Abreu, Hamilton Ferreira Gomes de, E-mail: venceslau@ifce.edu.br [Universidade Federal do Ceara (UFC), Fortaleza, CE (Brazil). Departamento de Engenharia Metalurgica e Materiais. Laboratorio de Caracterizacao de Materiais, Metalurgia Fisica e Grupo de Pesquisa de Transformacao de Fase

    2017-01-15

    Maraging 300 belongs to a family of metallic materials with extremely high mechanical strength and good toughness. Some works have been published about aging temperatures that improve ultimate strength resistance with acceptable toughness levels in this steel family, where the prior austenite grain size obtained by different solution annealing temperature influence in the final mechanical properties. Solution annealing temperatures ranging from 860 °C to 1150 deg C and were kept constant until the aging temperature. These treatments were used in order to investigate their influence on the microstructure and mechanical properties of maraging steel 300, especially with regard to toughness. The characterization of the microstructure was performed by optical microscopy, scanning electron microscope (SEM) and X-ray diffraction (XRD). Mechanical properties were evaluated by Rockwell C hardness and Charpy impact tests. The results showed that there is a temperature range where one can get some improvement in toughness without a large loss of mechanical strength. (author)

  2. 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

  3. 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

  4. 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

  5. Mechanism for suppression of radiation-induced segregation by oversized solute addition in austenitic stainless steel

    Science.gov (United States)

    Hackett, Micah Jeremiah

    The objective of this thesis is to quantify the effect of oversized solutes on radiation-induced segregation in austenitic stainless steels and to determine the mechanism of this effect. Zr or Hf additions to austenitic stainless steels demonstrated a reduction in radiation-induced segregation of Cr and Ni at the grain boundary after proton irradiation at 400°C and 500°C to low doses, but the solute effect disappeared at higher doses. Rate theory modeling of RIS was extended to incorporate a solute-vacancy trapping mechanism to predict the effect of solutes on RIS. The model showed that RIS is most sensitive to the solute-vacancy binding energy. First principles calculations were used to determine a binding energy of 1.08 eV for Zr and 0.71 eV for Hf. Model and experiment agreed in showing suppression of Cr depletion at doses of 3 dpa at 400°C and 1 dpa at 500°C, and experimental results were consistent with the model in showing greater effectiveness of Zr relative to Hf due to a larger binding energy. The dislocation loop microstructure was measured at 400°C, 3 and 7 dpa, and a significant decrease in loop density and total loop line length in the oversized solute alloys relative to the reference alloys. The loop microstructure results were consistent with RIS results by confirming enhanced recombination of point defects by solute-vacancy trapping. Increases in RIS with dose indicated a loss of solute effectiveness, which was consistent with an observed increase in loop line length from 3 to 7 dpa. The loss of solute effectiveness at high dose is attributed to a loss of oversized solute from the matrix due to coarsening of carbide precipitates. X-ray diffraction identified a microstructure with ZrC or HfC precipitates prior to irradiation. Precipitate coarsening was identified as the most likely mechanism for the loss of solute effectiveness on RIS by the following: (1) diffusion analysis suggested significant solute diffusion by the vacancy flux to

  6. 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.

  7. 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.

  8. 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.

  9. Morphology, thermal and mechanical properties of PVC/MMT nanocomposites prepared by solution blending and solution blending + melt compounding

    DEFF Research Database (Denmark)

    Madaleno, Liliana Andreia Oliveira; Schjødt-Thomsen, Jan; Pinto, José Cruz

    2010-01-01

    Two types of montmorillonite (MMT), natural sodium montmorillonite (Na-MMT) and organically modified montmorillonite (OMMT), in different amounts of 1, 2, 5, 10 and 25 phr (parts per hundred resin), were dispersed in rigid poly (vinyl chloride) by two different methods solution blending...... and solution blending + melt compounding The effects on morphology, thermal and mechanical properties of the PVC/MMT nanocomposites were studied by varying the amount of Na-MMT and OMMT in both methods SEM and XRD analysis revealed that possible intercalated and exfoliated structures were obtained in all...... prepared by solution blending + melt compounding method Experimental values for 1 and 2 phr are larger than the calculated values which directly suggest that the MMT particles are exfoliated (C) 2010 Elsevier Ltd All rights reserved...

  10. Elucidation of the electronic spectrum changes of KA-Al{sup 3+} complex by potentiometric titration, FTIR, {sup 13}C NMR and quantum mechanics

    Energy Technology Data Exchange (ETDEWEB)

    Piantavini, Mário S.; Gonçalves, Alan G.; Trindade, Ângela C.L.B.; Noseda, Miguel D.; Mercê, Ana L.R.; Pontarolo, Roberto, E-mail: pontarolo@ufpr.br [Universidade Federal do Paraná (UFPR), Curitiba (Brazil); Machado, Antonio E.H. [Universidade Federal de Uberlândia (UFU), MG (Brazil)

    2017-08-15

    Kojic acid (KA) is an organic acid widely used in pharmaceutical industry, mainly as a skin lightening agent. Based on the ability of KA to form complexes with ions, we found the most possible kind of complex formed with cation aluminum. KA-Al{sup 3+} complex structures were studied using potentiometric and spectrophotometric (UV) titrations, FTIR and {sup 13}C NMR. The electronic spectroscopy showed that the KA-Al{sup 3+} complexes absorb at higher wavelengths (λ{sub max}= 305 nm) than do the non-complexed KA (λ{sub max}= 269 nm), confirming complexation. The IR spectra of KA complexed and not complexed allowed to correlate the changes in the absorption of enol and carbonyl groups in absence and presence of Al{sup 3+} in aqueous solutions. The complexation suggested by the potentiometric titration and FTIR spectroscopy are in accordance with the data obtained from NMR results. Calculations based on quantum mechanics were utilized to understand the differences found in the non complexed and complexed KAH electronic spectra. (author)

  11. Chansporter complexes in cell signaling.

    Science.gov (United States)

    Abbott, Geoffrey W

    2017-09-01

    Ion channels facilitate diffusion of ions across cell membranes for such diverse purposes as neuronal signaling, muscular contraction, and fluid homeostasis. Solute transporters often utilize ionic gradients to move aqueous solutes up their concentration gradient, also fulfilling a wide variety of tasks. Recently, an increasing number of ion channel-transporter ('chansporter') complexes have been discovered. Chansporter complex formation may overcome what could otherwise be considerable spatial barriers to rapid signal integration and feedback between channels and transporters, the ions and other substrates they transport, and environmental factors to which they must respond. Here, current knowledge in this field is summarized, covering both heterologous expression structure/function findings and potential mechanisms by which chansporter complexes fulfill contrasting roles in cell signaling in vivo. © 2017 Federation of European Biochemical Societies.

  12. 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.

  13. Mechanism of management of competitiveness of production of agrarian and industrial complex

    Directory of Open Access Journals (Sweden)

    Buryak E. A.

    2016-04-01

    Full Text Available the concept of competitiveness and mechanisms of management of competitiveness of production is considered. Major factors of ensuring competitiveness of production of agrarian and industrial complex are allocated. The main problems of production of wheat in the Republic of Crimea making negative impact on the level of her competitiveness are revealed. The mechanism of management of competitiveness of production of agrarian and industrial complex is developed.

  14. A Complexity-Aware Video Adaptation Mechanism for Live Streaming Systems

    Directory of Open Access Journals (Sweden)

    Chen Homer H

    2007-01-01

    Full Text Available The paradigm shift of network design from performance-centric to constraint-centric has called for new signal processing techniques to deal with various aspects of resource-constrained communication and networking. In this paper, we consider the computational constraints of a multimedia communication system and propose a video adaptation mechanism for live video streaming of multiple channels. The video adaptation mechanism includes three salient features. First, it adjusts the computational resource of the streaming server block by block to provide a fine control of the encoding complexity. Second, as far as we know, it is the first mechanism to allocate the computational resource to multiple channels. Third, it utilizes a complexity-distortion model to determine the optimal coding parameter values to achieve global optimization. These techniques constitute the basic building blocks for a successful application of wireless and Internet video to digital home, surveillance, IPTV, and online games.

  15. A Complexity-Aware Video Adaptation Mechanism for Live Streaming Systems

    Science.gov (United States)

    Lu, Meng-Ting; Yao, Jason J.; Chen, Homer H.

    2007-12-01

    The paradigm shift of network design from performance-centric to constraint-centric has called for new signal processing techniques to deal with various aspects of resource-constrained communication and networking. In this paper, we consider the computational constraints of a multimedia communication system and propose a video adaptation mechanism for live video streaming of multiple channels. The video adaptation mechanism includes three salient features. First, it adjusts the computational resource of the streaming server block by block to provide a fine control of the encoding complexity. Second, as far as we know, it is the first mechanism to allocate the computational resource to multiple channels. Third, it utilizes a complexity-distortion model to determine the optimal coding parameter values to achieve global optimization. These techniques constitute the basic building blocks for a successful application of wireless and Internet video to digital home, surveillance, IPTV, and online games.

  16. Closed-form solutions for linear regulator design of mechanical systems including optimal weighting matrix selection

    Science.gov (United States)

    Hanks, Brantley R.; Skelton, Robert E.

    1991-01-01

    Vibration in modern structural and mechanical systems can be reduced in amplitude by increasing stiffness, redistributing stiffness and mass, and/or adding damping if design techniques are available to do so. Linear Quadratic Regulator (LQR) theory in modern multivariable control design, attacks the general dissipative elastic system design problem in a global formulation. The optimal design, however, allows electronic connections and phase relations which are not physically practical or possible in passive structural-mechanical devices. The restriction of LQR solutions (to the Algebraic Riccati Equation) to design spaces which can be implemented as passive structural members and/or dampers is addressed. A general closed-form solution to the optimal free-decay control problem is presented which is tailored for structural-mechanical system. The solution includes, as subsets, special cases such as the Rayleigh Dissipation Function and total energy. Weighting matrix selection is a constrained choice among several parameters to obtain desired physical relationships. The closed-form solution is also applicable to active control design for systems where perfect, collocated actuator-sensor pairs exist.

  17. Research on Evolutionary Mechanism of Agile Supply Chain Network via Complex Network Theory

    Directory of Open Access Journals (Sweden)

    Nai-Ru Xu

    2016-01-01

    Full Text Available The paper establishes the evolutionary mechanism model of agile supply chain network by means of complex network theory which can be used to describe the growth process of the agile supply chain network and analyze the complexity of the agile supply chain network. After introducing the process and the suitability of taking complex network theory into supply chain network research, the paper applies complex network theory into the agile supply chain network research, analyzes the complexity of agile supply chain network, presents the evolutionary mechanism of agile supply chain network based on complex network theory, and uses Matlab to simulate degree distribution, average path length, clustering coefficient, and node betweenness. Simulation results show that the evolution result displays the scale-free property. It lays the foundations of further research on agile supply chain network based on complex network theory.

  18. Effects of solution treatment on mechanical properties and corrosion resistance of 4A duplex stainless steel

    Energy Technology Data Exchange (ETDEWEB)

    Lu, Panpan; Wang, Aiqin; Wang, Wenyan [Henan Univ. of Science and Technology, Luoyang (China). School of Material Science and Engineering; Xie, Jingpei [Henan Univ. of Science and Technology, Luoyang (China). Collaborative Innovation Center of Nonferrous Metals

    2018-02-15

    In this study, 4A duplex stainless steels were prepared via remelting in an intermediate frequency furnace and subsequently solution treated at different temperatures. The effects of solution treatment on the mechanical properties and corrosion resistance of 4A duplex stainless steel were investigated. Microstructures were characterized via optical microscopy and scanning electron microscopy. The mechanical properties were evaluated via hardness test, tensile test, and impact test experiments. The point corrosion resistance was studied via chemical immersion and potentiodynamic anodic polarization. The results showed that with increasing solution temperature in the range of 1223 - 1423 K, the tensile strength and hardness first decreased and then increased, and minimum values were obtained at 1323 K. The σ phase precipitated at the boundaries of the α/γ phases in samples solution treated at 1223 K, decreasing both impact energy and pitting potential of the experimental steels. When experimental steels were solution treated at 1373 K for 2 h, a suitable volume fraction of α/γ was uniformly distributed throughout the microstructure, and the steels exhibited optimal mechanical properties and pitting corrosion resistance.

  19. Lectures on quantum mechanics with problems, exercises and their solutions

    CERN Document Server

    Basdevant, Jean-Louis

    2016-01-01

    The new edition of this remarkable text offers the reader a conceptually strong introduction to quantum mechanics, but goes beyond this to present a fascinating tour of modern theoretical physics. Beautifully illustrated and engagingly written, it starts with a brief overview of diverse topics across physics including nanotechnology, statistical physics, materials science, astrophysics, and cosmology. The core of the book covers both established and emerging aspects of quantum mechanics. A concise introduction to traditional quantum mechanics covers the Schrödinger equation, Hilbert space, the algebra of observables, hydrogen atom, spin and Pauli principle. Modern features of the field are presented by exploring entangled states, Bell's inequality, quantum cryptography, quantum teleportation and quantum mechanics in the universe. This new edition has been enchanced through the addition of numerous problems with detailed solutions, an introduction to the mathematical tools needed and expanded discussion of th...

  20. Complex and biofluids: From Maxwell to nowadays

    Science.gov (United States)

    Misbah, Chaouqi

    2009-11-01

    Complex fluids are the rule in biology and in many industrial applications. Typical examples are blood, cartilage, and polymer solutions. Unlike water (as well as domestic oils, soft clear drinks, and so on), the law(s) describing the behavior of complex fluids are not yet fully established. The complexity arises from strong coupling between microscopic scales (like the motion of a red blood cell in the case of blood, or a polymer molecule for a polymer solution) and the global scale of the flow (say at the scale of a blood artery, or a channel in laboratory experiments). In this issue entitled Complex and Biofluids a large panel of experimental and theoretical problems of complex fluids is exposed. The topics range from dilute polymer solutions, food products, to biology (blood flow, cell and tissue mechanics). One of the earliest model put forward as an attempt to describe a complex fluid was suggested a long time ago by James Clerk Maxwell (in 1867). Other famous scientists, like Einstein (in 1906), and Taylor (in 1932) have made important contributions to the field, but the topic of complex fluids still continues to pose a formidable challenge to science. This field has known during the past decade an unbelievable upsurge of interest in many branches of science (physics, mechanics, chemistry, biology, medical science, mathematics, and so on). Understanding complex fluids is viewed as one of the biggest challenge of the present century. This synthesis will provide a simple introduction to the topic, summarize the main contribution of this issue, and list major open questions in this field. To cite this article: C. Misbah, C. R. Physique 10 (2009).

  1. The influence of the "cage effect" on the mechanism of reversible bimolecular multistage chemical reactions in solutions.

    Science.gov (United States)

    Doktorov, Alexander B

    2015-08-21

    Manifestations of the "cage effect" at the encounters of reactants are theoretically treated by the example of multistage reactions in liquid solutions including bimolecular exchange reactions as elementary stages. It is shown that consistent consideration of quasi-stationary kinetics of multistage reactions (possible only in the framework of the encounter theory) for reactions proceeding near reactants contact can be made on the basis of the concepts of a "cage complex." Though mathematically such a consideration is more complicated, it is more clear from the standpoint of chemical notions. It is established that the presence of the "cage effect" leads to some important effects not inherent in reactions in gases or those in solutions proceeding in the kinetic regime, such as the appearance of new transition channels of reactant transformation that cannot be caused by elementary event of chemical conversion for the given mechanism of reaction. This results in that, for example, rate constant values of multistage reaction defined by standard kinetic equations of formal chemical kinetics from experimentally measured kinetics can differ essentially from real values of these constants.

  2. 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.

  3. KDP Aqueous Solution-in-Oil Microemulsion for Ultra-Precision Chemical-Mechanical Polishing of KDP Crystal

    Directory of Open Access Journals (Sweden)

    Hui Dong

    2017-03-01

    Full Text Available A novel functional KH2PO4 (KDP aqueous solution-in-oil (KDP aq/O microemulsion system for KDP crystal ultra-precision chemical-mechanical polishing (CMP was prepared. The system, which consisted of decanol, Triton X-100, and KH2PO4 aqueous solution, was available at room temperature. The functional KDP aq/O microemulsion system was systematically studied and applied as polishing solution to KDP CMP technology. In this study, a controlled deliquescent mechanism was proposed for KDP polishing with the KDP aq/O microemulsion. KDP aqueous solution, the chemical etchant in the polishing process, was caged into the micelles in the microemulsion, leading to a limitation of the reaction between the KDP crystal and KDP aqueous solution only if the microemulsion was deformed under the effect of the external force. Based on the interface reaction dynamics, KDP aqueous solutions with different concentrations (cKDP were applied to replace water in the traditional water-in-oil (W/O microemulsion. The practicability of the controlled deliquescent mechanism was proved by the decreasing material removal rate (MRR with the increasing of the cKDP. As a result, the corrosion pits on the KDP surface were avoided to some degree. Moreover, the roughnesses of KDP with KDP aq/O microemulsion (cKDP was changed from 10 mM to 100 mM as polishing solutions were smaller than that with the W/O microemulsion. The smallest surface root-mean-square roughness of 1.5 nm was obtained at a 30 mmol/L KDP aq solution, because of the most appropriate deliquescent rate and MRR.

  4. Nonlinear dynamics and complexity

    CERN Document Server

    Luo, Albert; Fu, Xilin

    2014-01-01

    This important collection presents recent advances in nonlinear dynamics including analytical solutions, chaos in Hamiltonian systems, time-delay, uncertainty, and bio-network dynamics. Nonlinear Dynamics and Complexity equips readers to appreciate this increasingly main-stream approach to understanding complex phenomena in nonlinear systems as they are examined in a broad array of disciplines. The book facilitates a better understanding of the mechanisms and phenomena in nonlinear dynamics and develops the corresponding mathematical theory to apply nonlinear design to practical engineering.

  5. 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

  6. 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

  7. Algebra of Complex Vectors and Applications in Electromagnetic Theory and Quantum Mechanics

    Directory of Open Access Journals (Sweden)

    Kundeti Muralidhar

    2015-08-01

    Full Text Available A complex vector is a sum of a vector and a bivector and forms a natural extension of a vector. The complex vectors have certain special geometric properties and considered as algebraic entities. These represent rotations along with specified orientation and direction in space. It has been shown that the association of complex vector with its conjugate generates complex vector space and the corresponding basis elements defined from the complex vector and its conjugate form a closed complex four dimensional linear space. The complexification process in complex vector space allows the generation of higher n-dimensional geometric algebra from (n — 1-dimensional algebra by considering the unit pseudoscalar identification with square root of minus one. The spacetime algebra can be generated from the geometric algebra by considering a vector equal to square root of plus one. The applications of complex vector algebra are discussed mainly in the electromagnetic theory and in the dynamics of an elementary particle with extended structure. Complex vector formalism simplifies the expressions and elucidates geometrical understanding of the basic concepts. The analysis shows that the existence of spin transforms a classical oscillator into a quantum oscillator. In conclusion the classical mechanics combined with zeropoint field leads to quantum mechanics.

  8. Coagulation mechanism of salt solution-extracted active component in Moringa oleifera seeds.

    Science.gov (United States)

    Okuda, T; Baes, A U; Nishijima, W; Okada, M

    2001-03-01

    This study focuses on the coagulation mechanism by the purified coagulant solution (MOC-SC-PC) with the coagulation active component extracted from M. oleifera seeds using salt solution. The addition of MOC-SC-PC tap water formed insoluble matters. This formation was responsible for kaolin coagulation. On the other hand, insoluble matters were not formed when the MOC-SC-PC was added into distilled water. The formation was affected by Ca2+ or other bivalent cations which may connect each molecule of the active coagulation component in MOC-SC-PC and form a net-like structure. The coagulation mechanism of MOC-SC-PC seemed to be an enmeshment of Kaolin by the insoluble matters with the net-like structure. In case of Ca2+ ion (bivalent cations), at least 0.2 mM was necessary for coagulation at 0.3 mgC l-1 dose of MOC-SC-PC. Other coagulation mechanisms like compression of double layer, interparticle bridging or charge neutralization were not responsible for the coagulation by MOC-SC-PC.

  9. 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.

  10. Coagulation mechanism of salt solution-extracted active component in Moringa oleifera seeds

    OpenAIRE

    Okuda, Tetsuji; Baes, Aloysius U.; Nishijima, Wataru; Okada, Mitsumasa

    2001-01-01

    This study focuses on the coagulation mechanism by the purified coagulant solution (MOC-SC-PC) with the coagulation active component extracted from M. oleifera seeds using salt solution. The addition of MOC-SC-PC into tap water formed insoluble matters. The formation was responsible for kaolin coagulation. On the other hand, insoluble matters were not formed when the MOC-SC-PC was added into distilled water. The formation was affected by Ca2+ or other bivalent cations which may connect each m...

  11. Grid-Based Projector Augmented Wave (GPAW) Implementation of Quantum Mechanics/Molecular Mechanics (QM/MM) Electrostatic Embedding and Application to a Solvated Diplatinum Complex.

    Science.gov (United States)

    Dohn, A O; Jónsson, E Ö; Levi, G; Mortensen, J J; Lopez-Acevedo, O; Thygesen, K S; Jacobsen, K W; Ulstrup, J; Henriksen, N E; Møller, K B; Jónsson, H

    2017-12-12

    A multiscale density functional theory-quantum mechanics/molecular mechanics (DFT-QM/MM) scheme is presented, based on an efficient electrostatic coupling between the electronic density obtained from a grid-based projector augmented wave (GPAW) implementation of density functional theory and a classical potential energy function. The scheme is implemented in a general fashion and can be used with various choices for the descriptions of the QM or MM regions. Tests on H 2 O clusters, ranging from dimer to decamer show that no systematic energy errors are introduced by the coupling that exceeds the differences in the QM and MM descriptions. Over 1 ns of liquid water, Born-Oppenheimer QM/MM molecular dynamics (MD) are sampled combining 10 parallel simulations, showing consistent liquid water structure over the QM/MM border. The method is applied in extensive parallel MD simulations of an aqueous solution of the diplatinum [Pt 2 (P 2 O 5 H 2 ) 4 ] 4- complex (PtPOP), spanning a total time period of roughly half a nanosecond. An average Pt-Pt distance deviating only 0.01 Å from experimental results, and a ground-state Pt-Pt oscillation frequency deviating by <2% from experimental results were obtained. The simulations highlight a remarkable harmonicity of the Pt-Pt oscillation, while also showing clear signs of Pt-H hydrogen bonding and directional coordination of water molecules along the Pt-Pt axis of the complex.

  12. Atomistic simulation of solid solution hardening in Mg/Al alloys: Examination of composition scaling and thermo-mechanical relationships

    International Nuclear Information System (INIS)

    Yi, Peng; Cammarata, Robert C.; Falk, Michael L.

    2016-01-01

    Dislocation mobility in a solid solution was studied using atomistic simulations of an Mg/Al system. The critical resolved shear stress (CRSS) for the dislocations on the basal plane was calculated at temperatures from 0 K to 500 K with solute concentrations from 0 to 7 at%, and with four different strain rates. Solute hardening of the CRSS is decomposed into two contributions: one scales with c 2/3 , where c is the solute concentration, and the other scales with c 1 . The former was consistent with the Labusch model for local solute obstacles, and the latter was related to the athermal plateau stress due to the long range solute effect. A thermo-mechanical model was then used to analyze the temperature and strain rate dependences of the CRSS, and it yielded self-consistent and realistic results. The scaling laws were confirmed and the thermo-mechanical model was successfully parameterized using experimental measurements of the CRSS for Mg/Al alloys under quasi-static conditions. The predicted strain rate sensitivity from the experimental measurements of the CRSS is in reasonable agreement with separate mechanical tests. The concentration scaling and the thermo-mechanical relationships provide a potential tool to analytically relate the structural and thermodynamic parameters on the microscopic level with the macroscopic mechanical properties arising from dislocation mediated deformation.

  13. Determinations of directions of the mean stress field in Sichuan-Yunnan region from a number of focal mechanism solutions

    Science.gov (United States)

    Zhong, Ji-Mao; Cheng, Wan-Zheng

    2006-07-01

    Based on the spatial orientation and slip direction of the fault plane solutions, we present the expression of corresponding mechanical axis tensor in geographic coordinate system, and then put forward a method for calculating average mechanical axis tensor and its eigenvalues, which involves solving the corresponding eigenequation. The method for deducing mean stress field from T, B, and P axes parameters of a number of focal mechanism solutions has been verified by inverting data of mean stress fields in Fuyun region and in Tangshan region with fitting method of slip direction, and both results are consistent. To study regional average stress field, we need to choose a population of focal mechanism solutions of earthquakes in the massifs where there are significant tectonic structures. According to the focal mechanism solutions of 256 moderate-strong earthquakes occurred in 13 seismic zones of Sichuan-Yunnan region, the quantitative analysis results of stress tensor in each seismic zone have been given. The algorithm of such method is simple and convenient, which makes the method for analyzing tectonic stress field with large amount of focal mechanism solution data become quantified.

  14. 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

  15. 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

  16. Application of Bipartite Entangled States to Quantum Mechanical Version of Complex Wavelet Transforms

    International Nuclear Information System (INIS)

    Fan Hongyi; Lu Hailiang; Xu Xuefen

    2006-01-01

    We introduce the bipartite entangled states to present a quantum mechanical version of complex wavelet transform. Using the technique of integral within an ordered product of operators we show that the complex wavelet transform can be studied in terms of various quantum state vectors in two-mode Fock space. In this way the creterion for mother wavelet can be examined quantum-mechanically and therefore more deeply.

  17. 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.

  18. Fast Coding Unit Encoding Mechanism for Low Complexity Video Coding

    OpenAIRE

    Gao, Yuan; Liu, Pengyu; Wu, Yueying; Jia, Kebin; Gao, Guandong

    2016-01-01

    In high efficiency video coding (HEVC), coding tree contributes to excellent compression performance. However, coding tree brings extremely high computational complexity. Innovative works for improving coding tree to further reduce encoding time are stated in this paper. A novel low complexity coding tree mechanism is proposed for HEVC fast coding unit (CU) encoding. Firstly, this paper makes an in-depth study of the relationship among CU distribution, quantization parameter (QP) and content ...

  19. Surface Complexation of Neptunium(V) with Goethite

    International Nuclear Information System (INIS)

    Jerden, James L.; Kropf, A. Jeremy

    2007-01-01

    Batch adsorption experiments in which neptunium-bearing solutions were reacted with goethite (alpha-FeOOH) have been performed to study uptake mechanisms in sodium chloride and calcium-bearing sodium silicate solutions. This paper presents results identifying and quantifying the mechanisms by which neptunium is adsorbed as a function of pH and reaction time (aging). Also presented are results from tests in which neptunium is reacted with goethite in the presence of other cations (uranyl and calcium) that may compete with neptunium for sorption sites. The desorption of neptunium from goethite has been studied by re-suspending the neptunium-loaded goethite samples in solutions containing no neptunium. Selected reacted sorbent samples were analyzed by x-ray absorption spectroscopy (XAS) to determine the oxidation state and molecular speciation of the adsorbed neptunium. Results have been used to establish the pH adsorption edge of neptunium on goethite in sodium chloride and calcium-bearing sodium silicate solutions. The results indicate that neptunium uptake on goethite reaches 95% at a pH of approximately 7 and begins to decrease at pH values greater than 8.5. Distribution coefficients for neptunium sorption range from less than 1000 (moles/kg) sorbed / (moles/kg) solution at pH less than 5.0 to greater than 10,000 (moles/kg) sorbed / (moles/kg) solution at pH greater than 7.0. Distribution coefficients as high as 100,000 (moles/kg) sorbed / (moles/kg) solution were recorded for the tests done in calcite equilibrated sodium silicate solutions. XAS results show that neptunium complexes with the goethite surface mainly as Np(V) (although Np(IV) is prevalent in some of the longer-duration sorption tests). The neptunium adsorbed to goethite shows Np-O bond length of approximately 1.8 angstroms which is representative of the Np-O axial bond in the neptunyl(V) complex. This neptunyl(V) ion is coordinated to 5 or 6 equatorial oxygens with Np-O bond lengths of 2

  20. Biomechanics of compensatory mechanisms in spinal-pelvic complex

    Science.gov (United States)

    Ivanov, D. V.; Hominets, V. V.; Kirillova, I. V.; Kossovich, L. Yu; Kudyashev, A. L.; Teremshonok, A. V.

    2018-04-01

    3D geometric solid computer model of spinal-pelvic complex was constructed on the basis of computed tomography and full body X-ray in standing position data. The constructed model was used for biomechanical analysis of compensatory mechanisms arising in the spine with anteversion and retroversion of the pelvis. The results of numerical biomechanical 3D modeling are in good agreement with the clinical data.

  1. Mechanism of recycling of post-termination ribosomal complexes in ...

    Indian Academy of Sciences (India)

    Madhu

    all pathway of ribosome recycling in eubacteria with especial reference to the important role of the initiation factor ... [Seshadri A and Varshney U 2006 Mechanism of recycling of post-termination ribosomal complexes in eubacteria: a new role of initiation factor 3 .... RRF binding results in a remarkable conformational change.

  2. 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.

  3. 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.)

  4. Possible mechanisms for interaction of poly electrolytes with ions in aqueous solution

    International Nuclear Information System (INIS)

    Siyam, T.

    1995-01-01

    The interaction between the active groups of water soluble poly electrolytes such as polyacrylamide 'neutral polymers PAM', poly sodium acrylate 'anionic polymer PAANA', polyacrylamide-diallyamine-hydrochloride 'cationic polymer PAM-DAA-HCl and polyacrylamide-diallylethylamine-hydrochloride 'cationic polymer PAM-DAEA-HCl' with copper sulphate has been carried out under different experimental conditions. Spectroscopic studies show that the mechanism of the flock formation due to interaction between the polymer and copper sulphate is a bond formation between the active group of polymeric chains and copper sulphate. This bond formation depends on the nature of polymer chain. It was also found that the amide groups form complexes with hydrated cations, while both carboxylate-and ammonium groups interact by ion-exchange mechanism. The same studies were applied on polyacrylamideacrylic acid resin 'PAM-AA' resin and copper sulphate. The obtained results show that the resin interacts by the same mechanism, where the amide groups form a complex with hydrated cations, while the carboxylic group interacts by ion-exchange mechanism. 1 fig., 1 tab

  5. The influence of the “cage effect” on the mechanism of reversible bimolecular multistage chemical reactions in solutions

    International Nuclear Information System (INIS)

    Doktorov, Alexander B.

    2015-01-01

    Manifestations of the “cage effect” at the encounters of reactants are theoretically treated by the example of multistage reactions in liquid solutions including bimolecular exchange reactions as elementary stages. It is shown that consistent consideration of quasi-stationary kinetics of multistage reactions (possible only in the framework of the encounter theory) for reactions proceeding near reactants contact can be made on the basis of the concepts of a “cage complex.” Though mathematically such a consideration is more complicated, it is more clear from the standpoint of chemical notions. It is established that the presence of the “cage effect” leads to some important effects not inherent in reactions in gases or those in solutions proceeding in the kinetic regime, such as the appearance of new transition channels of reactant transformation that cannot be caused by elementary event of chemical conversion for the given mechanism of reaction. This results in that, for example, rate constant values of multistage reaction defined by standard kinetic equations of formal chemical kinetics from experimentally measured kinetics can differ essentially from real values of these constants

  6. The influence of the “cage effect” on the mechanism of reversible bimolecular multistage chemical reactions in solutions

    Energy Technology Data Exchange (ETDEWEB)

    Doktorov, Alexander B., E-mail: doktorov@kinetics.nsc.ru [Voevodsky Institute of Chemical Kinetics & Combustion, Siberian Branch of the Russian Academy of Sciences, 630090 Novosibirsk, Russia and Novosibirsk State University, Novosibirsk 630090 (Russian Federation)

    2015-08-21

    Manifestations of the “cage effect” at the encounters of reactants are theoretically treated by the example of multistage reactions in liquid solutions including bimolecular exchange reactions as elementary stages. It is shown that consistent consideration of quasi-stationary kinetics of multistage reactions (possible only in the framework of the encounter theory) for reactions proceeding near reactants contact can be made on the basis of the concepts of a “cage complex.” Though mathematically such a consideration is more complicated, it is more clear from the standpoint of chemical notions. It is established that the presence of the “cage effect” leads to some important effects not inherent in reactions in gases or those in solutions proceeding in the kinetic regime, such as the appearance of new transition channels of reactant transformation that cannot be caused by elementary event of chemical conversion for the given mechanism of reaction. This results in that, for example, rate constant values of multistage reaction defined by standard kinetic equations of formal chemical kinetics from experimentally measured kinetics can differ essentially from real values of these constants.

  7. 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

  8. 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.

  9. Blow-up Mechanism of Classical Solutions to Quasilinear Hyperbolic Systems in the Critical Case

    Institute of Scientific and Technical Information of China (English)

    2006-01-01

    This paper deals with the blow-up phenomenon, particularly, the geometric blow-up mechanism, of classical solutions to the Cauchy problem for quasilinear hyperbolic systems in the critical case. We prove that it is still the envelope of the same family of characteristics which yields the blowup of classical solutions to the Cauchy problem in the critical case.

  10. Characteristic and mechanism of Th{sup 4+} sorption from nitric acid solutions by rice and wheat bran

    Energy Technology Data Exchange (ETDEWEB)

    Monji, Akbar Boveiri [Kharazmi Univ., Tehran (Iran, Islamic Republic of). Faculty of Chemistry; Nuclear Science and Technology Research Institute, Tehran (Iran, Islamic Republic of); Ghoulipour, Vanik [Kharazmi Univ., Tehran (Iran, Islamic Republic of). Faculty of Chemistry; Mallah, Mohammad Hassan [Nuclear Science and Technology Research Institute, Tehran (Iran, Islamic Republic of)

    2015-07-01

    In line with our previously conducted researches, various instrumental methods were applied to evaluate the adsorption features and mechanism of Th{sup 4+} from highly acidic solution (4M HNO{sub 3}) by rice and wheat bran. Although the results of cation exchange confirmed the existence of ion-exchange interaction in Th{sup 4+} adsorption, it had a trivial contribution in the biosorption process. The presence of Th{sup 4+} ions on the biomass surface was obviously revealed in SEM images and EDS elemental analysis. Moreover, the linkage of C=O, O-H and N-H functional groups on the biomass surface with Th{sup 4+} ions was clearly represented in the ATR-FTIR spectroscopic analysis. Additionally, desorption studies indicated that ammonium oxalate (>81.3%) and ammonium carbonate (>75.4%) were effective in desorbing Th{sup 4+} from the biomass surface due to strong interactions of hard functional groups of C=O with Th{sup 4+}. The overall observations unfold the fact that electrostatic complexation mechanism is dominant between biomass and Th{sup 4+} ions.

  11. Kinetics and mechanism of oxidation of 1-hydroxymethyl-eta/sup 3/-allypalladium chloride by p-benzoquinone in aqueous solutions

    Energy Technology Data Exchange (ETDEWEB)

    Belov, A.P.; Kalabin, S.M.; Statsenko, O.N.

    1988-03-01

    /sup 1/H NMR spectroscopy was used to show that the primary product of the oxidation of the eta/sup 3/-allyl complex of palladium, (based on 1,3-butadiene-1-hydroxymethyl-eta/sup 3/-allylpalladium chloride), by the action of p-benzoquinone in acid aqueous solutions is 4-chloro-2-buten-1-o1. The reaction kinetics were studied colorimetrically. It was found that the rate of reaction is described by a kinetic equation of the second order (first with respect to each of the reagents). It was shown that the second order rate constant increases nonlinearly with increase in the concentration of the chloride ions and hydrogen ions, and tends to a constant value in the region of high concentrations of these ions. The values of the activation parameters and the isotopic kinetic effect were determined. The kinetic equation and the mechanism of the reaction studied were compared with those of the oxidation processes of unsubstituted eta/sup 3/-allyl complexes of palladium.

  12. 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.

  13. Mechanism of nucleation and growth of hydrogen porosity in solidifying A356 aluminum alloy: an analytical solution

    International Nuclear Information System (INIS)

    Li, K.-D.; Chang, Edward

    2004-01-01

    This study derives an analytical solution for the mechanism of nucleation and growth of hydrogen pore in the solidifying A356 aluminum alloy. A model of initial transient hydrogen redistribution in the growing dendritic grain is used to modify the lever rule for the mechanism of nucleation of pore. The model predicts the fraction of solid at nucleation, the temperature range of nucleation, the radius of hydrogen diffusion cell, and the supersaturation of hydrogen needed for nucleation. The role of solidus velocity in nucleation is explained. The parameters calculated from the model of nucleation are used for analyzing the mechanism of kinetic diffusion-controlled growth of pore, in which the mathematical transformations of variables are introduced. With the transformations, it is argued that the diffusion problem involving the liquid and solid phases during solidification could be treated as a classic problem of precipitation in the single-phase medium treated by Ham or Avrami. The analytical solution for the nucleation of pore is compared with the mechanism of macrosegregation. The predicted volume percent of porosity and radius of pore based on the mechanism of growth of pore is discussed with respect to the thermodynamic solution, the published experimental data, the numerical solutions, and the role of interdendritic fluid flow governed by Darcy's law

  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. Mobility and Position Error Analysis of a Complex Planar Mechanism with Redundant Constraints

    Science.gov (United States)

    Sun, Qipeng; Li, Gangyan

    2018-03-01

    Nowadays mechanisms with redundant constraints have been created and attracted much attention for their merits. The mechanism of the redundant constraints in a mechanical system is analyzed in this paper. A analysis method of Planar Linkage with a repetitive structure is proposed to get the number and type of constraints. According to the difference of applications and constraint characteristics, the redundant constraints are divided into the theoretical planar redundant constraints and the space-planar redundant constraints. And the calculation formula for the number of redundant constraints and type of judging method are carried out. And a complex mechanism with redundant constraints is analyzed of the influence about redundant constraints on mechanical performance. With the combination of theoretical derivation and simulation research, a mechanism analysis method is put forward about the position error of complex mechanism with redundant constraints. It points out the direction on how to eliminate or reduce the influence of redundant constraints.

  16. 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.

  17. 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

  18. Microstructure, mechanical property and metal release of As-SLM CoCrW alloy under different solution treatment conditions.

    Science.gov (United States)

    Lu, Yanjin; Wu, Songquan; Gan, Yiliang; Zhang, Shuyuan; Guo, Sai; Lin, Junjie; Lin, Jinxin

    2015-03-01

    In the study, the microstructure, mechanical property and metal release behavior of selective laser melted CoCrW alloys under different solution treatment conditions were systemically investigated to assess their potential use in orthopedic implants. The effects of the solution treatment on the microstructure, mechanical properties and metal release were systematically studied by OM, SEM, XRD, tensile test, and ICP-AES, respectively. The XRD indicated that during the solution treatment the alloy underwent the transformation of γ-fcc to ε-hcp phase; the ε-hcp phase nearly dominated in the alloy when treated at 1200°C following the water quenching; the results from OM, SEM showed that the microstructural change was occurred under different solution treatments; solution at 1150°C with furnace cooling contributed to the formation of larger precipitates at the grain boundary regions, while the size and number of the precipitates was decreased as heated above 1100°C with the water quenching; moreover, the diamond-like structure was invisible at higher solution temperature over 1150°C following water quenching; compared with the furnace cooling, the alloy quenched by water showed excellent mechanical properties and low amount of metal release; as the alloy heated at 1200°C, the mechanical properties of the alloy reached their optimum combination at UTS=1113.6MPa, 0.2%YS=639.5MPa, and E%=20.1%, whilst showed the lower total quantity of metal release. It is suggested that a proper solution treatment is an efficient strategy for improving the mechanical properties and corrosion resistance of As-SLM CoCrW alloy that show acceptable tensile ductility. Copyright © 2015 Elsevier Ltd. All rights reserved.

  19. Theoretical Proposal for the Whole Phosphate Diester Hydrolysis Mechanism Promoted by a Catalytic Promiscuous Dinuclear Copper(II) Complex.

    Science.gov (United States)

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

    2016-03-21

    The catalytic mechanism that involves the cleavage of the phosphate diester model BDNPP (bis(2,4-dinitrophenyl) phosphate) catalyzed through a dinuclear copper complex is investigated in the current study. The metal complex was originally designed to catalyze catechol oxidation, and it showed an interesting catalytic promiscuity case in biomimetic systems. The current study investigates two different reaction mechanisms through quantum mechanics calculations in the gas phase, and it also includes the solvent effect through PCM (polarizable continuum model) single-point calculations using water as solvent. Two mechanisms are presented in order to fully describe the phosphate diester hydrolysis. Mechanism 1 is of the S(N)2 type, which involves the direct attack of the μ-OH bridge between the two copper(II) ions toward the phosphorus center, whereas mechanism 2 is the process in which hydrolysis takes place through proton transfer between the oxygen atom in the bridging hydroxo ligand and the other oxygen atom in the phosphate model. Actually, the present theoretical study shows two possible reaction paths in mechanism 1. Its first reaction path (p1) involves a proton transfer that occurs immediately after the hydrolytic cleavage, so that the proton transfer is the rate-determining step, which is followed by the entry of two water molecules. Its second reaction path (p2) consists of the entry of two water molecules right after the hydrolytic cleavage, but with no proton transfer; thus, hydrolytic cleavage is the rate-limiting step. The most likely catalytic path occurs in mechanism 1, following the second reaction path (p2), since it involves the lowest free energy activation barrier (ΔG(⧧) = 23.7 kcal mol(-1), in aqueous solution). A kinetic analysis showed that the experimental k(obs) value of 1.7 × 10(-5) s(-1) agrees with the calculated value k1 = 2.6 × 10(-5) s(-1); the concerted mechanism is kinetically favorable. The KIE (kinetic isotope effect) analysis

  20. 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.

  1. An adaptive quantum mechanics/molecular mechanics method for the infrared spectrum of water: incorporation of the quantum effect between solute and solvent.

    Science.gov (United States)

    Watanabe, Hiroshi C; Banno, Misa; Sakurai, Minoru

    2016-03-14

    Quantum effects in solute-solvent interactions, such as the many-body effect and the dipole-induced dipole, are known to be critical factors influencing the infrared spectra of species in the liquid phase. For accurate spectrum evaluation, the surrounding solvent molecules, in addition to the solute of interest, should be treated using a quantum mechanical method. However, conventional quantum mechanics/molecular mechanics (QM/MM) methods cannot handle free QM solvent molecules during molecular dynamics (MD) simulation because of the diffusion problem. To deal with this problem, we have previously proposed an adaptive QM/MM "size-consistent multipartitioning (SCMP) method". In the present study, as the first application of the SCMP method, we demonstrate the reproduction of the infrared spectrum of liquid-phase water, and evaluate the quantum effect in comparison with conventional QM/MM simulations.

  2. 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

  3. 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)

  4. 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

  5. Problems in quantum mechanics with solutions

    CERN Document Server

    d'Emilio, Emilio

    2017-01-01

    This second edition of an extremely well-received book presents more than 250 nonrelativistic quantum mechanics problems of varying difficulty with the aim of providing students didactic material of proven value, allowing them to test their comprehension and mastery of each subject. The coverage is extremely broad, from themes related to the crisis of classical physics through achievements within the framework of modern atomic physics to lively debated, intriguing aspects relating to, for example, the EPR paradox, the Aharonov-Bohm effect, and quantum teleportation. Compared with the first edition, a variety of improvements have been made and additional topics of interest included, especially focusing on elementary potential scattering. The problems themselves range from standard and straightforward ones to those that are complex but can be considered essential because they address questions of outstanding importance or aspects typically overlooked in primers. The book offers students both an excellent tool f...

  6. Effect of solution treatment temperature and cooling rate on the mechanical properties of tungsten heavy alloy

    Energy Technology Data Exchange (ETDEWEB)

    Kumari, Anjali, E-mail: anjalikumari1261@gmail.com; Prabhu, G.; Sankaranarayana, M.; Nandy, T.K.

    2017-03-14

    The present study investigates the effect of solution treatment temperature and cooling rate on mechanical properties of a tungsten heavy alloy (89.6W-6.2Ni-1.8Fe-2.4Co). In addition to water quenching, rapid argon quenching has been attempted in this study since it is a relatively cleaner process and it can be used in conjunction with vacuum treatment. Since in these alloys, there is a possibility of incomplete dissolution of intermetallics or segregation of impurities during heat treatment, which results in scatter in the mechanical properties, it was decided that the solution treatment temperature for both water and argon quenching would be varied from 1100 to 1250 °C in order to see its effect on the microstructure and mechanical properties. Solution treatment at varying temperatures followed by water quenching resulted in tensile strength ranging from 908 to 921 MPa and % elongation varied from 19% to 26%. On the other hand, the argon quenching heat treatment resulted in tensile strength in the range of 871–955 MPa and % elongation from 9% to 25%. No significant trend with respect to solution treatment temperature on tensile properties was seen in both argon and water quenched samples. % elongation to failure and impact values of water quenched specimens were better than those of argon quenched specimens for a given solution treatment temperature. The impact values appeared to improve with increasing solution treatment temperature in water quenched condition. The properties were correlated with underlying microstructure and fractographs of the failed specimens. The study showed the argon quenching may not be appropriate for the heat treatment of heavy alloys since it results in inferior mechanical properties as compared to water quenching.

  7. 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

  8. Towards a Coherent Theory of Project Alliancing: Discovering the System’s Complex Mechanisms Yielding Value for Money

    Directory of Open Access Journals (Sweden)

    Pertti Lahdenperä

    2017-06-01

    Full Text Available Alliancing is a relatively new construction project delivery method receiving increasing interest globally while also eliciting many questions about its effectiveness. That is why its operating logic should be clarified beyond the currently existing general views. Correspondingly, this paper aims to define the means and mechanisms which influence the capacity of alliancing to produce value for money. The work establishes the interlaced impact chains between formal basic solutions of alliancing and the key result areas defining the value-for-money ratio. This is made by focussing on a single alliance project and its procedural solutions and experiences. The case project of the study was an urban road tunnel under a city structure and the impact chains were explored by interviewing all eight members of the alliance leadership team covering all contracting parties. The two-stage personal interviews were conducted in accordance with the systematic modelling procedure resulting in eight cognitive maps which were then combined into a group map. The resulting model included around one hundred interlinked concepts initially, but was streamlined for the paper. Accordingly, alliancing offers a concrete framework which gives better than normal chances of success in the case of complex, challenging projects fraught with much uncertainty. Many diverse basic alliance solutions/features contribute to success, while each feature also seems to strengthen the impact of the others. This suggests that, at its best, pure project alliance is not only a coherent but also a holistic solution to challenging projects.

  9. Simple thermodynamic model of the extension of solid solution of Cu-Mo alloys processed by mechanical alloying

    International Nuclear Information System (INIS)

    Aguilar, C.; Guzman, D.; Rojas, P.A.; Ordonez, Stella; Rios, R.

    2011-01-01

    Highlights: → Extension of solid solution in Cu-Mo systems achieved by mechanical alloying. → Simple thermodynamic model to explain extension of solid solution of Mo in Cu. → Model gives results that are consistent with the solubility limit extension reported in other works. - Abstract: The objective of this work is proposing a simple thermodynamic model to explain the increase in the solubility limit of the powders of the Cu-Mo systems or other binary systems processed by mechanical alloying. In the regular solution model, the effects of crystalline defects, such as; dislocations and grain boundary produced during milling were introduced. The model gives results that are consistent with the solubility limit extension reported in other works for the Cu-Cr, Cu-Nb and Cu-Fe systems processed by mechanical alloying.

  10. Mechanism of action of sodium hypochlorite

    Directory of Open Access Journals (Sweden)

    Estrela Carlos

    2002-01-01

    Full Text Available The choice of an irrigating solution for use in infected root canals requires previous knowledge of the microorganisms responsible for the infectious process as well as the properties of different irrigating solutions. Complex internal anatomy, host defenses and microorganism virulence are important factors in the treatment of teeth with asymptomatic apical periodontitis. Irrigating solutions must have expressive antimicrobial action and tissue dissolution capacity. Sodium hypochlorite is the most used irrigating solution in endodontics, because its mechanism of action causes biosynthetic alterations in cellular metabolism and phospholipid destruction, formation of chloramines that interfere in cellular metabolism, oxidative action with irreversible enzymatic inactivation in bacteria, and lipid and fatty acid degradation. The aim of this work is to discuss the mechanism of action of sodium hypochlorite based on its antimicrobial and physico-chemical properties.

  11. Fluid Mechanics and Complex Variable Theory: Getting Past the 19th Century

    Science.gov (United States)

    Newton, Paul K.

    2017-01-01

    The subject of fluid mechanics is a rich, vibrant, and rapidly developing branch of applied mathematics. Historically, it has developed hand-in-hand with the elegant subject of complex variable theory. The Westmont College NSF-sponsored workshop on the revitalization of complex variable theory in the undergraduate curriculum focused partly on…

  12. Mechanisms Underlying the Formation of Complexes between Maize Starch and Lipids.

    Science.gov (United States)

    Chao, Chen; Yu, Jinglin; Wang, Shuo; Copeland, Les; Wang, Shujun

    2018-01-10

    This study aimed to reveal the mechanism of formation of complexes between native maize starch (NMS) and different types of lipids, namely palmitic acid (PA), monopalmitate glycerol (MPG), dipalmitate glycerol (DPG), and tripalmitate glycerol (TPG). The complexing index followed the order of MPG (96.3%) > PA (41.8%) > TPG (8.3%) > DPG (1.1%), indicating that MPG formed more complexes with NMS than PA, and that few complexes were formed between NMS and DPG and TPG. The NMS-PA complex presented higher thermal transition temperatures and lower enthalpy change than the NMS-MPG complex, indicating that although MPG formed more starch complexes, they had less stable crystalline structures than the complex between NMS and PA. X-ray diffraction (XRD) and Raman spectroscopy showed that both MPG and PA formed V-type crystalline structures with NMS, and confirmed that no complexes were formed between NMS and DPG and TPG. We conclude that the monoglyceride formed more starch-lipid complex with maize starch than PA, but that the monoglyceride complex had a less stable structure than that formed with PA. The di- and triglycerides did not form complexes with maize starch.

  13. 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.

  14. Thermal, dielectric characteristics and conduction mechanism of azodyes derived from quinoline and their copper complexes.

    Science.gov (United States)

    El-Ghamaz, N A; Diab, M A; El-Bindary, A A; El-Sonbati, A Z; Nozha, S G

    2015-05-15

    A novel series of (5-(4'-derivatives phenyl azo)-8-hydroxy-7-quinolinecarboxaldehyde) (AQLn) (n=1, p-OCH3; n=2, R=H; and n=3; p-NO2) and their complexes [Cu(AQLn)2]·5H2O are synthesized and investigated. The optimized bond lengths, bond angles and the calculated quantum chemical parameters for AQLn are investigated. HOMO-LUMO energy gap, absolute electronegativities, chemical potentials, and absolute hardness are also calculated. The thermal properties, dielectric properties, alternating current conductivity (σac) and conduction mechanism are investigated in the frequency range 0.1-100kHz and temperature range 293-568K for AQL1-3 and 318-693K for [Cu(AQL1-3)2]·5H2O complexes. The thermal properties are of ligands (AQLn) and their Cu(II) complexes investigated by thermogravimetric analysis (TGA). The temperature and frequency dependence of the real and the imaginary part of the dielectric constant are studied. The values of the thermal activation energy of conduction mechanism for AQLn and their complexes [Cu(AQLn)2]·5H2O under investigation are calculated at different test frequencies. The values of thermal activation energies ΔE1 and ΔE2 for AQLn and [Cu(AQLn)2]·5H2O decrease with increasing the values of frequency. The ac conductivity is found to be depending on the chemical structure of the compounds. Different conduction mechanisms have been proposed to explain the obtained experimental data. The small polaron tunneling (SPT) is the dominant conduction mechanism for AQL1 and its complex [Cu(AQL1)2]·5H2O. The quantum mechanical tunneling (QMT) is the dominant conduction mechanism for AQL2 and its complex [Cu(AQL2)2]·5H2O. The correlated barrier hopping (CBH) is the dominant conduction mechanism for AQL3 and its complex [Cu(AQL3)2]·5H2O, and the values of the maximum barrier height (Wm) are calculated. Copyright © 2015 Elsevier B.V. All rights reserved.

  15. First order mean field games - explicit solutions, perturbations and connection with classical mechanics

    KAUST Repository

    Gomes, Diogo A.

    2016-01-06

    We present recent developments in the theory of first-order mean-field games (MFGs). A standard assumption in MFGs is that the cost function of the agents is monotone in the density of the distribution. This assumption leads to a comprehensive existence theory and to the uniqueness of smooth solutions. Here, our goals are to understand the role of local monotonicity in the small perturbation regime and the properties of solutions for problems without monotonicity. Under a local monotonicity assumption, we show that small perturbations of MFGs have unique smooth solutions. In addition, we explore the connection between first-order MFGs and classical mechanics and KAM theory. Next, for non-monotone problems, we construct non-unique explicit solutions for a broad class of first-order mean-field games. We provide an alternative formulation of MFGs in terms of a new current variable. These examples illustrate two new phenomena: the non-uniqueness of solutions and the breakdown of regularity.

  16. First order mean field games - explicit solutions, perturbations and connection with classical mechanics

    KAUST Repository

    Gomes, Diogo A.; Nurbekyan, Levon; Prazeres, Mariana

    2016-01-01

    We present recent developments in the theory of first-order mean-field games (MFGs). A standard assumption in MFGs is that the cost function of the agents is monotone in the density of the distribution. This assumption leads to a comprehensive existence theory and to the uniqueness of smooth solutions. Here, our goals are to understand the role of local monotonicity in the small perturbation regime and the properties of solutions for problems without monotonicity. Under a local monotonicity assumption, we show that small perturbations of MFGs have unique smooth solutions. In addition, we explore the connection between first-order MFGs and classical mechanics and KAM theory. Next, for non-monotone problems, we construct non-unique explicit solutions for a broad class of first-order mean-field games. We provide an alternative formulation of MFGs in terms of a new current variable. These examples illustrate two new phenomena: the non-uniqueness of solutions and the breakdown of regularity.

  17. 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.

  18. BlenX-based compositional modeling of complex reaction mechanisms

    Directory of Open Access Journals (Sweden)

    Judit Zámborszky

    2010-02-01

    Full Text Available Molecular interactions are wired in a fascinating way resulting in complex behavior of biological systems. Theoretical modeling provides a useful framework for understanding the dynamics and the function of such networks. The complexity of the biological networks calls for conceptual tools that manage the combinatorial explosion of the set of possible interactions. A suitable conceptual tool to attack complexity is compositionality, already successfully used in the process algebra field to model computer systems. We rely on the BlenX programming language, originated by the beta-binders process calculus, to specify and simulate high-level descriptions of biological circuits. The Gillespie's stochastic framework of BlenX requires the decomposition of phenomenological functions into basic elementary reactions. Systematic unpacking of complex reaction mechanisms into BlenX templates is shown in this study. The estimation/derivation of missing parameters and the challenges emerging from compositional model building in stochastic process algebras are discussed. A biological example on circadian clock is presented as a case study of BlenX compositionality.

  19. Mechanics of Cellulose Synthase Complexes in Living Plant Cells

    Science.gov (United States)

    Zehfroosh, Nina; Liu, Derui; Ramos, Kieran P.; Yang, Xiaoli; Goldner, Lori S.; Baskin, Tobias I.

    The polymer cellulose is one of the major components of the world's biomass with unique and fascinating characteristics such as its high tensile strength, renewability, biodegradability, and biocompatibility. Because of these distinctive aspects, cellulose has been the subject of enormous scientific and industrial interest, yet there are still fundamental open questions about cellulose biosynthesis. Cellulose is synthesized by a complex of transmembrane proteins called ``Cellulose Synthase A'' (CESA) in the plasma membrane. Studying the dynamics and kinematics of the CESA complex will help reveal the mechanism of cellulose synthesis and permit the development and validation of models of CESA motility. To understand what drives these complexes through the cell membrane, we used total internal reflection fluorescence microscopy (TIRFM) and variable angle epi-fluorescence microscopy to track individual, fluorescently-labeled CESA complexes as they move in the hypocotyl and root of living plants. A mean square displacement analysis will be applied to distinguish ballistic, diffusional, and other forms of motion. We report on the results of these tracking experiments. This work was funded by NSF/PHY-1205989.

  20. Sorption mechanism of Cd(II) from water solution onto chicken eggshell

    Science.gov (United States)

    Flores-Cano, Jose Valente; Leyva-Ramos, Roberto; Mendoza-Barron, Jovita; Guerrero-Coronado, Rosa María; Aragón-Piña, Antonio; Labrada-Delgado, Gladis Judith

    2013-07-01

    The mechanism and capacity of eggshell for sorbing Cd(II) from aqueous solution was examined in detail. The eggshell was characterized by several techniques. The eggshell was mainly composed of Calcite (CaCO3). The surface charge distribution was determined by acid-base titration and the point of zero charge (PZC) of the eggshell was found to be 11.4. The sorption equilibrium data were obtained in a batch adsorber, and the adsorption isotherm of Langmuir fitted the data quite well. The sorption capacity of eggshell increased while raising the pH from 4 to 6, this tendency was attributed to the electrostatic interaction between the Cd2+ in solution and the surface of the eggshell. Furthermore, the sorption capacity was augmented by increasing the temperature from 15 to 35 °C because the sorption was endothermic. The sorption of Cd(II) occurred mainly onto the calcareous layer of the eggshell, but slightly on the membrane layer. It was demonstrated that the sorption of Cd(II) was not reversible, and the main sorption mechanisms were precipitation and ion exchange. The precipitation of (Cd,Ca)CO3 on the surface of the eggshell was corroborated by SEM and XRD analysis.

  1. Inhibition Mechanism of Uranyl Reduction Induced by Calcium-Carbonato Complexes

    Science.gov (United States)

    Jones, M. E.; Bargar, J.; Fendorf, S. E.

    2015-12-01

    Uranium mobility in the subsurface is controlled by the redox state and chemical speciation, generally as minimally soluble U(IV) or soluble U(VI) species. In the presence of even low carbonate concentrations the uranyl-carbonato complex quickly becomes the dominant aqueous species; they are, in fact, the primary aqueous species in most groundwaters. Calcium in groundwater leads to ternary calcium-uranyl-carbonato complexes that limit the rate and extent of U(VI) reduction. This decrease in reduction rate has been attributed to surface processes, thermodynamic limitations, and kinetic factors. Here we present a new mechanism for the inhibition of ferrous iron reduction of uranyl-carbonato species in the presence of calcium. A series of experiments under variable Ca conditions were preformed to determine the role of Ca in the inhibition of U reduction by ferrous iron. Calcium ions in the Ca2UO2(CO3)3 complex sterically prevent the interaction of Fe(II) with U(VI), in turn preventing the Fe(II)-U(VI) distance required for electron transfer. The mechanism described here helps to predict U redox transformations in suboxic environments and clarifies the role of Ca in the fate and mobility of U. Electrochemical measurements further show the decrease of the U(VI) to U(V) redox potential of the uranyl-carbonato complex with decreasing pH suggesting the first electron transfer is critical determining the rate and extent of uranium reduction.

  2. Mechanism of central ion exchange between ytterbium(3) and neodymium(3) diethylenetriaminepentaacetate in aqueous solution

    Energy Technology Data Exchange (ETDEWEB)

    Nikitenko, S.I.; Martynenko, L.I.; Pechurova, N.I. (Moskovskij Gosudarstvennyj Univ. (USSR))

    1984-11-01

    Kinetics and exchange mechanism in the NdL/sup 2 -/Yb/sup 3 +/ system, where L/sup 5 -/ is diethylene triaminepentaacetate-ion, are studied spectrophotometrically. It is shown that in the pH range of 4.0-4.5 the exchange occurs according to dissociative mechanism with the formation of biprotonated intermediate complexes. In the pH 4.5-5.0 range the formation of monoprotonated inermediates is possible. At pH values of 5.0-6.0 the exchange is mainly performed according to the associative mechanism with the formation of biprotonated intermediate complexes. In the pH 4.5-5.0 range the formation of monoprotonated intermediates is possible. At pH values of 5.0-6.0 the exchange is mainly performed according to the associative mechanism. It is found that under conditions of the experiment the binuclear complex of the ((YbL)Nd)/sup +/ composition is the association mechanism exchange product. It is also formed in the case of mixing YbL/sup 2 -/ and Nd/sup 3 +/. Rate constants of exchange according to dissociative mechanism and constant of intraspheric isomerization ((NdL)Yb)/sup +/ ..-->.. ((YbL)Nd)/sup +/ are calculated. Stability constants of ((NdL)Yb)/sup +/ and ((YbL)Nd)/sup +/ are determined.

  3. 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

  4. Travelling wave solutions for a surface wave equation in fluid mechanics

    Directory of Open Access Journals (Sweden)

    Tian Yi

    2016-01-01

    Full Text Available This paper considers a non-linear wave equation arising in fluid mechanics. The exact traveling wave solutions of this equation are given by using G'/G-expansion method. This process can be reduced to solve a system of determining equations, which is large and difficult. To reduce this process, we used Wu elimination method. Example shows that this method is effective.

  5. Localized solid-state amorphization at grain boundaries in a nanocrystalline Al solid solution subjected to surface mechanical attrition

    Energy Technology Data Exchange (ETDEWEB)

    Wu, X [State Key Laboratory of Nonlinear Mechanics, Institute of Mechanics, Chinese Academy of Sciences, Beijing 100080 (China); Tao, N [Shenyang National Laboratory for Materials Science, Institute of Metal Research, Chinese Academy of Sciences, Shenyang 110016 (China); Hong, Y [State Key Laboratory of Nonlinear Mechanics, Institute of Mechanics, Chinese Academy of Sciences, Beijing 100080 (China); Lu, J [LASMIS, University of Technology of Troyes, 10000, Troyes (France); Lu, K [Shenyang National Laboratory for Materials Science, Institute of Metal Research, Chinese Academy of Sciences, Shenyang 110016 (China)

    2005-11-21

    Using high-resolution electron microscopy, localized solid-state amorphization (SSA) was observed in a nanocrystalline (NC) Al solid solution (weight per cent 4.2 Cu, 0.3 Mn, the rest being Al) subjected to a surface mechanical attrition treatment. It was found that the deformation-induced SSA may occur at the grain boundary (GB) where either the high density dislocations or dislocation complexes are present. It is suggested that lattice instability due to elastic distortion within the dislocation core region plays a significant role in the initiation of the localized SSA at defective sites. Meanwhile, the GB of severely deformed NC grains exhibits a continuously varying atomic structure in such a way that while most of the GB is ordered but reveals corrugated configurations, localized amorphization may occur along the same GB.

  6. Features of the ESI mechanism that affect the observation of multiply charged noncovalent protein complexes and the determination of the association constant by the titration method.

    Science.gov (United States)

    Peschke, Michael; Verkerk, Udo H; Kebarle, Paul

    2004-10-01

    Several factors, attributable to the ESIMS mechanism, that can affect the assumptions of the titration method are examined: (1) The assumption that the concentrations in solution of the protein P, the ligand L, and the complex PL are proportional to the respective ion intensities observed with ESIMS, is examined with experiments in which ion intensities of two non-interacting proteins are compared with the respective concentrations. The intensities are found to be approximately proportional to the concentrations. The proportionality factors are found to increase as the mass of the protein is decreased. Very small proteins have much higher intensities. The results suggest that it is preferable to use only the intensity ratio of PL and P, whose masses are very close to each other when L is small, to determine the association constant KA in solution. (2) From the charge residue model (CRM) one expects that the solution will experience a very large increase of concentration due to evaporation of the precursor droplets, before the proteins P and PL are produced in the gas phase. This can shift the equilibrium in the droplets: P + L = PL, towards PL. Analysis of the droplet evaporation history shows that such a shift is not likely, because the time of droplet evolution is very short, only several micros, and the equilibrium relaxation time is much longer. (3) The droplet history shows that unreacted P and L can be often present together in the same droplet. On complete evaporation of such droplets L will land on P leading to PL and this effect will lead to values of KA that are too high. However, it is argued that mostly accidental, weakly bonded, complexes will form and these will dissociate in the clean up stages (heated transfer capillary and CAD region). Thus only very small errors are expected due to this cause. (4) Some PL complexes may have bonding that is too weak in the gas phase even though they have KA values in solution that predict high solution PL yields

  7. Sturm solutions of the two-centre problem in quantum mechanics

    International Nuclear Information System (INIS)

    Truskova, N.F.

    1984-01-01

    Algorithm of computer calculation of the Sturm solutions of the two-body problem in quantum mechanics has been presented for different magnitudes of internuclear distance R and at energies E<0, which correspond to a definite term of the above problem or to a constants. Formulae of transition from spherical quantum numbers to parabolic ones have been presented, and asymptotics of eigen values at R→0 and R→infinity have been obtained. Calculation results are presented in a graphical form

  8. 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

  9. 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)

  10. 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)

  11. 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.

  12. Reality and dimension of space and the complexity of quantum mechanics

    International Nuclear Information System (INIS)

    Mirman, R.

    1988-01-01

    The dimension (and signature) of space is a result of distances being real numbers and quantum mechanical state functions being complex ones; it is an inescapable consequence of quantum mechanics and group theory. So nonrelativistic quantum mechanics cannot be complete (it requires ad hoc additional assumptions) and consistent (nor can classical physics), leading to relativity, quantum mechanics, and field theory. Implications of the constraints of consistency and physical reasonableness and of group theory for the structure of these theories are considered. It appears that there are simple, perhaps unavoidable reasons for the laws of physics, the nature of the world they describe, and the space in which they act

  13. Existence and asymptotic estimates of periodic solutions of El Niño mechanism of atmospheric physics

    International Nuclear Information System (INIS)

    Xiao-Jing, Li

    2010-01-01

    This paper is devoted to studying the El Niño mechanism of atmospheric physics. The existence and asymptotic estimates of periodic solutions for its model are obtained by employing the technique of upper and lower solution, and using the continuation theorem of coincidence degree theory. (general)

  14. Effect of solution volume covariation on the growth mechanism of Au nanorods using the seed-mediated method

    International Nuclear Information System (INIS)

    Ma, Xiao; Wang, Moo-Chin; Feng, Jinyang; Zhao, Xiujian

    2015-01-01

    The effect of solution volume covariation on the growth mechanism of Au nanorods synthesized using a seed-mediated method was studied. The results from the ultraviolet–visible absorption spectra of gold nanorods (GNRs) revealed that the transverse surface plasmon resonance was ∼550 nm for all GNR samples synthesized in various total volumes of growth solutions. The wavelength of longitudinal surface plasmon resonance of GNRs increased from 757 to 915 nm, with the total volume of growth solution being raised from 10 to 320 ml. Moreover, the calculated aspect ratio (AR) also increased from 3.55 to 5.21 while the total volume of growth solution increased from 10 to 320 ml. Transmission electron microscopy microstructures showed that the growth mechanism of GNRs along 〈1 0 0〉 is in accordance with the hypothesis that the ratio of the number of monodispersed Au atoms existing in the growth solution to the number of seeds explain the behavior of Au atoms deposited on the nanorods with respect to all of the constituent concentrations in the growth solution on the AR of GNRs

  15. 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

  16. 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

  17. 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

  18. Geometry of real and complex canonical transformations in quantum mechanics

    International Nuclear Information System (INIS)

    Grossmann, A.

    1977-08-01

    Quantum mechanics of finitely many particles involves the group of linear (and affine) canonical transformations. A well-defined ray representation of this group acts in the space of states of any quantum-mechanical system with finitely many degrees of freedom and plays a central role in many different contexts. This representation appears quite naturally in quantum mechanics over phase space (Weyl-Wigner correspondence), that it becomes, when suitably written, just a matter of looking at one object from different symplectic reference frames. This is particularly interesting for complex canonical transformations which are represented by unbounded operators. The list of references gives an idea of the variety of motivations and points of view in the subject

  19. 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

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

    International Nuclear Information System (INIS)

    Tatsuya Suzuki

    2013-01-01

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

  1. Exact solutions of the Fokker-Planck equation from an nth order supersymmetric quantum mechanics approach

    Energy Technology Data Exchange (ETDEWEB)

    Schulze-Halberg, Axel [Escuela Superior de Fisica y Matematicas, IPN, Unidad Profesional Adolfo Lopez Mateos, Col. San Pedro Zacatenco, Edificio 9, 07738 Mexico D.F. (Mexico)], E-mail: xbataxel@gmail.com; Rivas, Jesus Morales [Universidad Autonoma Metropolitana - Azcapotzalco, CBI - Area de Fisica Atomica Molecular Aplicada, Av. San Pablo 180, Reynosa Azcapotzalco, 02200 Mexico D.F. (Mexico)], E-mail: jmr@correo.azc.uam.mx; Pena Gil, Jose Juan [Universidad Autonoma Metropolitana - Azcapotzalco, CBI - Area de Fisica Atomica Molecular Aplicada, Av. San Pablo 180, Reynosa Azcapotzalco, 02200 Mexico D.F. (Mexico)], E-mail: jjpg@correo.azc.uam.mx; Garcia-Ravelo, Jesus [Escuela Superior de Fisica y Matematicas, IPN, Unidad Profesional Adolfo Lopez Mateos, Col. San Pedro Zacatenco, Edificio 9, 07738 Mexico D.F. (Mexico)], E-mail: ravelo@esfm.ipn.mx; Roy, Pinaki [Physics and Applied Mathematics Unit, Indian Statistical Institute, Calcutta-700108 (India)], E-mail: pinaki@isical.ac.in

    2009-04-20

    We generalize the formalism of nth order Supersymmetric Quantum Mechanics (n-SUSY) to the Fokker-Planck equation for constant diffusion coefficient and stationary drift potential. The SUSY partner drift potentials and the corresponding solutions of the Fokker-Planck equation are given explicitly. As an application, we generate new solutions of the Fokker-Planck equation by means of our first- and second-order transformation.

  2. Exact solutions of the Fokker-Planck equation from an nth order supersymmetric quantum mechanics approach

    International Nuclear Information System (INIS)

    Schulze-Halberg, Axel; Rivas, Jesus Morales; Pena Gil, Jose Juan; Garcia-Ravelo, Jesus; Roy, Pinaki

    2009-01-01

    We generalize the formalism of nth order Supersymmetric Quantum Mechanics (n-SUSY) to the Fokker-Planck equation for constant diffusion coefficient and stationary drift potential. The SUSY partner drift potentials and the corresponding solutions of the Fokker-Planck equation are given explicitly. As an application, we generate new solutions of the Fokker-Planck equation by means of our first- and second-order transformation.

  3. Oxidation mechanism of diethyl ether: a complex process for a simple molecule.

    Science.gov (United States)

    Di Tommaso, Stefania; Rotureau, Patricia; Crescenzi, Orlando; Adamo, Carlo

    2011-08-28

    A large number of organic compounds, such as ethers, spontaneously form unstable peroxides through a self-propagating process of autoxidation (peroxidation). Although the hazards of organic peroxides are well known, the oxidation mechanisms of peroxidizable compounds like ethers reported in the literature are vague and often based on old experiments, carried out in very different conditions (e.g. atmospheric, combustion). With the aim to (partially) fill the lack of information, in this paper we present an extensive Density Functional Theory (DFT) study of autoxidation reaction of diethyl ether (DEE), a chemical that is largely used as solvent in laboratories, and which is considered to be responsible for various accidents. The aim of the work is to investigate the most probable reaction paths involved in the autoxidation process and to identify all potential hazardous intermediates, such as peroxides. Beyond the determination of a complex oxidation mechanism for such a simple molecule, our results suggest that the two main reaction channels open in solution are the direct decomposition (β-scission) of DEE radical issued of the initiation step and the isomerization of the peroxy radical formed upon oxygen attack (DEEOO˙). A simple kinetic evaluation of these two competing reaction channels hints that radical isomerization may play an unexpectedly important role in the global DEE oxidation process. Finally industrial hazards could be related to the hydroperoxide formation and accumulation during the chain propagation step. The resulting information may contribute to the understanding of the accidental risks associated with the use of diethyl ether.

  4. Chaperone-client complexes: A dynamic liaison

    Science.gov (United States)

    Hiller, Sebastian; Burmann, Björn M.

    2018-04-01

    Living cells contain molecular chaperones that are organized in intricate networks to surveil protein homeostasis by avoiding polypeptide misfolding, aggregation, and the generation of toxic species. In addition, cellular chaperones also fulfill a multitude of alternative functionalities: transport of clients towards a target location, help them fold, unfold misfolded species, resolve aggregates, or deliver clients towards proteolysis machineries. Until recently, the only available source of atomic resolution information for virtually all chaperones were crystal structures of their client-free, apo-forms. These structures were unable to explain details of the functional mechanisms underlying chaperone-client interactions. The difficulties to crystallize chaperones in complexes with clients arise from their highly dynamic nature, making solution NMR spectroscopy the method of choice for their study. With the advent of advanced solution NMR techniques, in the past few years a substantial number of structural and functional studies on chaperone-client complexes have been resolved, allowing unique insight into the chaperone-client interaction. This review summarizes the recent insights provided by advanced high-resolution NMR-spectroscopy to understand chaperone-client interaction mechanisms at the atomic scale.

  5. 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.

  6. 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.

  7. A Comparative Study on Recently-Introduced Nature-Based Global Optimization Methods in Complex Mechanical System Design

    Directory of Open Access Journals (Sweden)

    Abdulbaset El Hadi Saad

    2017-10-01

    Full Text Available Advanced global optimization algorithms have been continuously introduced and improved to solve various complex design optimization problems for which the objective and constraint functions can only be evaluated through computation intensive numerical analyses or simulations with a large number of design variables. The often implicit, multimodal, and ill-shaped objective and constraint functions in high-dimensional and “black-box” forms demand the search to be carried out using low number of function evaluations with high search efficiency and good robustness. This work investigates the performance of six recently introduced, nature-inspired global optimization methods: Artificial Bee Colony (ABC, Firefly Algorithm (FFA, Cuckoo Search (CS, Bat Algorithm (BA, Flower Pollination Algorithm (FPA and Grey Wolf Optimizer (GWO. These approaches are compared in terms of search efficiency and robustness in solving a set of representative benchmark problems in smooth-unimodal, non-smooth unimodal, smooth multimodal, and non-smooth multimodal function forms. In addition, four classic engineering optimization examples and a real-life complex mechanical system design optimization problem, floating offshore wind turbines design optimization, are used as additional test cases representing computationally-expensive black-box global optimization problems. Results from this comparative study show that the ability of these global optimization methods to obtain a good solution diminishes as the dimension of the problem, or number of design variables increases. Although none of these methods is universally capable, the study finds that GWO and ABC are more efficient on average than the other four in obtaining high quality solutions efficiently and consistently, solving 86% and 80% of the tested benchmark problems, respectively. The research contributes to future improvements of global optimization methods.

  8. Electrospray ionization mass spectrometry for the hydrolysis complexes of cisplatin: implications for the hydrolysis process of platinum complexes.

    Science.gov (United States)

    Feifan, Xie; Pieter, Colin; Jan, Van Bocxlaer

    2017-07-01

    Non-enzyme-dependent hydrolysis of the drug cisplatin is important for its mode of action and toxicity. However, up until today, the hydrolysis process of cisplatin is still not completely understood. In the present study, the hydrolysis of cisplatin in an aqueous solution was systematically investigated by using electrospray ionization mass spectrometry coupled to liquid chromatography. A variety of previously unreported hydrolysis complexes corresponding to monomeric, dimeric and trimeric species were detected and identified. The characteristics of the Pt-containing complexes were investigated by using collision-induced dissociation (CID). The hydrolysis complexes demonstrate distinctive and correlative CID characteristics, which provides tools for an informative identification. The most frequently observed dissociation mechanism was sequential loss of NH 3 , H 2 O and HCl. Loss of the Pt atom was observed as the final step during the CID process. The formation mechanisms of the observed complexes were explored and experimentally examined. The strongly bound dimeric species, which existed in solution, are assumed to be formed from the clustering of the parent compound and its monohydrated or dihydrated complexes. The role of the electrospray process in the formation of some of the observed ions was also evaluated, and the electrospray ionization-related cold clusters were identified. The previously reported hydrolysis equilibria were tested and subsequently refined via a hydrolysis study resulting in a renewed mechanistic equilibrium system of cisplatin as proposed from our results. Copyright © 2017 John Wiley & Sons, Ltd. Copyright © 2017 John Wiley & Sons, Ltd.

  9. 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

  10. 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.

  11. 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

  12. Regulatory Mechanisms in the P4-ATPase Complex

    DEFF Research Database (Denmark)

    Costa, Sara

    . The functionality on the P4-ATPase complex is essential for several cellular processes, such as vesicle-mediated transport. However, the specific role of flippase activity in vesicle biogenesis and the regulatory mechanism behind this process is still poorly understood. In these studies, we identified...... affordable alternative using a microscope-based cytometer. This system can simultaneously provide information on flippase activity and expression levels. Taken together, the findings described in this thesis provide new tools for P4-ATPase characterization and valuable insights into the regulation...

  13. 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...

  14. 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.

  15. Anomalous diffusion in niobium. Study of solute diffusion mechanism of iron in niobium

    International Nuclear Information System (INIS)

    Ablitzer, D.

    1977-01-01

    In order to explain anomalously high diffusion velocities observed for iron diffusion in niobium, the following parameters were measured: isotope effect, b factor (which expresses the effect of iron on niobium self-diffusion), self-diffusion coefficient of niobium, solute diffusion coefficient of iron in niobium. The results obtained show that neither pure vacancy models, nor diffusion in the lattice defects (dislocations, sub-boundaries, grain boundaries), nor pure interstitialy mechanisms, nor simple or cyclic exchange mechanisms agree with experiments. A mechanism is proposed which considers an equilibrium between substitution iron atoms and interstitial iron atoms. The diffusion of iron then occurs through interstitial vancancy pairs [fr

  16. 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

  17. 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)

  18. 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)

  19. 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)

  20. Closed-form solutions for linear regulator-design of mechanical systems including optimal weighting matrix selection

    Science.gov (United States)

    Hanks, Brantley R.; Skelton, Robert E.

    1991-01-01

    This paper addresses the restriction of Linear Quadratic Regulator (LQR) solutions to the algebraic Riccati Equation to design spaces which can be implemented as passive structural members and/or dampers. A general closed-form solution to the optimal free-decay control problem is presented which is tailored for structural-mechanical systems. The solution includes, as subsets, special cases such as the Rayleigh Dissipation Function and total energy. Weighting matrix selection is a constrained choice among several parameters to obtain desired physical relationships. The closed-form solution is also applicable to active control design for systems where perfect, collocated actuator-sensor pairs exist. Some examples of simple spring mass systems are shown to illustrate key points.

  1. Reliability Issues and Solutions in Flexible Electronics Under Mechanical Fatigue

    Science.gov (United States)

    Yi, Seol-Min; Choi, In-Suk; Kim, Byoung-Joon; Joo, Young-Chang

    2018-03-01

    Flexible devices are of significant interest due to their potential expansion of the application of smart devices into various fields, such as energy harvesting, biological applications and consumer electronics. Due to the mechanically dynamic operations of flexible electronics, their mechanical reliability must be thoroughly investigated to understand their failure mechanisms and lifetimes. Reliability issue caused by bending fatigue, one of the typical operational limitations of flexible electronics, has been studied using various test methodologies; however, electromechanical evaluations which are essential to assess the reliability of electronic devices for flexible applications had not been investigated because the testing method was not established. By employing the in situ bending fatigue test, we has studied the failure mechanism for various conditions and parameters, such as bending strain, fatigue area, film thickness, and lateral dimensions. Moreover, various methods for improving the bending reliability have been developed based on the failure mechanism. Nanostructures such as holes, pores, wires and composites of nanoparticles and nanotubes have been suggested for better reliability. Flexible devices were also investigated to find the potential failures initiated by complex structures under bending fatigue strain. In this review, the recent advances in test methodology, mechanism studies, and practical applications are introduced. Additionally, perspectives including the future advance to stretchable electronics are discussed based on the current achievements in research.

  2. 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.

  3. MECHANISM OF FINANCIAL SAFETY FORMATION OF ENTERPRISES OF AGROINDUSTRIAL COMPLEX

    Directory of Open Access Journals (Sweden)

    Aleksandr Khomenko

    2016-11-01

    Full Text Available The purpose of work is research of essence of mechanism of forming of financial safety of subjects of agro-industrial complex as to the economic category. Basic financial interests of business entity and financial tasks are certain for their achievement. Considered organization of forming of financial safety of enterprises of agroindustrial complex and offered the measures of realization of the effective system of defence of subjects. The system of financial safety is directed foremost on providing of the own functioning, however, it is necessary to underline that at the same time it is a component part, both at the level of structural subdivisions of subject and at the level of industry, region, state. Financial safety of agrarian sphere is the important constituent of economic security of the state, which acquires an important value for further development of country. Methodology. Methodological basis of the article are methods of scientific cognition, which enable to expose basic conformities to law of development of the probed phenomena and processes, their key problems and priority ways of decision. Such methods are in particular used: analysis and synthesis – during research of constituents of economic security of agricultural enterprises, in particular such as financial safety, and to their aggregate on the whole; systematizations – for dismemberment and more rich in content understanding of essence of the separate probed phenomena and processes; to scientific abstraction – with the purpose of forming of theoretical generalizations and conclusions. A research result is opening of mechanism of financial safety forming of agro-industrial enterprises on the modern stage of socio-economic development of Ukraine. The offered model of strategic prognostication has for an object development of strategy of forming of financial safety of enterprises of agro-industrial complex. Such strategy must avouch for financial prospects enterprises, to

  4. 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

  5. Development of a resilient mechanical sealing solution to resist electro corrosion in ultrapure feedwater applications

    Energy Technology Data Exchange (ETDEWEB)

    Loenhout, Gerard van [Flowservice Flow Solutions Division, Etten-Leur (Netherlands); Enders, Klaus; Schmerberg, Rainer [Vattenfall Europe Generation AG, Peitz (Germany)

    2012-11-01

    Ever since the introduction of mechanical seals on high speed boiler feed pumps in the sixties, mechanical seals have proven to be a reliable, cost effective sealing method. However, since the introduction of combined water treatment chemistry used in today's modern fossil-fuelled power stations, keeping mechanical seal reliability high, became a challenge. A pragmatic approach is presented. A resilient sealing solution was developed to resist electro corrosion for such critical feed water pumps. (orig.)

  6. Geometric Mechanics Reveals Optimal Complex Terrestrial Undulation Patterns

    Science.gov (United States)

    Gong, Chaohui; Astley, Henry; Schiebel, Perrin; Dai, Jin; Travers, Matthew; Goldman, Daniel; Choset, Howie; CMU Team; GT Team

    Geometric mechanics offers useful tools for intuitively analyzing biological and robotic locomotion. However, utility of these tools were previously restricted to systems that have only two internal degrees of freedom and in uniform media. We show kinematics of complex locomotors that make intermittent contacts with substrates can be approximated as a linear combination of two shape bases, and can be represented using two variables. Therefore, the tools of geometric mechanics can be used to analyze motions of locomotors with many degrees of freedom. To demonstrate the proposed technique, we present studies on two different types of snake gaits which utilize combinations of waves in the horizontal and vertical planes: sidewinding (in the sidewinder rattlesnake C. cerastes) and lateral undulation (in the desert specialist snake C. occipitalis). C. cerastes moves by generating posteriorly traveling body waves in the horizontal and vertical directions, with a relative phase offset equal to +/-π/2 while C. occipitalismaintains a π/2 offset of a frequency doubled vertical wave. Geometric analysis reveals these coordination patterns enable optimal movement in the two different styles of undulatory terrestrial locomotion. More broadly, these examples demonstrate the utility of geometric mechanics in analyzing realistic biological and robotic locomotion.

  7. Solution mechanism guide: implementing innovation within a research & development organization.

    Science.gov (United States)

    Keeton, Kathryn E; Richard, Elizabeth E; Davis, Jeffrey R

    2014-10-01

    In order to create a culture more open to novel problem-solving mechanisms, NASA's Human Health and Performance Directorate (HH&P) created a strategic knowledge management tool that educates employees about innovative problem-solving techniques, the Solution Mechanism Guide (SMG). The SMG is a web-based, interactive guide that leverages existing and innovative problem-solving methods and presents this information as a unique user experience so that the employee is empowered to make the best decision about which problem-solving tool best meets their needs. By integrating new and innovative methods with existing problem solving tools, the SMG seamlessly introduces open innovation and collaboration concepts within HH&P to more effectively address human health and performance risks. This commentary reviews the path of creating a more open and innovative culture within HH&P and the process and development steps that were taken to develop the SMG.

  8. 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.

  9. 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

  10. 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.

  11. 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.

  12. Resistometric studies of anodic dissolution and passivation of chromium in weakly acid solutions

    International Nuclear Information System (INIS)

    Shlepakov, M.N.; Sukhotin, A.M.

    1984-01-01

    The method of calculating the rate of Cr anodic solution according to the change of electric resistance of chromium anodes under the effect of potentiostatic polarization, is applied. The maximum corresponding to ranges of active-passive transition is absent in weakly acid solutions with pH>3. The range of existence of active-passive transition is expanded to pH approximately 5.2. The existence of a dissolving section in Cr in the chemical mechanism is proved. Cr passivation mechanism with the formation of passivating oxide of a complex composition is suggested

  13. 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

  14. 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.

  15. 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.

  16. 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.

  17. Quantum mechanics/molecular mechanics modeling of photoelectron spectra: the carbon 1s core-electron binding energies of ethanol-water solutions.

    Science.gov (United States)

    Löytynoja, T; Niskanen, J; Jänkälä, K; Vahtras, O; Rinkevicius, Z; Ågren, H

    2014-11-20

    Using ethanol-water solutions as illustration, we demonstrate the capability of the hybrid quantum mechanics/molecular mechanics (QM/MM) paradigm to simulate core photoelectron spectroscopy: the binding energies and the chemical shifts. An integrated approach with QM/MM binding energy calculations coupled to preceding molecular dynamics sampling is adopted to generate binding energies averaged over the solute-solvent configurations available at a particular temperature and pressure and thus allowing for a statistical assessment with confidence levels for the final binding energies. The results are analyzed in terms of the contributions in the molecular mechanics model-electrostatic, polarization, and van der Waals-with atom or bond granulation of the corresponding MM charge and polarizability force-fields. The role of extramolecular charge transfer screening of the core-hole and explicit hydrogen bonding is studied by extending the QM core to cover the first solvation shell. The results are compared to those obtained from pure electrostatic and polarizable continuum models. Particularly, the dependence of the carbon 1s binding energies with respect to the ethanol concentration is studied. Our results indicate that QM/MM can be used as an all-encompassing model to study photoelectron binding energies and chemical shifts in solvent environments.

  18. 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).

  19. Mechanical Design Optimization Using Advanced Optimization Techniques

    CERN Document Server

    Rao, R Venkata

    2012-01-01

    Mechanical design includes an optimization process in which designers always consider objectives such as strength, deflection, weight, wear, corrosion, etc. depending on the requirements. However, design optimization for a complete mechanical assembly leads to a complicated objective function with a large number of design variables. It is a good practice to apply optimization techniques for individual components or intermediate assemblies than a complete assembly. Analytical or numerical methods for calculating the extreme values of a function may perform well in many practical cases, but may fail in more complex design situations. In real design problems, the number of design parameters can be very large and their influence on the value to be optimized (the goal function) can be very complicated, having nonlinear character. In these complex cases, advanced optimization algorithms offer solutions to the problems, because they find a solution near to the global optimum within reasonable time and computational ...

  20. Mechanical behavior and coupling between mechanical and oxidation in alloy 718: effect of solide solution elements

    International Nuclear Information System (INIS)

    Max, Bertrand

    2014-01-01

    Alloy 718 is the superalloy the most widely used in industry due to its excellent mechanical properties, as well as oxidation and corrosion resistance in wide range of temperatures and solicitation modes. Nevertheless, it is a well-known fact that this alloy is sensitive to stress corrosion cracking and oxidation assisted cracking under loading in the range of temperatures met in service. Mechanisms explaining this phenomenon are not well understood: nevertheless, it is well established that a relation exists between a change in fracture mode and the apparition of plastic instabilities phenomenon. During this study, the instability phenomenon, Portevin-Le Chatelier effect, in alloy 718 was studied by tensile tests in wide ranges of temperatures and strain rates. Different domains of plastic instabilities have been evidenced. Their characteristics suggest the existence of interactions between dislocations and different types of solute elements: interstitials for lower temperatures and substitutionals for higher testing temperatures. Mechanical spectroscopy tests have been performed on alloy 718 and various alloys which composition is comparable to that of alloy 718. These tests prove the mobility of molybdenum atoms in the alloy in the studied temperature range. Specific tests have been performed to study interaction phenomenon between plasticity and oxidation. These results highlight the strong effect of plastic strain rate on both mechanical behavior and intergranular cracking in alloy 718. The subsequent discussion leads to propose hypothesis on coupling effects between deformation mechanisms and oxidation assisted embrittlement in the observed cracking processes. (author)

  1. Macro and micro observations on mortar alternation mechanism under the various solution conditions

    International Nuclear Information System (INIS)

    Fujiwara, A.; Tashiro, S.; Takemura, T.; Sakogaichi, K.; Yokomoto, S.; Katsuyama, K.

    1995-01-01

    Accelerated aging tests have been conducted to evaluate the long-term durability of cementitious material against aggressive ions. In tests, cementitious specimens were immersed in the solutions containing concentrated aggressive ions at high temperature and it promoted diffusion of the ions in the specimen. This method would be suitable for the evaluation on the aging as the alteration of the specimen would be expected to resemble the natural behavior. This paper presents a classification of alteration mechanism in the immersion tests using MgCl 2 and Na 2 SO 4 solution. This classification was done by relating the changes of compressive strength to microscopic and mineralogical changes

  2. Spectral methods and their implementation to solution of aerodynamic and fluid mechanic problems

    Science.gov (United States)

    Streett, C. L.

    1987-01-01

    Fundamental concepts underlying spectral collocation methods, especially pertaining to their use in the solution of partial differential equations, are outlined. Theoretical accuracy results are reviewed and compared with results from test problems. A number of practical aspects of the construction and use of spectral methods are detailed, along with several solution schemes which have found utility in applications of spectral methods to practical problems. Results from a few of the successful applications of spectral methods to problems of aerodynamic and fluid mechanic interest are then outlined, followed by a discussion of the problem areas in spectral methods and the current research under way to overcome these difficulties.

  3. Microstructure and Mechanical Strengths of Metastable FCC Solid Solutions in Al-Ce-Fe System

    OpenAIRE

    A., Inoue; H., Yamaguchi; M., Kikuchi; T., Masumoto; Institute for Materials Research; Institute for Materials Research; Institute for Materials Research; Institute for Materials Research

    1990-01-01

    A metastable fcc solid solution (SS) with high mechanical strengths and good bending ductility was found to be formed in rapidly solidified Al-Ce-Fe alloys containing the solute elements below about 6 at%. The SS consists of equiaxed grains with a size of about 2μm and contains a high density of internal defects. The highest hardness (H_v) and tensile fracture strengtn (σ_f) are 440 and 860 MPa in the as-quenched state and remain almost unchanged up to about 600 K for 1 h, though fine compoun...

  4. Complex fluids modeling and algorithms

    CERN Document Server

    Saramito, Pierre

    2016-01-01

    This book presents a comprehensive overview of the modeling of complex fluids, including many common substances, such as toothpaste, hair gel, mayonnaise, liquid foam, cement and blood, which cannot be described by Navier-Stokes equations. It also offers an up-to-date mathematical and numerical analysis of the corresponding equations, as well as several practical numerical algorithms and software solutions for the approximation of the solutions. It discusses industrial (molten plastics, forming process), geophysical (mud flows, volcanic lava, glaciers and snow avalanches), and biological (blood flows, tissues) modeling applications. This book is a valuable resource for undergraduate students and researchers in applied mathematics, mechanical engineering and physics.

  5. Biosorption behaviors of uranium (VI) from aqueous solution by sunflower straw and insights of binding mechanism

    International Nuclear Information System (INIS)

    Lian Ai; Xuegang Luo; Xiaoyan Lin; Sizhao Zhang

    2013-01-01

    Uranium (VI)-containing water has been recognized as a potential longer-term radiological health hazard. In this work, the sorptive potential of sunflower straw for U (VI) from aqueous solution was investigated in detail, including the effect of initial solution pH, adsorbent dosage, temperature, contact time and initial U (VI) concentration. A dose of 2.0 g L -1 of sunflower straw in an initial U (VI) concentration of 20 mg L -1 with an initial pH of 5.0 and a contact time of 10 h resulted in the maximum U (VI) uptake (about 6.96 mg g -1 ) at 298 K. The isotherm adsorption data was modeled best by the nonlinear Langmuir-Freundlich equation. The equilibrium sorption capacity of sunflower straw was observed to be approximately seven times higher than that of coconut-shell activated carbon as 251.52 and 32.37 mg g -1 under optimal conditions, respectively. The positive enthalpy and negative free energy suggested the endothermic and spontaneous nature of sorption, respectively. The kinetic data conformed successfully to the pseudo-second-order equation. Furthermore, energy dispersive X-ray, fourier transform infrared spectroscopy and X-ray photoelectron spectroscopy demonstrated that U (VI) adsorption onto sunflower straw was predominantly controlled by ion exchange as well as complexation mechanism. The study revealed that sunflower straw could be exploited for uranium remediation of aqueous streams as a promising adsorbent. (author)

  6. Fabrication of nanocrystalline alloys Cu–Cr–Mo super satured solid solution by mechanical alloying

    Energy Technology Data Exchange (ETDEWEB)

    Aguilar, C., E-mail: claudio.aguilar@usm.cl [Departamento de Ingeniería Metalúrgica y Materiales, Universidad Técnica Federico Santa María, Av. España 1680, Valparaíso (Chile); Guzmán, D. [Departamento de Ingeniería en Metalurgia, Facultad de Ingeniería, Universidad de Atacama y Centro Regional de Investigación y Desarrollo Sustentable de Atacama (CRIDESAT), Av. Copayapu 485, Copiapó (Chile); Castro, F.; Martínez, V.; Cuevas, F. de las [Centro de Estudios e Investigaciones Técnicas de Gipuzkoa, Paseo de Manuel Lardizábal, N° 15, 20018 San Sebastián (Spain); Lascano, S. [Departamento de Ingeniería Mecánica, Universidad Técnica Federico Santa María, Av. España 1680, Valparaíso (Chile); Muthiah, T. [Departamento de Ingeniería Metalúrgica y Materiales, Universidad Técnica Federico Santa María, Av. España 1680, Valparaíso (Chile)

    2014-08-01

    This work discusses the extension of solid solubility of Cr and Mo in Cu processed by mechanical alloying. Three alloys processed, Cu–5Cr–5Mo, Cu–10Cr–10Mo and Cu–15Cr–15Mo (weight%) using a SPEX mill. Gibbs free energy of mixing values 10, 15 and 20 kJ mol{sup −1} were calculated for these three alloys respectively by using the Miedema's model. The crystallite size decreases and dislocation density increases when the milling time increases, so Gibbs free energy storage in powders increases by the presence of crystalline defects. The energy produced by crystallite boundaries and strain dislocations were estimated and compared with Gibbs free energy of mixing values. The energy storage values by the presence of crystalline defects were higher than Gibbs free energy of mixing at 120 h for Cu–5Cr–5Mo, 130 h for Cu–10Cr–10Mo and 150 h for Cu–15Cr–15Mo. During milling, crystalline defects are produced that increases the Gibbs free energy storage and thus the Gibbs free energy curves are moved upwards and hence the solubility limit changes. Therefore, the three alloys form solid solutions after these milling time, which are supported with the XRD results. - Highlights: • Extension of solid solution Cr and Mo in Cu achieved by mechanical alloying. • X-ray characterization of Cu–Cr–Mo system processed by mechanical alloying. • Thermodynamics analysis of formation of solid solution of the Cu–Cr–Mo system.

  7. Swelling, mechanical and friction properties of PVA/PVP hydrogels after swelling in osmotic pressure solution.

    Science.gov (United States)

    Shi, Yan; Xiong, Dangsheng; Liu, Yuntong; Wang, Nan; Zhao, Xiaoduo

    2016-08-01

    The potential of polyvinyl alcohol/polyvinylpyrrolidone (PVA/PVP) hydrogels as articular cartilage replacements was in vitro evaluated by using a macromolecule-based solution to mimic the osmotic environment of cartilage tissue. The effects of osmotic pressure solution on the morphology, crystallinity, swelling, mechanical and friction properties of PVA/PVP hydrogels were investigated by swelling them in non-osmotic and osmotic pressure solutions. The results demonstrated that swelling ratio and equilibrium water content were greatly reduced by swelling in osmotic solution, and the swelling process was found to present pseudo-Fickian diffusion character. The crystallization degree of hydrogels after swelling in osmotic solution increased more significantly when it compared with that in non-osmotic solution. After swelling in osmotic solution for 28days, the compressive tangent modulus and storage modulus of hydrogels were significantly increased, and the low friction coefficient was reduced. However, after swelling in the non-osmotic solution, the compressive tangent modulus and friction coefficient of hydrogels were comparable with those of as-prepared hydrogels. The better material properties of hydrogels in vivo than in vitro evaluation demonstrated their potential application in cartilage replacement. Copyright © 2016 Elsevier B.V. All rights reserved.

  8. 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...

  9. 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.

  10. Mechanical Properties of Additively Manufactured Thick Honeycombs

    Directory of Open Access Journals (Sweden)

    Reza Hedayati

    2016-07-01

    Full Text Available Honeycombs resemble the structure of a number of natural and biological materials such as cancellous bone, wood, and cork. Thick honeycomb could be also used for energy absorption applications. Moreover, studying the mechanical behavior of honeycombs under in-plane loading could help understanding the mechanical behavior of more complex 3D tessellated structures such as porous biomaterials. In this paper, we study the mechanical behavior of thick honeycombs made using additive manufacturing techniques that allow for fabrication of honeycombs with arbitrary and precisely controlled thickness. Thick honeycombs with different wall thicknesses were produced from polylactic acid (PLA using fused deposition modelling, i.e., an additive manufacturing technique. The samples were mechanically tested in-plane under compression to determine their mechanical properties. We also obtained exact analytical solutions for the stiffness matrix of thick hexagonal honeycombs using both Euler-Bernoulli and Timoshenko beam theories. The stiffness matrix was then used to derive analytical relationships that describe the elastic modulus, yield stress, and Poisson’s ratio of thick honeycombs. Finite element models were also built for computational analysis of the mechanical behavior of thick honeycombs under compression. The mechanical properties obtained using our analytical relationships were compared with experimental observations and computational results as well as with analytical solutions available in the literature. It was found that the analytical solutions presented here are in good agreement with experimental and computational results even for very thick honeycombs, whereas the analytical solutions available in the literature show a large deviation from experimental observation, computational results, and our analytical solutions.

  11. 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.

  12. Quantum Mechanical Simulations of Complex Nanostructures for Photovoltaic Applications

    Energy Technology Data Exchange (ETDEWEB)

    Wu, Zhigang [Colorado School of Mines, Golden, CO (United States)

    2017-05-31

    A quantitative understanding of the electronic excitations in nanostructures, especially complex nanostructures, is crucial for making new-generation photovoltaic (PV) cells based on nanotechnology, which have high efficiency and low cost. Yet current quantum mechanical simulation methods are either computationally too expensive or not accurate and reliable enough, hindering the rational design of the nanoscale PV cells. The PI seeks to develop new methodologies to overcome the challenges in this very difficult and long-lasting problem, pushing the field forward so that electronic excitations can be accurately predicted for systems involving thousands of atoms. The primary objective of this project is to develop new approaches for electronic excitation calculations that are more accurate than traditional density functional theory (DFT) and are applicable to systems larger than what current beyond-DFT methods can treat. In this proposal, the PI will first address the excited-state problem within the DFT framework to obtain quasiparticle energies from both Kohn-Sham (KS) eigenvalues and orbitals; and the electron-hole binding energy will be computed based on screened Coulomb interaction of corresponding DFT orbitals. The accuracy of these approaches will be examined against many-body methods of GW/BSE and quantum Monte Carlo (QMC). The PI will also work on improving the accuracy and efficiency of the GW/BSE and QMC methods in electronic excitation computations by using better KS orbitals obtained from orbital-dependent DFT as inputs. Then an extended QMC database of ground- and excited-state properties will be developed, and this will be spot checked and supplemented with data from GW/BSE calculations. The investigation will subsequently focus on the development of an improved exchange-correlation (XC) density functional beyond the current generalized gradient approximation (GGA) level of parameterization, with parameters fitted to the QMC database. This will allow

  13. Investigation of cadmium(2) electrolytic reduction kinetics from α-aminoacetic solutions

    International Nuclear Information System (INIS)

    Nikitenko, V.N.; Litovchenko, K.I.; Kublanovskij, V.S.

    1980-01-01

    Kinetics and reduction mechanism of cadmium(2) reduction from α-amino acetic solutions is studied. It is shown that glycine and hydrogen ions take part directly in the electrode reaction of cadmium (2) reduction from α-amino acetic solutions. It is established that complex ion of the composition CdCl + is electroactive forM of the substance, which takes part in the transfer reaction. The rate of electrode process is limited with reduced ion supply to the electrode surface

  14. 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.

  15. 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.

  16. Removal mechanism of phosphate from aqueous solution by fly ash.

    Science.gov (United States)

    Lu, S G; Bai, S Q; Zhu, L; Shan, H D

    2009-01-15

    This work studied the effectiveness of fly ash in removing phosphate from aqueous solution and its related removal mechanism. The adsorption and precipitation of phosphate by fly ash were investigated separately in order to evaluate their role in the removal of phosphate. Results showed that the removal of phosphate by fly ash was rapid. The removal percentage of phosphate in the first 5min reached 68-96% of the maximum removal of phosphate by fly ash. The removal processes of phosphate by fly ash included a fast and large removal representing precipitation, then a slower and longer removal due to adsorption. The adsorption of phosphate on fly ash could be described well by Freundlich isotherm equation. The pH and Ca2+ concentration of fly ash suspension were decreased with the addition of phosphate, which suggests that calcium phosphate precipitation is a major mechanism of the phosphate removal. Comparison of the relative contribution of the adsorption and precipitation to the total removal of phosphate by fly ash showed that the adsorption accounted for 30-34% of the total removal of phosphate, depending on the content of CaO in fly ash. XRD patterns of the fly ash before and after phosphate adsorption revealed that phosphate salt (CaHPO4 x 2H2O) was formed in the adsorption process. Therefore, the removal of phosphate by fly ash can be attributed to the formation of phosphate precipitation as a brushite and the adsorption on hydroxylated oxides. The results suggested that the use of fly ash could be a promising solution to the removal of phosphate in the wastewater treatment and pollution control.

  17. Complex Reaction Kinetics in Chemistry: A Unified Picture Suggested by Mechanics in Physics

    Directory of Open Access Journals (Sweden)

    Elena Agliari

    2018-01-01

    Full Text Available Complex biochemical pathways can be reduced to chains of elementary reactions, which can be described in terms of chemical kinetics. Among the elementary reactions so far extensively investigated, we recall the Michaelis-Menten and the Hill positive-cooperative kinetics, which apply to molecular binding and are characterized by the absence and the presence, respectively, of cooperative interactions between binding sites. However, there is evidence of reactions displaying a more complex pattern: these follow the positive-cooperative scenario at small substrate concentration, yet negative-cooperative effects emerge as the substrate concentration is increased. Here, we analyze the formal analogy between the mathematical backbone of (classical reaction kinetics in Chemistry and that of (classical mechanics in Physics. We first show that standard cooperative kinetics can be framed in terms of classical mechanics, where the emerging phenomenology can be obtained by applying the principle of least action of classical mechanics. Further, since the saturation function plays in Chemistry the same role played by velocity in Physics, we show that a relativistic scaffold naturally accounts for the kinetics of the above-mentioned complex reactions. The proposed formalism yields to a unique, consistent picture for cooperative-like reactions and to a stronger mathematical control.

  18. 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)

  19. 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.

  20. Catecholase activity of dicopper(II)-bispidine complexes: stabilities and structures of intermediates, kinetics and reaction mechanism.

    Science.gov (United States)

    Born, Karin; Comba, Peter; Daubinet, André; Fuchs, Alexander; Wadepohl, Hubert

    2007-01-01

    A mechanism for the oxidation of 3,5-di-tert-butylcatechol (dtbc) with dioxygen to the corresponding quinone (dtbq), catalyzed by bispidine-dicopper complexes (bispidines are various mono- and dinucleating derivatives of 3,7-diazabicyclo[3.3.1]nonane with bis-tertiary-amine-bispyridyl or bis-tertiary-amine-trispyridyl donor sets), is proposed on the basis of (1) the stoichiometry of the reaction as well as the stabilities and structures [X-ray, density functional theory (B3LYP, TZV)] of the bispidine-dicopper(II)-3,4,5,6-tetrachlorcatechol intermediates, (2) formation kinetics and structures (molecular mechanics, MOMEC) of the end-on peroxo-dicopper(II) complexes and (3) kinetics of the stoichiometric (anaerobic) and catalytic (aerobic) copper-complex-assisted oxidation of dtbc. This involves (1) the oxidation of the dicopper(I) complexes with dioxygen to the corresponding end-on peroxo-dicopper(II) complexes, (2) coordination of dtbc as a bridging ligand upon liberation of H(2)O(2) and (3) intramolecular electron transfer to produce dtbq, which is liberated, and the dicopper(I) catalyst. Although the bispidine complexes have reactivities comparable to those of recently published catalysts with macrocyclic ligands, which seem to reproduce the enzyme-catalyzed process in various reaction sequences, a strikingly different oxidation mechanism is derived from the bispidine-dicopper-catalyzed reaction.

  1. Research on a scheduling mechanism in a complex system based on TOC

    International Nuclear Information System (INIS)

    Wen, Zhang; Ya-Ming, Zhang; Jinbo, Chen; Kaijun, Leng

    2016-01-01

    Under the condition where there is no seasonal demand fluctuation, short life cycle product supply chain should confront the market environment such as the decreasing of product value, the launch of substitutes and the appearance of competitors’ similar products, and the supply chain will become a very complex system. In this paper, the authors consider a TOC-based scheduling mechanism in this complex supply chain system. under the constant total production cost, it is more important to improve the availability of the wanted product in order to enhance the overall supply chain competitiveness so to obtain more effective output(profit rate) for the supply chain in a long period. Especially we try to apply the SDBR concept into a schedule mechanism in a particular supply chain system, and use numerical analysis to test the efficiency of the proposed method.

  2. 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

  3. Experimental and Computational Evidence for the Mechanism of Intradiol Catechol Dioxygenation by Non-Heme Iron(III) Complexes

    Science.gov (United States)

    Jastrzebski, Robin; Quesne, Matthew G; Weckhuysen, Bert M; de Visser, Sam P; Bruijnincx, Pieter C A

    2014-01-01

    Catechol intradiol dioxygenation is a unique reaction catalyzed by iron-dependent enzymes and non-heme iron(III) complexes. The mechanism by which these systems activate dioxygen in this important metabolic process remains controversial. Using a combination of kinetic measurements and computational modelling of multiple iron(III) catecholato complexes, we have elucidated the catechol cleavage mechanism and show that oxygen binds the iron center by partial dissociation of the substrate from the iron complex. The iron(III) superoxide complex that is formed subsequently attacks the carbon atom of the substrate by a rate-determining C=O bond formation step. PMID:25322920

  4. 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 ...

  5. Hydrogen-Bonded Polymer-Small Molecule Complexes with Tunable Mechanical Properties.

    Science.gov (United States)

    Liu, Tianqi; Peng, Xin; Chen, Ya-Nan; Bai, Qing-Wen; Shang, Cong; Zhang, Lin; Wang, Huiliang

    2018-03-13

    A novel type of polymeric material with tunable mechanical properties is fabricated from polymers and small molecules that can form hydrogen-bonded intermolecular complexes (IMCs). In this work, poly(vinyl alcohol) (PVA)-glycerol hydrogels are first prepared, and then they are dried to form IMCs. The tensile strengths and moduli of IMCs decrease dramatically with increasing glycerol content, while the elongations increase gradually. The mechanical properties are comparable with or even superior to those of common engineering plastics and rubbers. The IMCs with high glycerol content also show excellent flexibility and cold-resistance at subzero temperatures. Cyclic tensile and stress relaxation tests prove that there is an effective energy dissipation mechanism in IMCs and dynamic mechanical analysis confirms their physical crosslinking nature. FTIR and NMR characterizations prove the existence of hydrogen bonding between glycerol and PVA chains, which suppresses the crystallization of PVA from X-ray diffraction measurement. These PVA-glycerol IMCs may find potential applications in barrier films, biomedical packaging, etc., in the future. © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  6. Dioxins: diagnostic and prognostic challenges arising from complex mechanisms

    DEFF Research Database (Denmark)

    Rysavy, Noel M.; Maaetoft-Udsen, Kristina; Turner, Helen

    2013-01-01

    Dioxins are ubiquitous environmental challenges to humans, with a pervasiveness that arises from 200?years of rapid industrialization and mechanization of Western societies and which is now extending into the developing world. In spite of their penetrance of the human biota, these compounds...... such as cancer and diabetes, which are already multifactorial and highly complex, creates the context for the current review paper. Here, we summarize dioxin exposure paradigms and the resulting physiological effects that have been documented in animals and humans. Novel insights into potential endogenous end...... exogenous ligands, as well as the mechanisms by which these ligands impact acute and chronic cellular processes, are discussed. We develop the idea that the diagnosis of dioxin exposure, the subtleties of the cellular effects of the compounds and prognosis of the long-term effects of exposure are problems...

  7. 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.

  8. Mechanics of metal-catecholate complexes: The roles of coordination state and metal types

    Science.gov (United States)

    Xu, Zhiping

    2013-01-01

    There have been growing evidences for the critical roles of metal-coordination complexes in defining structural and mechanical properties of unmineralized biological materials, including hardness, toughness, and abrasion resistance. Their dynamic (e.g. pH-responsive, self-healable, reversible) properties inspire promising applications of synthetic materials following this concept. However, mechanics of these coordination crosslinks, which lays the ground for predictive and rational material design, has not yet been well addressed. Here we present a first-principles study of representative coordination complexes between metals and catechols. The results show that these crosslinks offer stiffness and strength near a covalent bond, which strongly depend on the coordination state and type of metals. This dependence is discussed by analyzing the nature of bonding between metals and catechols. The responsive mechanics of metal-coordination is further mapped from the single-molecule level to a networked material. The results presented here provide fundamental understanding and principles for material selection in metal-coordination-based applications. PMID:24107799

  9. Azobenzene as a photoregulator covalently attached to RNA: a quantum mechanics/molecular mechanics-surface hopping dynamics study.

    Science.gov (United States)

    Mondal, Padmabati; Granucci, Giovanni; Rastädter, Dominique; Persico, Maurizio; Burghardt, Irene

    2018-05-28

    The photoregulation of nucleic acids by azobenzene photoswitches has recently attracted considerable interest in the context of emerging biotechnological applications. To understand the mechanism of photoinduced isomerisation and conformational control in these complex biological environments, we employ a Quantum Mechanics/Molecular Mechanics (QM/MM) approach in conjunction with nonadiabatic Surface Hopping (SH) dynamics. Two representative RNA-azobenzene complexes are investigated, both of which contain the azobenzene chromophore covalently attached to an RNA double strand via a β-deoxyribose linker. Due to the pronounced constraints of the local RNA environment, it is found that trans -to- cis isomerization is slowed down to a time scale of ∼10-15 picoseconds, in contrast to 500 femtoseconds in vacuo , with a quantum yield reduced by a factor of two. By contrast, cis -to- trans isomerization remains in a sub-picosecond regime. A volume-conserving isomerization mechanism is found, similarly to the pedal-like mechanism previously identified for azobenzene in solution phase. Strikingly, the chiral RNA environment induces opposite right-handed and left-handed helicities of the ground-state cis -azobenzene chromophore in the two RNA-azobenzene complexes, along with an almost completely chirality conserving photochemical pathway for these helical enantiomers.

  10. Formation of Ni(Al, Mo) solid solutions by mechanical alloying and their ordering on heating

    International Nuclear Information System (INIS)

    Portnoj, V.K.; Tomilin, I.A.; Blinov, A.M.; Kulik, T.

    2002-01-01

    The Ni(Al, Mo) solid solutions with different crystalline lattice periods (0.3592 and 0.3570 nm correspondingly) are formed in the course of the Ni 70 Al 25 Mo 5 and Ni 75 Al 20 Mo 5 powder mixtures mechanical alloying (MA) (through the mechanical activation in a vibrating mill). After MA the Mo atoms in the Ni 75 Al 20 Mo 5 mixture completely replace the aluminium positions with formation of the Ni 75 (AlMo) 25 (the L1 2 -type) ternary ordered phase, whereby such a distribution remains after heating up to 700 deg C. The Ni(Al, Mo) metastable solution is formed by MA in the Ni 75 Al 20 Mo 5 mixture, which decays with the release of molybdenum and the remained aluminide undergoes ordering by the L1 2 -type [ru

  11. Passivation of mechanically polished, chemically etched and anodized zirconium in various aqueous solutions: Impedance measurements

    International Nuclear Information System (INIS)

    Abo-Elenien, G.M.; Abdel-Salam, O.E.

    1987-01-01

    Zirconium and its alloys are finding increasing applications especially in water-cooled nuclear reactors. Because of the fact that zirconium is electronegative (E 0 = -1.529V) its corrosion resistance in aqueous solutions is largely determined by the existence of a thin oxide film on its surface. The structure and properties of this film depend in the first place on the method of surface pre-treatment. This paper presents an experimental study of the nature of the oxide film on mechanically polished, chemically etched and anodized zirconium. Ac impedance measurements carried out in various acidic, neutral and alkaline solutions show that the film thickness depends on the method of surface pre-treatment and the type of electrolyte solution. The variation of the potential and impedance during anodization of zirconium at low current density indicates that the initial stages of polarization consist of oxide build-up at a rate dependent on the nature of the electrode surface and the electrolyte. Oxygen evolution commences at a stage where oxide thickening starts to decline. The effect of frequency on the measured impedance indicates that the surface reactivity, and hence the corrosion rate, decreases in the following order: mechanically polished > chemically etched > anodized

  12. 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.

  13. Carbon Nanotube Dispersion in Solvents and Polymer Solutions: Mechanisms, Assembly, and Preferences.

    Science.gov (United States)

    Pramanik, Chandrani; Gissinger, Jacob R; Kumar, Satish; Heinz, Hendrik

    2017-12-26

    Debundling and dispersion of carbon nanotubes (CNTs) in polymer solutions play a major role in the preparation of carbon nanofibers due to early effects on interfacial ordering and mechanical properties. A roadblock toward ultrastrong fibers is the difficulty to achieve homogeneous dispersions of CNTs in polyacrylonitrile (PAN) and poly(methyl methacrylate) (PMMA) precursor solutions in solvents such as dimethyl sulfoxide (DMSO), N,N-dimethylacetamide (DMAc), and N,N-dimethylformamide (DMF). In this contribution, molecular dynamics simulations with accurate interatomic potentials for graphitic materials that include virtual π electrons are reported to analyze the interaction of pristine single wall CNTs with the solvents and polymer solutions at 25 °C. The results explain the barriers toward dispersion of SWCNTs and quantify CNT-solvent, polymer-solvent, as well as CNT-polymer interactions in atomic detail. Debundling of CNTs is overall endothermic and unfavorable with dispersion energies of +20 to +30 mJ/m 2 in the pure solvents, + 20 to +40 mJ/m 2 in PAN solutions, and +20 to +60 mJ/m 2 in PMMA solutions. Differences arise due to molecular geometry, polar, van der Waals, and CH-π interactions. Among the pure solvents, DMF restricts CNT dispersion less due to the planar geometry and stronger van der Waals interactions. PAN and PMMA interact favorably with the pure solvents with dissolution energies of -0.7 to -1.1 kcal per mole monomer and -1.5 to -2.2 kcal per mole monomer, respectively. Adsorption of PMMA onto CNTs is stronger than that of PAN in all solvents as the molecular geometry enables more van der Waals contacts between alkyl groups and the CNT surface. Polar side groups in both polymers prefer interactions with the polar solvents. Higher polymer concentrations in solution lead to polymer aggregation via alkyl groups and reduce adsorption onto CNTs. PAN and PMMA solutions in DMSO and dilute solutions in DMF support CNT dispersion more than other

  14. 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.

  15. Kinetic and mechanism formation reaction of complex compound Cu with di-n-buthildithiocarbamate (dbdtc) ligand

    Science.gov (United States)

    Haryani, S.; Kurniawan, C.; Kasmui

    2018-04-01

    Synthesis of complex compound is one field of research which intensively studied. Metal-dithiocarbamate complexes find wide-ranging applications in nanomaterial and metal separation science, and have potential use as chemotherapeutic, pesticides, and as additives to lubricants. However, the information about is reaction kinetic and mechanism are very much lacking. The research and analyzes results show that reaction synthesis ligand DBDTC and complex compounds Cu-DBDTC. Optimum reaction condition of formation of complex compounds Cu with DBDTC at pH=3, [DBDTC] = 4.10-3 M, and the time of reaction 5 minutes. Based the analysis varian reaction of complex compounds at pH 3 and 4, diffrence significance at the other pH: 5; 5,5; 6; 6,5 ; 7; and 8. The various of mole with reactants comosition difference sigbificance, those the time reaction for 5 and 6 minutes diffrence by significance with the other time, it is 3,4,8, and 10 minutes. The great product to at condition pH 6, the time optimum at 5 minutes and molar ratio of logam: ligand = 1:2. The reaction kinetic equation of complex compound Cu with chelathing ligand DBDTC is V=0.917106 [Cu2+]0.87921 [DBDTC]2.03021. Based on the kinetic data, and formed complex compounds estimation, the mechanism explaining by 2 stages. In the first stage formation of [Cu(DBDTC)], and then [Cu(DBDTC)2] with the last structure geomethry planar rectangle. The result of this research will be more useful if an effort is being done in reaction mechanism by chemical computation method for obtain intermediate, and for constant “k” in same stage, k1.k2. and compound complex constanta (β).

  16. Mechanism for elevated temperature leaching

    International Nuclear Information System (INIS)

    Kenna, B.T.; Murphy, K.D.

    1979-01-01

    Long-term, elevated temperature leaching and subsequent electron microprobe analysis of simulated waste glass and ceramic materials have been completed. A cyclic leaching pattern was found in all systems over a 20-month period. It appears that the leaching of mobile ions by simple diffusional processes is modified by more complex chemical interactions. The release of immobile ions is primarily a function of their chemical interactions in the matrix which suggests that these ions may be complex species when released into solution. A mechanism is proposed which incorporates these ideas and the cyclic phenomenon observed

  17. Effect of solution heat treatment on the precipitation behavior and strengthening mechanisms of electron beam smelted Inconel 718 superalloy

    Energy Technology Data Exchange (ETDEWEB)

    You, Xiaogang [School of Materials Science and Engineering, Dalian University of Technology, Dalian 116023 (China); Laboratory for New Energy Material Energetic Beam Metallurgical Equipment Engineering of Liaoning Province, Dalian 116024 (China); Tan, Yi, E-mail: tanyi@dlut.edu.cn [School of Materials Science and Engineering, Dalian University of Technology, Dalian 116023 (China); Laboratory for New Energy Material Energetic Beam Metallurgical Equipment Engineering of Liaoning Province, Dalian 116024 (China); Shi, Shuang [School of Materials Science and Engineering, Dalian University of Technology, Dalian 116023 (China); Laboratory for New Energy Material Energetic Beam Metallurgical Equipment Engineering of Liaoning Province, Dalian 116024 (China); Yang, Jenn-Ming [Department of Materials Science and Engineering, University of California, Los Angeles, CA 90095 (United States); Wang, Yinong [School of Materials Science and Engineering, Dalian University of Technology, Dalian 116023 (China); Li, Jiayan; You, Qifan [School of Materials Science and Engineering, Dalian University of Technology, Dalian 116023 (China); Laboratory for New Energy Material Energetic Beam Metallurgical Equipment Engineering of Liaoning Province, Dalian 116024 (China)

    2017-03-24

    Inconel 718 superalloy was fabricated by electron beam smelting (EBS) technique. The effect of solution heat treatment on the precipitation behavior and mechanical properties of EBS 718 superalloys were studied, the strengthening mechanisms were analyzed and related to the mechanical properties. The results indicate that the optimized microstructures can be acquired by means of EBS, which is attributed to the rapid cooling rate of approximately 280 ℃/min. The solution heat treatment shows a great impact on the microstructures, precipitation behavior and mechanical properties of EBS 718 superalloy. The γ'' phase shows an apt to precipitate at relatively lower solution temperatures followed by aging, while the γ' precipitates are prone to precipitate at higher temperatures. When solution treated at 1150 ℃, the γ' precipitates are dispersively distributed in the matrix with size and volume fraction of 8.43 nm and 21.66%, respectively, a Vickers hardness of approximately 489 HV{sub 0.1} is observed for the aged superalloy. The precipitation strengthening effect of EBS 718 superalloy could be elucidated by considering the interaction between the dislocations and γ''/γ' precipitates. The shearing of γ' is resisted by the coherency strengthening and formation of antiphase boundary (APB), which shows equal effect as weakly coupled dislocation (WCD) model. And for γ'', the strengthening effect is much more prominent with the primary strengthening mechanism of ordering. Moreover, it is interestingly found that the strengthening mechanism of stacking fault (SF) shearing coexists with APB shearing, and SF shearing plays a major role in strengthening of EBS 718 superalloy.

  18. 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

  19. Causes and mechanisms of thermal embrittlement and corrosion cracking of complex α-titanium alloys

    International Nuclear Information System (INIS)

    Ushkov, S.S.; Rybin, V.V.; Razuvaeva, I.N.; Nesterova, E.V.; Gunbina, O.A.

    1995-01-01

    Effect of aging under 500 deg C on mechanical and corrosion-mechanical properties of Ti-6Al base titanium α-alloys with zirconium and carbon additions is studied. Using electron microscopy one determines the reasons of reduction of plasticity and of corrosion-mechanical strength of alloys after aging. It is determined that in the given alloys there are two different processes with occurrence different kinetics: the first one-formation of grain-boundary precipitations of Ti 2 (Fe, Ni) intermetallic compound responsible for plasticity reduction; and the second one-homogeneous decomposition of Ti-Al solid solution responsible for reduction of corrosion-mechanical properties. 14 refs., 6 figs

  20. The mechanism of solute-enriched clusters formation in neutron-irradiated pressure vessel steels: The case of Fe-Cu model alloys

    Energy Technology Data Exchange (ETDEWEB)

    Subbotin, A.V., E-mail: Alexey.V.Subbotin@gmail.com [Scientific and Production Complex Atomtechnoprom, Moscow 119180 (Russian Federation); Panyukov, S.V., E-mail: panyukov@lpi.ru [PN Lebedev Physics Institute, Russian Academy of Sciences, Moscow 117924 (Russian Federation)

    2016-08-15

    Mechanism of solute-enriched clusters formation in neutron-irradiated pressure vessel steels is proposed and developed in case of Fe-Cu model alloys. The suggested solute-drag mechanism is analogous to the well-known zone-refining process. We show that the obtained results are in good agreement with available experimental data on the parameters of clusters enriched with the alloying elements. Our model explains why the formation of solute-enriched clusters does not happen in austenitic stainless steels with fcc lattice structure. It also allows to quantify the method of evaluation of neutron irradiation dose for the process of RPV steels hardening.

  1. 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)

  2. Structure of the CaMKIIdelta/calmodulin complex reveals the molecular mechanism of CaMKII kinase activation.

    Directory of Open Access Journals (Sweden)

    Peter Rellos

    2010-07-01

    Full Text Available Long-term potentiation (LTP, a long-lasting enhancement in communication between neurons, is considered to be the major cellular mechanism underlying learning and memory. LTP triggers high-frequency calcium pulses that result in the activation of Calcium/Calmodulin (CaM-dependent kinase II (CaMKII. CaMKII acts as a molecular switch because it remains active for a long time after the return to basal calcium levels, which is a unique property required for CaMKII function. Here we describe the crystal structure of the human CaMKIIdelta/Ca2+/CaM complex, structures of all four human CaMKII catalytic domains in their autoinhibited states, as well as structures of human CaMKII oligomerization domains in their tetradecameric and physiological dodecameric states. All four autoinhibited human CaMKIIs were monomeric in the determined crystal structures but associated weakly in solution. In the CaMKIIdelta/Ca2+/CaM complex, the inhibitory region adopted an extended conformation and interacted with an adjacent catalytic domain positioning T287 into the active site of the interacting protomer. Comparisons with autoinhibited CaMKII structures showed that binding of calmodulin leads to the rearrangement of residues in the active site to a conformation suitable for ATP binding and to the closure of the binding groove for the autoinhibitory helix by helix alphaD. The structural data, together with biophysical interaction studies, reveals the mechanism of CaMKII activation by calmodulin and explains many of the unique regulatory properties of these two essential signaling molecules.This article can also be viewed as an enhanced version in which the text of the article is integrated with interactive 3-D representations and animated transitions. Please note that a web plugin is required to access this enhanced functionality. Instructions for the installation and use of the Web plugin are available in Text S1.

  3. 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

  4. Development of technology for the process of neutralization of pickling solution of metallurgical production

    Directory of Open Access Journals (Sweden)

    Lamzina I.V.

    2016-12-01

    Full Text Available The leading branch of territorial-production complex of Russia - mechanical engineering. Companies of the industry throw dirt in the form of used organic solvents, toxic compounds of metals with waste galvanic and etching solutions, cutting fluids (coolant and emulsions. you need to create complex regeneration treatment system of the most valuable components for these liquids. Reset electroplating and etching solutions can lead to the accumulation of heavy metals in the bio-organisms of the coastal zone and to enter them through the food chain to humans. To prevent contamination, a scheme neutralizing acid waste, accompanied by a reduction in the hazard class of the etching solution to IV class with the ability to accommodate long-term storage solid industrial waste in landfills.

  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. Deep Learning Fluid Mechanics

    Science.gov (United States)

    Barati Farimani, Amir; Gomes, Joseph; Pande, Vijay

    2017-11-01

    We have developed a new data-driven model paradigm for the rapid inference and solution of the constitutive equations of fluid mechanic by deep learning models. Using generative adversarial networks (GAN), we train models for the direct generation of solutions to steady state heat conduction and incompressible fluid flow without knowledge of the underlying governing equations. Rather than using artificial neural networks to approximate the solution of the constitutive equations, GANs can directly generate the solutions to these equations conditional upon an arbitrary set of boundary conditions. Both models predict temperature, velocity and pressure fields with great test accuracy (>99.5%). The application of our framework for inferring and generating the solutions of partial differential equations can be applied to any physical phenomena and can be used to learn directly from experiments where the underlying physical model is complex or unknown. We also have shown that our framework can be used to couple multiple physics simultaneously, making it amenable to tackle multi-physics problems.

  7. Mechanical properties of the normal human cartilage-bone complex in relation to age

    DEFF Research Database (Denmark)

    Ding, Ming; Dalstra, M; Linde, F

    1998-01-01

    OBJECTIVE: This study investigates the age-related variations in the mechanical properties of the normal human tibial cartilage-bone complex and the relationships between cartilage and bone. DESIGN: A novel technique was applied to assess the mechanical properties of the cartilage and bone by mea...... that are of importance for the understanding of the etiology and pathogenesis of degenerative joint diseases, such as arthrosis....

  8. Thermo-mechanical analysis of FG nanobeam with attached tip mass: an exact solution

    Science.gov (United States)

    Ghadiri, Majid; Jafari, Ali

    2016-12-01

    Present disquisition proposes an analytical solution method for exploring the vibration characteristics of a cantilever functionally graded nanobeam with a concentrated mass exposed to thermal loading for the first time. Thermo-mechanical properties of FGM nanobeam are supposed to change through the thickness direction of beam based on the rule of power-law (P-FGM). The small-scale effect is taken into consideration based on nonlocal elasticity theory of Eringen. Linear temperature rise (LTR) through thickness direction is studied. Existence of centralized mass in the free end of nanobeam influences the mechanical and physical properties. Timoshenko beam theory is employed to derive the nonlocal governing equations and boundary conditions of FGM beam attached with a tip mass under temperature field via Hamilton's principle. An exact solution procedure is exploited to achieve the non-dimensional frequency of FG nanobeam exposed to temperature field with a tip mass. A parametric study is led to assess the efficacy of temperature changes, tip mass, small scale, beam thickness, power-law exponent, slenderness and thermal loading on the natural frequencies of FG cantilever nanobeam with a point mass at the free end. It is concluded that these parameters play remarkable roles on the dynamic behavior of FG nanobeam subjected to LTR with a tip mass. The results for simpler states are confirmed with known data in the literature. Presented numerical results can serve as benchmarks for future thermo-mechanical analyses of FG nanobeam with tip mass.

  9. Kinetics and mechanism of superoxide radical reactions with some biologically important compounds in aqueous solutions. Pulse radiolysis

    Science.gov (United States)

    Revina, A. A.; Amiragova, M. I.; Volod'ko, V. V.; Vannikov, A. V.

    Microsecond pulse radiolysis of oxygenated aqueous solutions containing 0.02 mol dm -3 sodium formate and 2 mmol dm -3 phosphate buffer at pH 7 was used to generate superoxide anion radicals. The influence of some biologically important compounds upon the rate of O ⨪2 decay was monitored spectrophotometrically in the range of 245-300 nm. Hematoporphyrin (HP), hemin C (HC), catalase (Cat), cobalt sulfophthalocyanine (CoTSPc) were studied. Among the investigated compounds only Cat was found to show a high catalytic efficiency towards the self-decay of O ⨪2. A red shift of O ⨪2 absorption band and slowing down of its decay were observed to take place by adding HP or CoTSPc to the solutions containing formate ions in excess. This effect is associated with the formation of a transient superoxo-complex. An appearance of an intermediate species with absorption maxima at 350 nm and half-life of about 2s was observed to accompany the superoxo-complex of CoTSPc decay. In the aerated solution of HP the intensity of absorbance at 260 nm was found to be independent of the presence of formate ions.

  10. Kinetics and mechanism of superoxide radical reactions with some biologically important compounds in aqueous solutions. Pulse radiolysis

    International Nuclear Information System (INIS)

    Revina, A.A.; Volod'ko, V.V.; Vannikov, A.V.

    1989-01-01

    Microsecond pulse radiolysis of oxygenated aqueous solutions containing 0.02 mol dm -3 sodium formate and 2 mmol dm -3 phosphate buffer at pH 7 was used to generate superoxide anion radicals. The influence of some biologically important compounds upon the rate of O 2 .-bar decay as monitored spectrophotometrically in the range of 245-300 nm. Hematoporphyrin (HP), hemin C (HC), catalase (Cat), cobalt sulfophthalocyanine (CoTSPc) were studied. Among the investigated compounds only Cat was found to show a high catalytic efficiency towards the self-decay of O 2 .-bar . A red shift of 0 2 .-bar absorption band and slowing down of its decay were observed to take place by adding HP or CoTSPc to the solutions containing formate ions in excess. This effect is associated with the formation of a transient superoxo-complex. An appearance of an intermediate species with absorption maxima at 350 nm and half-life of about 2 s was observed to accompany the superoxo-complex of CoTSPc decay. In the aerated solution of HP the intensity of absorbance at 260 nm was found to be independent of the presence of formate ions. (author)

  11. 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

  12. Complex performance in construction

    DEFF Research Database (Denmark)

    Bougrain, Frédéric; Forman, Marianne; Gottlieb, Stefan Christoffer

    To fulfil the expectations of demanding clients, new project-delivery mechanisms have been developed. Approaches focusing on performance-based building or new procurement processers such as new forms of private-public partnerships are considered as solutions improving the overall performance...... to the end users. This report summarises the results from work undertaken in the international collaborative project “Procuring and Operating Complex Products and Systems in Construction” (POCOPSC). POCOPSC was carried out in the period 2010-2014. The project was executed in collaboration between CSTB...

  13. Statistical mechanics of protein solutions

    NARCIS (Netherlands)

    Prinsen, P.

    2007-01-01

    We study theoretically thermodynamic properties of spherical globular proteins in aqueous solution with added monovalent salt. We show how one can determine an effective interaction potential between the proteins from experimental data as a function of salt concentration and we apply this to the

  14. Effect of heating rate on mechanical property, microstructure and texture evolution of Al–Mg–Si–Cu alloy during solution treatment

    Energy Technology Data Exchange (ETDEWEB)

    Wang, Xiaofeng; Guo, Mingxing, E-mail: mingxingguo@skl.ustb.edu.cn; Cao, Lingyong; Luo, Jinru; Zhang, Jishan; Zhuang, Linzhong

    2015-01-05

    The effect of heating rate on the mechanical properties, microstructure and texture of Al–Mg–Si–Cu alloy during solution treatment was investigated through tensile testing, scanning electron microscope, scanning transmission electron microscope, metallographic observation and EBSD measurement. The experimental results reveal that there are great differences in the mechanical properties, microstructures and textures after the solution treatment with two different heating rates. Compared with the alloy sheet solution treated with slow heating rate, the alloy sheet solution treated with rapid heating rate possesses weak mechanical property anisotropy and higher average r value. The equiaxed grain is the main recrystallization microstructure for the case of rapid heating rate, while the elongated grain appears in the case of slow heating rate. The texture components are also quite different in the two cases, Cube{sub ND} orientation is the main texture component for the former case, while the latter one includes Cube, R, Goss, P and Brass orientations. The relationship between r value, texture components and microstructure has also been established in this paper.

  15. Effect of heating rate on mechanical property, microstructure and texture evolution of Al–Mg–Si–Cu alloy during solution treatment

    International Nuclear Information System (INIS)

    Wang, Xiaofeng; Guo, Mingxing; Cao, Lingyong; Luo, Jinru; Zhang, Jishan; Zhuang, Linzhong

    2015-01-01

    The effect of heating rate on the mechanical properties, microstructure and texture of Al–Mg–Si–Cu alloy during solution treatment was investigated through tensile testing, scanning electron microscope, scanning transmission electron microscope, metallographic observation and EBSD measurement. The experimental results reveal that there are great differences in the mechanical properties, microstructures and textures after the solution treatment with two different heating rates. Compared with the alloy sheet solution treated with slow heating rate, the alloy sheet solution treated with rapid heating rate possesses weak mechanical property anisotropy and higher average r value. The equiaxed grain is the main recrystallization microstructure for the case of rapid heating rate, while the elongated grain appears in the case of slow heating rate. The texture components are also quite different in the two cases, Cube ND orientation is the main texture component for the former case, while the latter one includes Cube, R, Goss, P and Brass orientations. The relationship between r value, texture components and microstructure has also been established in this paper

  16. Orbital classical solutions, non-perturbative phenomena and singularity at the zero coupling constant point

    International Nuclear Information System (INIS)

    Vourdas, A.

    1982-01-01

    We try to extend previous arguments on orbital classical solutions in non-relativistic quantum mechanics to the 1/4lambda vertical stroke phi vertical stroke 4 complex relativistic field theory. The single valuedness of the Green function in the semiclassical (Planksche Konstante → 0) limit leads to a Bohr-Sommerfeld quantization. A path integral formalism for the Green functions analogous to that in non-relativistic quantum mechanics is employed and a semiclassical approach which uses our classical solutions indicates non-perturbative effects. They reflect an esub(1/lambda) singularity at the zero coupling constant point. (orig.)

  17. 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.

  18. Experimental qualification of mechanical and electrical sub-systems of a complex mechanism against fatigue failure

    International Nuclear Information System (INIS)

    Patri, Sudheer; Vijayashree, R.; Rajan Babu, V.; Suresh Kumar, S.; Chandramouli, S.; Meikandamurthy, C.; Prakash, V.; Rajan, K.K.; Srinivasan, G.

    2016-01-01

    Absorber rod drive mechanisms (ARDM) play an important role in ensuring safety of a reactor by rapid insertion of an Absorber rod (AR) during abnormal conditions. Various components/sub-systems of ARDMs, both mechanical and electrical, are subjected to different cyclic loadings during service life. Thus, qualifying these systems against fatigue is an important step for gaining confidence in their safe operation for the design life. ASME in Sec. III, Div. 1, Appendices (Para II - 1500) provides guidelines for the experimental evaluation of the capability of components to withstand cyclic loading. These rules are developed for static components like pressure vessels. Since no such rules are available for moving components like mechanisms, the same were adopted for the ARDMs, with an understanding that the effect of inertia loads of a moving component are to be accounted in the experiments. In application of these rules to a complex mechanisms such as ARDM, various special cases arise which are not addressed explicitly in the code. The paper describes the intelligent adoption of the fatigue life rules given in ASME to various special cases and their extension to electrical systems. The paper also outlines the experiments carried out for qualifying the ARDM against fatigue. (author)

  19. Structural requirements for the assembly of LINC complexes and their function in cellular mechanical stiffness

    International Nuclear Information System (INIS)

    Stewart-Hutchinson, P.J.; Hale, Christopher M.; Wirtz, Denis; Hodzic, Didier

    2008-01-01

    The evolutionary-conserved interactions between KASH and SUN domain-containing proteins within the perinuclear space establish physical connections, called LINC complexes, between the nucleus and the cytoskeleton. Here, we show that the KASH domains of Nesprins 1, 2 and 3 interact promiscuously with luminal domains of Sun1 and Sun2. These constructs disrupt endogenous LINC complexes as indicated by the displacement of endogenous Nesprins from the nuclear envelope. We also provide evidence that KASH domains most probably fit a pocket provided by SUN domains and that post-translational modifications are dispensable for that interaction. We demonstrate that the disruption of endogenous LINC complexes affect cellular mechanical stiffness to an extent that compares to the loss of mechanical stiffness previously reported in embryonic fibroblasts derived from mouse lacking A-type lamins, a mouse model of muscular dystrophies and cardiomyopathies. These findings support a model whereby physical connections between the nucleus and the cytoskeleton are mediated by interactions between diverse combinations of Sun proteins and Nesprins through their respective evolutionary-conserved domains. Furthermore, they emphasize, for the first time, the relevance of LINC complexes in cellular mechanical stiffness suggesting a possible involvement of their disruption in various laminopathies, a group of human diseases linked to mutations of A-type lamins

  20. Deciphering deterioration mechanisms of complex diseases based on the construction of dynamic networks and systems analysis

    Science.gov (United States)

    Li, Yuanyuan; Jin, Suoqin; Lei, Lei; Pan, Zishu; Zou, Xiufen

    2015-03-01

    The early diagnosis and investigation of the pathogenic mechanisms of complex diseases are the most challenging problems in the fields of biology and medicine. Network-based systems biology is an important technique for the study of complex diseases. The present study constructed dynamic protein-protein interaction (PPI) networks to identify dynamical network biomarkers (DNBs) and analyze the underlying mechanisms of complex diseases from a systems level. We developed a model-based framework for the construction of a series of time-sequenced networks by integrating high-throughput gene expression data into PPI data. By combining the dynamic networks and molecular modules, we identified significant DNBs for four complex diseases, including influenza caused by either H3N2 or H1N1, acute lung injury and type 2 diabetes mellitus, which can serve as warning signals for disease deterioration. Function and pathway analyses revealed that the identified DNBs were significantly enriched during key events in early disease development. Correlation and information flow analyses revealed that DNBs effectively discriminated between different disease processes and that dysfunctional regulation and disproportional information flow may contribute to the increased disease severity. This study provides a general paradigm for revealing the deterioration mechanisms of complex diseases and offers new insights into their early diagnoses.

  1. Analysis of Americium in Transplutonium Process Solutions

    International Nuclear Information System (INIS)

    Ferguson, R.B.

    2001-01-01

    One of the more difficult analyses in the transplutonium field is the determination of americium at trace levels in a complex matrix such as a process dissolver solution. Because of these conditions a highly selective separation must precede the measurement of americium. The separation technique should be mechanically simple to permit remote operation with master-slave manipulators. For subsequent americium measurement by the mass spectroscopic isotopic-dilution technique, plutonium and curium interferences must also have been removed

  2. On the existence of the H3 tautomer of adenine in aqueous solution. Rationalizations based on hybrid quantum mechanics/molecular mechanics predictions

    DEFF Research Database (Denmark)

    Aidas, Kestutis; Mikkelsen, Kurt V; Kongsted, Jacob

    2010-01-01

    The (15)N NMR spectrum of adenine in aqueous solution has been modeled using high-level combined density functional theory/molecular mechanics techniques coupled to a dynamical averaging scheme. The explicit consideration of the three lowest-energy tautomers of adenine-H9, H7 and H3-allows...

  3. 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.

  4. 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.

  5. Possible mechanisms for the interaction of polymeric composite resins with Cu(II) ions in aqueous solution

    International Nuclear Information System (INIS)

    El-Zahhhar, A.A.; Abdel-Aziz, H.M.; Siyam, T.

    2005-01-01

    The interaction between the active groups of polymeric composite resins such as Poly(acrylamide-acrylic acid)-ethylenediaminetetra acetic acid disodium salt P(AM-AA)EDTANa 2 , Poly(acrylamide-acrylic acid)- montmorillonite P(AM-AA)-montmorillonite, and Poly(acrylamide-acrylic acid)-potassium nickel hexacyanoferrate P(AM-AA)-KNiHCF, with copper sulfate as a test ion has been studied. The spectroscopic studies show that the mechanism of interaction between polymeric composite resins and copper sulfate is a bond formation between the active groups of polymeric chains and copper ion. The bond formation depends on nature of polymeric chains. It was also found that the amide groups form complexes with hydrated cations, while carboxylate group interact by ion exchange mechanism through complex formation. Montmorillonite and hexacyanoferrate of the resins interact with metal ions by ion exchange mechanism

  6. 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.

  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. 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

  9. 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

  10. 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

  11. 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.

  12. Devitrification and recrystallization of nanoparticle-containing glycerol and PEG-600 solutions.

    Science.gov (United States)

    Lv, Fukou; Liu, Baolin; Li, Weijie; Jaganathan, Ganesh K

    2014-02-01

    Nanoparticles in solution offer unique electrical, mechanical and thermal properties due to their physical presence and interaction with the state of dispersion. This work is aimed to study the effects of hydroxyapatite (HA) nanoparticles on the devitrification and recrystallization events of two important cryoprotective solutions used in cell and tissue preservation namely glycerol (60%w/w) and PEG-600 (50%w/w). HA nanoparticles (20, 40 or 60 nm) were incorporated into solutions at the content of 0.1% or 0.5%(w/w), and were studied by differential scanning calorimeter (DSC) and cryomicroscopy. The presence of nanoparticles does not change the glass transition temperatures and melting temperatures of quenched solutions, but significantly affects the behavior of devitrification and recrystallization upon warming. Cryomicroscopic investigation showed the complex interactions among solution type, nanoparticle size and nanoparticle content, which apparently influence ice crystal growth or recrystallization in the quenched dispersions. These findings have significant implications for biomaterial cryopreservation, cryosurgery, and food manufacturing. The complexity of ice crystal growth kinetics in nanoparticle-containing dispersions remains to be poorly understood at the moment. Copyright © 2013 Elsevier Inc. All rights reserved.

  13. Methods for constructing exact solutions of partial differential equations mathematical and analytical techniques with applications to engineering

    CERN Document Server

    Meleshko, Sergey V

    2005-01-01

    Differential equations, especially nonlinear, present the most effective way for describing complex physical processes. Methods for constructing exact solutions of differential equations play an important role in applied mathematics and mechanics. This book aims to provide scientists, engineers and students with an easy-to-follow, but comprehensive, description of the methods for constructing exact solutions of differential equations.

  14. A new technique in constructing closed-form solutions for nonlinear PDEs appearing in fluid mechanics and gas dynamics

    Directory of Open Access Journals (Sweden)

    Panayotounakos D. E.

    1996-01-01

    Full Text Available We develop a new unique technique in constructing closed-form solutions for several nonlinear partial differential systems appearing in fluid mechanics and gas dynamics. The obtained solutions include fewer arbitrary functions than needed for general solutions, fact that permits us to specify them according to the initial state, or the geometry, of each specific problem under consideration. In order to apply the before mentioned technique we construct closed-form solutions concerning the gas-dynamic equations with constant pressure, the dynamic equations of an ideal gas in isentropic flow, and the two-dimensional incompressible boundary layer flow.

  15. Pole solutions for flame front propagation

    CERN Document Server

    Kupervasser, Oleg

    2015-01-01

    This book deals with solving mathematically the unsteady flame propagation equations. New original mathematical methods for solving complex non-linear equations and investigating their properties are presented. Pole solutions for flame front propagation are developed. Premixed flames and filtration combustion have remarkable properties: the complex nonlinear integro-differential equations for these problems have exact analytical solutions described by the motion of poles in a complex plane. Instead of complex equations, a finite set of ordinary differential equations is applied. These solutions help to investigate analytically and numerically properties of the flame front propagation equations.

  16. Mechanism of S-oxygenation by a cysteine dioxygenase model complex

    OpenAIRE

    Kumar, Devesh; Sastry, G. Narahari; Goldberg, David P.; de Visser, Sam P.

    2011-01-01

    In this work we present the first computational study on a biomimetic cysteine dioxygenase model complex, [FeII(LN3S)]+ where LN3S is a tetradentate ligand with a bis(imino)pyridyl scaffold and a pendant arylthiolate group. The reaction mechanism of sulfur dioxygenation with O2 was examined by density functional theory (DFT) methods, and compared to results obtained for cysteine dioxygenase. The reaction proceeds via multistate reactivity patterns on competing singlet, triplet and quintet spi...

  17. Sixth-Grade Students' Progress in Understanding the Mechanisms of Global Climate Change

    Science.gov (United States)

    Visintainer, Tammie; Linn, Marcia

    2015-01-01

    Developing solutions for complex issues such as global climate change requires an understanding of the mechanisms involved. This study reports on the impact of a technology-enhanced unit designed to improve understanding of global climate change, its mechanisms, and their relationship to everyday energy use. Global Climate Change, implemented in…

  18. 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.

  19. 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.

  20. Microstructure and mechanical properties of a novel Ti–Al–Cr–Fe titanium alloy after solution treatment

    International Nuclear Information System (INIS)

    Wang, Zhenguo; Cai, Haijiao; Hui, Songxiao

    2015-01-01

    Highlights: • Microstructure and mechanical properties of a novel Ti–3.0Al–3.7Cr–2.0Fe alloy were studied. • The effects of cooling rates and solution temperature were considered. • The strength–ductility combination were investigated through different heat treatment. - Abstract: The relationship between microstructure and mechanical properties of a novel Ti–3.0Al–3.7Cr–2.0Fe alloy were studied. The effects of cooling rates and solution temperature were considered. The analysis methods of optical microscope (OM), X-ray diffractometer (XRD), scanning electron microscope (SEM) and transmission electron microscope (TEM) were used. The results indicate that β and α phase in this alloy are obtained after solution treated at 1183 K on the cooling ways of air cooling and furnace cooling; and β and α″ martensite are observed after quenching in water. Besides, the volume of α phase is decreased with increasing solution temperature. In the present study, the ultimate strength 1065 MPa with 12.0% in elongation of the alloy is acquired under the heat treatment condition of 1183 K/30 min/AC, and the strength–ductility combination in this case is also the best. Under the heat treatment condition of 1183 K/30 min/WQ, the elasticity modulus of the alloy is only 91.3 GPa, as a result of the lower elasticity modulus of β phase

  1. Identifying partial topology of complex dynamical networks via a pinning mechanism

    Science.gov (United States)

    Zhu, Shuaibing; Zhou, Jin; Lu, Jun-an

    2018-04-01

    In this paper, we study the problem of identifying the partial topology of complex dynamical networks via a pinning mechanism. By using the network synchronization theory and the adaptive feedback controlling method, we propose a method which can greatly reduce the number of nodes and observers in the response network. Particularly, this method can also identify the whole topology of complex networks. A theorem is established rigorously, from which some corollaries are also derived in order to make our method more cost-effective. Several numerical examples are provided to verify the effectiveness of the proposed method. In the simulation, an approach is also given to avoid possible identification failure caused by inner synchronization of the drive network.

  2. Chitosan–Zinc(II Complexes as a Bio-Sorbent for the Adsorptive Abatement of Phosphate: Mechanism of Complexation and Assessment of Adsorption Performance

    Directory of Open Access Journals (Sweden)

    Maryam Roza Yazdani

    2017-12-01

    Full Text Available This study examines zinc(II–chitosan complexes as a bio-sorbent for phosphate removal from aqueous solutions. The bio-sorbent is prepared and is characterized via Fourier Transform Infrared Spectroscopy (FT-IR, Scanning Electron Microscopy (SEM, and Point of Zero Charge (pHPZC–drift method. The adsorption capacity of zinc(II–chitosan bio-sorbent is compared with those of chitosan and ZnO–chitosan and nano-ZnO–chitosan composites. The effect of operational parameters including pH, temperature, and competing ions are explored via adsorption batch mode. A rapid phosphate uptake is observed within the first three hours of contact time. Phosphate removal by zinc(II–chitosan is favored when the surface charge of bio-sorbent is positive/or neutral e.g., within the pH range inferior or around its pHPZC, 7. Phosphate abatement is enhanced with decreasing temperature. The study of background ions indicates a minor effect of chloride, whereas nitrate and sulfate show competing effect with phosphate for the adsorptive sites. The adsorption kinetics is best described with the pseudo-second-order model. Sips (R2 > 0.96 and Freundlich (R2 ≥ 0.95 models suit the adsorption isotherm. The phosphate reaction with zinc(II–chitosan is exothermic, favorable and spontaneous. The complexation of zinc(II and chitosan along with the corresponding mechanisms of phosphate removal are presented. This study indicates the introduction of zinc(II ions into chitosan improves its performance towards phosphate uptake from 1.45 to 6.55 mg/g and provides fundamental information for developing bio-based materials for water remediation.

  3. A study on elongation/contraction behavior and mechanical properties of oxy-polyacrylonitrile(PAN) fiber in basic/acidic solution for artificial muscle applications

    Energy Technology Data Exchange (ETDEWEB)

    Lee, Y.K.; Kim, S.W.; Lee, K.S.; Cho, I.H.; Lee, J.H.; Lee, J.W. [Sungkyunkwan University, Suwon (Korea); Kim, K.J. [University of Nevada, Reno (United States); Nam, J.D. [Sungkyunkwan University, Suwon (Korea)

    2002-07-01

    Oxy-PAN fiber prepared from the preoxidation and saponification of raw PAN fiber is known to elongate and contract when immersed in basic and acidic solutions, respectively. In this study, about 30% elongation in NaOH solution and 30{approx}50% contraction in HCl solution have been observed. In mechanical test, the mechanical properties of oxy-PAN fiber in the contracted state was stronger than that in the elongated state. These behaviors and mechanical properties are compared to those of living muscle and linear actuator. The change of length in NaOH and HCl solutions is due to switching between a hydrophilic and a hydrophobic structure. Other reasons are exchange of ion and water in/out of oxy-PAN fiber, and osmotic pressure difference associated with relevant ions. Much studies are needed to clarify the effective factors on but the oxy-PAN fiber's elongation/contraction behavior and mechanical properties, but the oxy-PAN fiber prepared in our laboratory has a sufficient potential for application as artificial muscle and linear actuator. (author). 20 refs., 1 tab., 9 figs.

  4. Decaying states as complex energy eigenvectors in generalized quantum mechanics

    International Nuclear Information System (INIS)

    Sudarshan, E.C.G.; Chiu, C.B.; Gorini, V.

    1977-04-01

    The problem of particle decay is reexamined within the Hamiltonian formalism. By deforming contours of integration, the survival amplitude is expressed as a sum of purely exponential contributions arising from the simple poles of the resolvent on the second sheet plus a background integral along a complex contour GAMMA running below the location of the poles. One observes that the time dependence of the survival amplitude in the small time region is strongly correlated to the asymptotic behaviour of the energy spectrum of the system; one computes the small time behavior of the survival amplitude for a wide variety of asymptotic behaviors. In the special case of the Lee model, using a formal procedure of analytic continuation, it is shown that a complete set of complex energy eigenvectors of the Hamiltonian can be associated with the poles of the resolvent of the background contour GAMMA. These poles and points along GAMMA correspond to the discrete and the continuum states respectively. In this context, each unstable particle is associated with a well defined object, which is a discrete generalized eigenstate of the Hamiltonian having a complex eigenvalue, with its real and negative imaginary parts being the mass and half width of the particle respectively. Finally, one briefly discusses the analytic continuation of the scattering amplitude within this generalized scheme, and notes the appearance of ''redundant poles'' which do not correspond to discrete solutions of the modified eigenvalue problem

  5. ADAPTATION OF N-HEPTANE AUTOIGNITION TABULATION FOR COMPLEX CHEMISTRY MECHANISMS

    Directory of Open Access Journals (Sweden)

    Neven Duić

    2011-01-01

    Full Text Available The adaptation of auto-ignition tabulation for effective use of complex chemical mechanisms will be presented in this paper. Taking cool flame ignition phenomenon into account could improve numerical simulations of combustion in compression ignition engines. Current approaches of successful simulation of this phenomenon are based on the extraction of ignition delay times, heat releases and also reaction rates from tabulated data dependant on four parameters: temperature, pressure, equivalence ratio and exhaust gasses mass fraction. The methods described here were used to create lookup tables including cool flame using a comprehensive chemical mechanism without including reaction rates data (as used by other authors. The method proved to be stable for creating tables and these results will be shown, as well as initial implementation results using the tables in computational fluid dynamics software.

  6. 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.

  7. The homeostasis solutionMechanical homeostasis in architecturally homeostatic buildings

    International Nuclear Information System (INIS)

    Wang, Lin-Shu; Ma, Peizheng

    2016-01-01

    Highlights: • Architectural homeostatic buildings (AHBs) make sense because of the laws of physics. • However, high efficiency can be obtained only with AHBs and equipment considered as systems. • Mechanical homeostasis facilitates AHB-equipment system synergy with heat extraction. • Entropically speaking a building needs neither energy nor a fixed amount of heat, but its homeostatic existence. • Homeostatic buildings can reduce building energy consumption from 80% to 90%. - Abstract: We already know, for energy-saving potential, the necessary architectural features in well-designed buildings: high performance building envelope, sufficient interior thermal mass, and hydronic-network activated radiant surfaces for cooling and heating. Buildings with these features may be referred to as architecturally homeostatic buildings (AHBs); such a building-system is thermally semi-autonomous in the sense that its temperature variation stays within a certain range even without conditioning equipment, and, with conditioning equipment in operation, its thermal regulation is handled by its hydronic heat-distribution-network for controlling the temperature level of the building. At the present time conventional HVAC equipment is used for maintaining the heat-distribution-network: this arrangement, however, has resulted in great energy saving only for AHBs with accessible natural water bodies. In operation of general AHBs, a case is made here for a new kind of mechanical equipment having the attribute of mechanical homeostasis (MH). MH is a new energy transformation concept in a triadic framework. Superlative energy efficiency is predicted as a result of combined improvements in higher triadCOPs and lower total (inducted + removed) heat rates—evincing existence of synergy in architectural and mechanical homeostasis, which together will be referred to as the homeostasis solution.

  8. Complex Teichmüller Space below the Planck Length for the Interpretation of Quantum Mechanics

    Science.gov (United States)

    Winterberg, Friedwardt

    2014-03-01

    As Newton's mysterious action at a distance law of gravity was explained as a Riemannian geometry by Einstein, it is proposed that the likewise mysterious non-local quantum mechanics is explained by the analytic continuation below the Planck length into a complex Teichmüller space. Newton's theory worked extremely well, as does quantum mechanics, but no satisfactory explanation has been given for quantum mechanics. In one space dimension, sufficient to explain the EPR paradox, the Teichmüller space is reduced to a space of complex Riemann surfaces. Einstein's curved space-time theory of gravity was confirmed by a tiny departure from Newton's theory in the motion of the planet Mercury, and an experiment is proposed to demonstrate the possible existence of a Teichmüller space below the Planck length.

  9. A comparative study of iterative solutions to linear systems arising in quantum mechanics

    International Nuclear Information System (INIS)

    Jing Yanfei; Huang Tingzhu; Duan Yong; Carpentieri, Bruno

    2010-01-01

    This study is mainly focused on iterative solutions with simple diagonal preconditioning to two complex-valued nonsymmetric systems of linear equations arising from a computational chemistry model problem proposed by Sherry Li of NERSC. Numerical experiments show the feasibility of iterative methods to some extent when applied to the problems and reveal the competitiveness of our recently proposed Lanczos biconjugate A-orthonormalization methods to other classic and popular iterative methods. By the way, experiment results also indicate that application specific preconditioners may be mandatory and required for accelerating convergence.

  10. 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.

  11. 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)

  12. Multilayer Stochastic Block Models Reveal the Multilayer Structure of Complex Networks

    Directory of Open Access Journals (Sweden)

    Toni Vallès-Català

    2016-03-01

    Full Text Available In complex systems, the network of interactions we observe between systems components is the aggregate of the interactions that occur through different mechanisms or layers. Recent studies reveal that the existence of multiple interaction layers can have a dramatic impact in the dynamical processes occurring on these systems. However, these studies assume that the interactions between systems components in each one of the layers are known, while typically for real-world systems we do not have that information. Here, we address the issue of uncovering the different interaction layers from aggregate data by introducing multilayer stochastic block models (SBMs, a generalization of single-layer SBMs that considers different mechanisms of layer aggregation. First, we find the complete probabilistic solution to the problem of finding the optimal multilayer SBM for a given aggregate-observed network. Because this solution is computationally intractable, we propose an approximation that enables us to verify that multilayer SBMs are more predictive of network structure in real-world complex systems.

  13. Analytical mechanics

    CERN Document Server

    Helrich, Carl S

    2017-01-01

    This advanced undergraduate textbook begins with the Lagrangian formulation of Analytical Mechanics and then passes directly to the Hamiltonian formulation and the canonical equations, with constraints incorporated through Lagrange multipliers. Hamilton's Principle and the canonical equations remain the basis of the remainder of the text. Topics considered for applications include small oscillations, motion in electric and magnetic fields, and rigid body dynamics. The Hamilton-Jacobi approach is developed with special attention to the canonical transformation in order to provide a smooth and logical transition into the study of complex and chaotic systems. Finally the text has a careful treatment of relativistic mechanics and the requirement of Lorentz invariance. The text is enriched with an outline of the history of mechanics, which particularly outlines the importance of the work of Euler, Lagrange, Hamilton and Jacobi. Numerous exercises with solutions support the exceptionally clear and concise treatment...

  14. 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

  15. Potential mechanisms of cadmium removal from aqueous solution by Canna indica derived biochar

    International Nuclear Information System (INIS)

    Cui, Xiaoqiang; Fang, Siyu; Yao, Yiqiang; Li, Tingqiang; Ni, Qijun; Yang, Xiaoe; He, Zhenli

    2016-01-01

    The objective of this study was to investigate the mechanisms of cadmium (Cd) sorption on biochars produced at different temperature (300–600 °C) and their quantitative contribution. The sorption isotherms and kinetics of Cd 2+ sorption on biochars were determined and fitted to different models. The Cd 2+ sorption data could be well described by a simple Langmuir model, and the pseudo second order kinetic model best fitted the kinetic data. The maximum sorption capacity (Q m ) obtained from the Langmuir model for CIB500 was 188.8 mg g −1 , which was greater than that of biochars produced at other temperature. Precipitation with minerals, ion exchange, complexation with surface oxygen-containing functional groups, and coordination with π electrons were the possible mechanisms of Cd 2+ sorption on the biochars. The contribution of each mechanism varied with the pyrolysis temperature. With increasing pyrolysis temperature, the contribution of surface complexation and metal ion exchange decreased from 24.5% and 43.3% to 0.7% and 4.7%, while the contribution of precipitation and Cd 2+ -π interaction significantly increased from 29.7% and 2.5% to 89.5% and 5.1%, respectively. Overall, the precipitation with minerals and metal ion exchange dominated Cd 2+ sorption on the biochars (accounted for 73.0–94.1%), and precipitation with minerals was the primary mechanism of Cd 2+ sorption on the high-temperature biochars (≥ 500 °C) (accounted for 86.1–89.5%). - Highlights: • Sorption capacity of metal on biochars is affected by pyrolysis temperature. • Biochar derived from Canna indica at 500 °C has a high sorption capacity for Cd 2+ . • Cd 2+ sorption on the biochars fits a pseudo second order and Langmuir model. • Precipitation and ion exchange mechanisms dominated Cd 2+ sorption on the biochars.

  16. PREFACE: Counting Complexity: An international workshop on statistical mechanics and combinatorics

    Science.gov (United States)

    de Gier, Jan; Warnaar, Ole

    2006-07-01

    On 10-15 July 2005 the conference `Counting Complexity: An international workshop on statistical mechanics and combinatorics' was held on Dunk Island, Queensland, Australia in celebration of Tony Guttmann's 60th birthday. Dunk Island provided the perfect setting for engaging in almost all of Tony's life-long passions: swimming, running, food, wine and, of course, plenty of mathematics and physics. The conference was attended by many of Tony's close scientific friends from all over the world, and most talks were presented by his past and present collaborators. This volume contains the proceedings of the meeting and consists of 24 refereed research papers in the fields of statistical mechanics, condensed matter physics and combinatorics. These papers provide an excellent illustration of the breadth and scope of Tony's work. The very first contribution, written by Stu Whittington, contains an overview of the many scientific achievements of Tony over the past 40 years in mathematics and physics. The organizing committee, consisting of Richard Brak, Aleks Owczarek, Jan de Gier, Emma Lockwood, Andrew Rechnitzer and Ole Warnaar, gratefully acknowledges the Australian Mathematical Society (AustMS), the Australian Mathematical Sciences Institute (AMSI), the ARC Centre of Excellence for Mathematics and Statistics of Complex Systems (MASCOS), the ARC Complex Open Systems Research Network (COSNet), the Institute of Physics (IOP) and the Department of Mathematics and Statistics of The University of Melbourne for financial support in organizing the conference. Tony, we hope that your future years in mathematics will be numerous. Count yourself lucky! Tony Guttman

  17. PT-symmetry breaking in complex nonlinear wave equations and their deformations

    International Nuclear Information System (INIS)

    Cavaglia, Andrea; Fring, Andreas; Bagchi, Bijan

    2011-01-01

    We investigate complex versions of the Korteweg-deVries equations and an Ito-type nonlinear system with two coupled nonlinear fields. We systematically construct rational, trigonometric/hyperbolic and elliptic solutions for these models including those which are physically feasible in an obvious sense, that is those with real energies, but also those with complex energy spectra. The reality of the energy is usually attributed to different realizations of an antilinear symmetry, as for instance PT-symmetry. It is shown that the symmetry can be spontaneously broken in two alternative ways either by specific choices of the domain or by manipulating the parameters in the solutions of the model, thus leading to complex energies. Surprisingly, the reality of the energies can be regained in some cases by a further breaking of the symmetry on the level of the Hamiltonian. In many examples, some of the fixed points in the complex solution for the field undergo a Hopf bifurcation in the PT-symmetry breaking process. By employing several different variants of the symmetries we propose many classes of new invariant extensions of these models and study their properties. The reduction of some of these models yields complex quantum mechanical models previously studied.

  18. Characterization of the sorption of uranium(VI) on different complexing resins

    Energy Technology Data Exchange (ETDEWEB)

    Pesavento, Maria; Biesuz, Raffaela; Alberti, Giancarla; Sturini, Michela [Dipartimento di Chimica Generale dell' Universita degli Studi di Pavia, Via Taramelli 12, 27100, Pavia (Italy)

    2003-08-01

    The sorption of uranium(VI) on two cationic resins containing different complexing groups, the iminodiacetic resin Chelex 100 and the weak carboxylic resin Amberlite CG-50, was investigated. The Gibbs-Donnan model was used to describe and to predict the sorption through the determination of the intrinsic complexation constants. These quantities, even though non-thermodynamic, characterize the sorption as being independent of experimental conditions. The sorption mechanism of the metal on the complexing resins was also studied by adding a competitive soluble ligand that shifts the sorption curves to higher pH values. The ligand competes with the resin for the complexation with the metal ion. Uranium is also strongly sorbed on Chelex 100 at very acid pH, through formation of two complexes in the resin phase: ML with log{beta}{sub 110i}=-1.16, in more acidic solution, and ML{sub 2}with log {beta}{sub 120i}=-5.72. Only the presence of the competitive ligand in solution makes the determination of the second complex possible. Also on Amberlite CG-50 the sorption is strong and involves the formation of the complex ML {sub 2}, in more acidic solution, with log {beta}{sub 120i}=-3.16. In the presence of the ligand EDTA, the complex ML {sub 2}(OH) {sub 2}was characterized with log {beta}{sub 12-2i}=-5.15. In all the experiments the hydrolysis reaction in the aqueous phase was quantitatively considered. (orig.)

  19. Characterization of the sorption of uranium(VI) on different complexing resins

    International Nuclear Information System (INIS)

    Pesavento, Maria; Biesuz, Raffaela; Alberti, Giancarla; Sturini, Michela

    2003-01-01

    The sorption of uranium(VI) on two cationic resins containing different complexing groups, the iminodiacetic resin Chelex 100 and the weak carboxylic resin Amberlite CG-50, was investigated. The Gibbs-Donnan model was used to describe and to predict the sorption through the determination of the intrinsic complexation constants. These quantities, even though non-thermodynamic, characterize the sorption as being independent of experimental conditions. The sorption mechanism of the metal on the complexing resins was also studied by adding a competitive soluble ligand that shifts the sorption curves to higher pH values. The ligand competes with the resin for the complexation with the metal ion. Uranium is also strongly sorbed on Chelex 100 at very acid pH, through formation of two complexes in the resin phase: ML with logβ 110i =-1.16, in more acidic solution, and ML 2 with log β 120i =-5.72. Only the presence of the competitive ligand in solution makes the determination of the second complex possible. Also on Amberlite CG-50 the sorption is strong and involves the formation of the complex ML 2 , in more acidic solution, with log β 120i =-3.16. In the presence of the ligand EDTA, the complex ML 2 (OH) 2 was characterized with log β 12-2i =-5.15. In all the experiments the hydrolysis reaction in the aqueous phase was quantitatively considered. (orig.)

  20. Fluorimetric study of the mechanism of molecular association in aqueous solutions of polymethacrylic acid and sodium dodecylbenzenesulfonate

    Science.gov (United States)

    Sachko, A. V.; Zakordonskii, V. P.; Voloshinovskii, A. S.

    2013-03-01

    Fluorescent spectroscopy is used to investigate the processes of intermolecular association in mixed solutions of polymethacrylic acid (PMAA) and anionic sodium dodecylbenzenesulfonate (SDBS). We propose a model for describing the stage-by-stage mechanism of association processes and conclude that the nature of intermolecular associates depends on the PMAA-SDBS concentration ratio in the solution. Studying the kinetics of fluorescence decay reveals the simultaneous existence of two types of formations capable of pyrene solubilization.

  1. Quantum mechanics and molecular dynamics simulations of complexation of alkaline-earth and lanthanide cations by poly-amino-carboxylate ligands

    International Nuclear Information System (INIS)

    Durand, S.

    1999-01-01

    Molecular dynamics (MD) simulations on lanthanide(III) and alkaline-earth(II) complexes with poly-amino-carboxylates (ethylene-diamino-tetra-acetate EDTA 4- , ethylene-diamino-tri-acetate-acetic acid EDTA(H) 3- , tetra-aza-cyclo-dodecane-tetra-acetate DOTA 4- , methylene-imidine-acetate MIDA 2- ) are reported. First, a consistent set of Lennard-Jones parameters for La 3+ , Eu 3+ and Lu 3+ cations has been derived from free energy calculations in aqueous solution. Observed differences in hydration free energies, coordination distances and hydration numbers are reproduced. Then, the solution structures of 1:1 complexes of alkaline-earth and/or lanthanide cations with EDTA 4- , EDTA(H) 3- , DOTA 4- and 1:2 complexes of lanthanide cations with MIDA 2- were studied by MD in water. In addition, free energy calculations were performed to study, for each ligand, the relative thermodynamic stabilities of complexes with Ca 2+ vs Sr 2+ and vs Ba 2+ on the one hand, and with La 3+ vs Eu 3+ and vs Lu 3+ on the other hand. Model does not take into account explicitly polarization and charge transfer. However, the results qualitatively agree with experimental complexation data (structure and selectivities). (author)

  2. 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.

  3. Crystal nucleation in simple and complex fluids.

    Science.gov (United States)

    Oxtoby, David W

    2003-03-15

    The application of density-functional methods from statistical mechanics to the nucleation of crystals from the melt is described. Simple fluids such as metals, with sizes comparable with the range of their attractive forces, are compared with complex fluids such as colloidal suspensions and proteins dissolved in solution. A different mechanism for crystal nucleation is proposed in the latter case, in which density (concentration) changes before periodic crystalline order appears. This leads to a theoretical foundation for empirical observations on the 'crystallization window' in protein crystallization. Comparisons are made with the results of computer simulation via molecular dynamics.

  4. Stochastic epidemic-type model with enhanced connectivity: exact solution

    International Nuclear Information System (INIS)

    Williams, H T; Mazilu, I; Mazilu, D A

    2012-01-01

    We present an exact analytical solution to a one-dimensional model of the susceptible–infected–recovered (SIR) epidemic type, with infection rates dependent on nearest-neighbor occupations. We use a quantum mechanical approach, transforming the master equation via a quantum spin operator formulation. We calculate exactly the time-dependent density of infected, recovered and susceptible populations for random initial conditions. Our results compare well with those of previous work, validating the model as a useful tool for additional and extended studies in this important area. Our model also provides exact solutions for the n-point correlation functions, and can be extended to more complex epidemic-type models

  5. Efficiency and mechanisms of Cd removal from aqueous solution by biochar derived from water hyacinth (Eichornia crassipes).

    Science.gov (United States)

    Zhang, Feng; Wang, Xin; Yin, Daixia; Peng, Bo; Tan, Changyin; Liu, Yunguo; Tan, Xiaofei; Wu, Shixue

    2015-04-15

    This study investigated the efficiency and mechanisms of Cd removal by biochar pyrolyzed from water hyacinth (BC) at 250-550 °C. BC450 out-performed the other BCs at varying Cd concentrations and can remove nearly 100% Cd from aqueous solution within 1 h at initial Cd ≤ 50 mg l(-1). The process of Cd sorption by BC450 followed the pseudo-second order kinetics with the equilibrium being achieved after 24 h with initial Cd ranging from 100 to 500 mg l(-1). The maximum Cd sorption capacity of BC450 was estimated to be 70.3 mg g(-1) based on Langmuir model, which is prominent among a range of low-cost sorbents. Based on the balance analysis between cations released and Cd sorbed onto BC450 in combination with SEM-EDX and XPS data, ion-exchange followed by surface complexation is proposed as the dominant mechanism responsible for Cd immobilization by BC450. In parallel, XRD analysis also suggested the formation of insoluble Cd minerals (CdCO3, Cd3P2, Cd3(PO4)2 and K4CdCl6) from either (co)-precipitation or ion exchange. Results from this study highlighted that the conversion of water hyacinth into biochar is a promising method to achieve effective Cd immobilization and improved management of this highly problematic invasive species. Copyright © 2015 Elsevier Ltd. All rights reserved.

  6. 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.)

  7. Interfacial properties of chitosan/sodium dodecyl sulfate complexes

    Directory of Open Access Journals (Sweden)

    Milinković Jelena R.

    2017-01-01

    Full Text Available Contemporary formulations of cosmetic and pharmaceutical emulsions may be achieved by using combined polymer/surfactant system, which can form complexes with different structure and physicochemical properties. Such complexation can lead to additional stabilization of the emulsion products. For these reasons, the main goal of this study was to investigate the interfacial properties of chitosan/sodium dodecyl sulfate complexes. In order to understand the stabilization mechanism, the interface of the oil/water systems that contained mixtures of chitosan and sodium dodecyl sulfate, was studied by measuring the interfacial tension. Considering the fact that the properties of the oil phase has influence on the adsorption process, three different types of oil were investigated: medium-chain triglycerides (semi-synthetic oil, paraffin oil (mineral oil and natural oil obtained from the grape seed. The surface tension measurements at the oil/water interface, for chitosan water solutions, indicate a poor surface activity of this biopolymer. Addition of sodium dodecyl sulfate to chitosan solution causes a significant decrease in the interfacial tension for all investigated oils. The results of this study are important for understanding the influence of polymer-surfactant interactions on the properties of the solution and stability of dispersed systems. [Project of the Serbian Ministry of Education, Science and Technological Development, Grant no. III46010

  8. 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)

  9. Complex Correspondence Principle

    International Nuclear Information System (INIS)

    Bender, Carl M.; Meisinger, Peter N.; Hook, Daniel W.; Wang Qinghai

    2010-01-01

    Quantum mechanics and classical mechanics are distinctly different theories, but the correspondence principle states that quantum particles behave classically in the limit of high quantum number. In recent years much research has been done on extending both quantum and classical mechanics into the complex domain. These complex extensions continue to exhibit a correspondence, and this correspondence becomes more pronounced in the complex domain. The association between complex quantum mechanics and complex classical mechanics is subtle and demonstrating this relationship requires the use of asymptotics beyond all orders.

  10. Oxidative dehydrogenation of the 2-aminomethylpyridine (EDTA) ruthenium (III) complex

    International Nuclear Information System (INIS)

    Toma, H.E.; Tsurumaki, M.

    1990-01-01

    The oxidative dehydrogenation of the 2-aminomethylpyridine (ampy) ligand coordinated to the (EDTA)RU(III) complex was investigated based on cyclic voltammetry, spectoelectrochemistry and stopped-flow kinetic measurements in aqueous solution. The reaction mechanism is consistent with the deprotonation of the ampy ligand (pk a =7.48), followed by a reversible one-electron transfer step. The intermediate species generated at this step undergoes a metal-induced electron transfer process, with k=227 s -1 , converting into the corresponding 2-iminomethylpyridine complex. (author) [pt

  11. Radiolysis of nucleosides in aqueous solutions: base liberation by the base attack mechanism

    International Nuclear Information System (INIS)

    Fujita, S.

    1984-01-01

    On the radiolysis of uridine and some other nucleosides in aqueous solution, a pH-dependent liberation of uracil or the corresponding base was found. e - sub(aq) and HOsup(anion radicals) 2 gave no freed bases, although many oxidizing radicals, including OH, Clsup(anion radicals) 2 , Brsup(anion radicals) 2 , (CNS)sup(anion radicals) 2 and SOsup(anion radicals) 4 , did cause the release of unaltered bases, depending on the pH of the solutions. The base yields were generally high at pH >= 11, with the exception of SOsup(anion radicals) 4 , which gave a rather high yield of uracil (from uridine) even in the pH region of - , present at high pH as the dissociated form of OH, may act partly as an oxidizing radical. A plausible mechanism of 3 1 -radical formation is discussed. (author)

  12. Electrodeposition of ZnO from DMSO solution: influence of anion nature and its concentration in the nucleation and growth mechanisms

    Energy Technology Data Exchange (ETDEWEB)

    Riveros, Gonzalo; Ramirez, Daniel, E-mail: gonzalo.riveros@uv.cl [Departamento de Quimica y Bioquimica, Facultad de Ciencias, Universidad de Valparaiso, Valparaiso (Chile); Tello, Alejandra; Schrebler, Ricardo; Henriquez, Rodrigo; Gomez, Humberto [Instituto de Quimica, Pontificia Universidad Catolica de Valparaiso, Curauma, Valparaiso (Chile)

    2012-03-15

    The influence of the anion nature and its concentration in the electrodeposition of ZnO onto a gold electrode from dimethylsulfoxide (DMSO) solutions was studied. Voltammetric experiments revealed important changes in the zinc oxide electrodeposition process depending on the employed anion as electrolyte. From chronoamperometric experiments, the corresponding current-time curves were fitted with different nucleation and growth mechanism models. The analysis of these results showed changes from an instantaneous to a progressive growth when the solution composition was changed from ZnCl{sub 2} to ZnCl{sub 2} + LiCl. The change of the mechanism is associated to the adsorption of chloride ion on the active sites of the electrode surface when LiCl is present in the solution. (author)

  13. Solutions Stability of Initial Boundary Problem, Modeling of Dynamics of Some Discrete Continuum Mechanical System

    Directory of Open Access Journals (Sweden)

    D. A. Eliseev

    2015-01-01

    Full Text Available The solution stability of an initial boundary problem for a linear hybrid system of differential equations, which models the rotation of a rigid body with two elastic rods located in the same plane is studied in the paper. To an axis passing through the mass center of the rigid body perpendicularly to the rods location plane is applied the stabilizing moment proportional to the angle of the system rotation, derivative of the angle, integral of the angle. The external moment provides a feedback. A method of studying the behavior of solutions of the initial boundary problem is proposed. This method allows to exclude from the hybrid system of differential equations partial differential equations, which describe the dynamics of distributed elements of a mechanical system. It allows us to build one equation for an angle of the system rotation. Its characteristic equation defines the stability of solutions of all the system. In the space of feedback-coefficients the areas that provide the asymptotic stability of solutions of the initial boundary problem are built up.

  14. Extraction mechanism of Sc(III) from sulphuric acid solution by primary amine N1923

    International Nuclear Information System (INIS)

    Le Shaoming; Li Deqian; Ni Jiazan

    1987-01-01

    The extraction mechanism of Sc(III) from sulphuric acid solution by primary amine N 1923 (RNH 2 ) has been investigated by means of slope, isomolar continuous variation and saturation methods. The effect of temperature on the extraction of Sc(III) is observed. The extraction equilibrium constant and thermodynamic functions (ΔH, ΔS and ΔG) are obtained. The IR and NMR of extracted compound are measured

  15. An Approach to Implementing A Threshold Adjusting Mechanism in Very Complex Negotiations : A Preliminary Result

    OpenAIRE

    Fujita, Katsuhide; Ito, Takayuki; Hattori, Hiromitsu; Klein, Mark

    2007-01-01

    In this paper, we propose a threshold adjusting mechanism in very complex negotiations among software agents. The proposed mechanism can facilitate agents to reach an agreement while keeping their private information as much as possible. Multi-issue negotiation protocols have been studied widely and represent a promising field since most negotiation problems in the real world involve interdependent multiple issues. We have proposed negotiation protocols where a bidding-based mechanism is used...

  16. Mechanism of mechanochemical synthesis of complex oxides and the peculiarities of their nano-structurization determining sintering

    Directory of Open Access Journals (Sweden)

    Zyryanov V.V.

    2005-01-01

    Full Text Available A mechanism of superfast mechanosynthesis reaction for oxide systems is proposed on the base of a dynamics study. The threshold effect and linear dependence of the chemical response on the effective temperature of the reaction zone are established. Major factors are determined: molecular mass of reagents, enthalpy and difference of reagents in Mohs’s hardness, which also influence the composition of the primary product. Primary acts are characterized by a superfast roller mechanism of mass transfer with the formation of a transient dynamic state (D*. Secondary acts slowly approximate the composition of the product to the composition of the starting mixture by diffusion mass transfer in a deformation mixing regime with a contribution of a rotation (roller mechanism. The list of structure types for complex oxides derived by mechanosynthesis includes perovskites, fluorites, pyrochlors, sheelites, and some other ones. Powders of crystal products display multilevel structurization. In all studied complex oxides strong disordering of the “anti-glass” type was observed. The mechanism of sintering was studied in BaTiO3 powders of different origin and in metastable complex oxides derived by mechanosynthesis. The major contribution in shrinkage belongs to rearrangements of crystalline particles as a whole. Structure transformations accompany, as a rule, sintering of inhomogeneous powders derived by mechanosynthesis.

  17. MWCNTs/Cellulose Hydrogels Prepared from NaOH/Urea Aqueous Solution with Improved Mechanical Properties

    Directory of Open Access Journals (Sweden)

    Yingpu Zhang

    2015-01-01

    Full Text Available Novel high strength composite hydrogels were designed and synthesized by introducing multiwalled carbon nanotubes (MWCNTs into cellulose/NaOH/urea aqueous solution and then cross-linked by epichlorohydrin. MWCNTs were used to modify the matrix of cellulose. The structure and morphology of the hydrogels were characterized by Fourier transform infrared (FT-IR spectroscopy, high resolution transmission electron microscopy (HR-TEM, and scanning electron microscopy (SEM. The results from swelling testing revealed that the equilibrium swelling ratio of hydrogels decreased with the increment of MWCNTs content. Thermogravimetric analysis (TGA and dynamic mechanical analysis (DMA results demonstrated that the introduction of MWCNT into cellulose hydrogel networks remarkably improved both thermal and mechanical properties of the composite hydrogels. The preparation of MWCNTs modifiedcellulose-based composites with improved mechanical properties was the first important step towards the development of advanced functional materials.

  18. Equilibrium and extraction mechanism from monomeric and polimeric species of zirconium in solution. part. 2

    International Nuclear Information System (INIS)

    Azevedo, H.L.P. de.

    1980-01-01

    The mechanism of extraction and the equilibrium of chemical species from Zirconium solutions was studied. The multiple extraction method was used to show the species envolved in the extraction process and qualitative informations was obtained about the equilibrium between extractable species (monomers) and non-extractable species (polymers) in the aqueous phase. (M.J.C.) [pt

  19. Photochemistry and exciplex of the uranyl ion in aqueous solution

    International Nuclear Information System (INIS)

    Marcantonatos, M.D.

    1980-01-01

    The effects of acidity, temperature, self-quenching and H-donor concentration on the luminescent state of the aqua-uranyl(VI) ion have been studied in aqueous acidic nitrate and perchlorate solution. The detailed results cannot be explained by any single simple mechanism such as radiative, non-radiative or spontaneous collisional quenching, or irreversible hydrogen abstraction from water. Quantitative analysis of the results shows a far more complex mechanism, involving the adiabatic formation of the species *UO 2 H 2+ and *U 2 O 4 H 4+ , as already proposed by the author. This mechanism is supported by state and m.o. correlations. The abstraction of hydrogen from water is shown to take place by H atom transfer in a *uranyl-water complex intermediate, rather than by attack of H + on the fully occupied πsub(u) orbitals of uranium(V) in a well-defined uranyl water complex with strong charge transfer character. A qualitative description of the exciplex *U 2 O 4 H 4+ is shown to be possible in a v.b. formalism and the origin of its radiative properties is discussed on this basis. (author)

  20. 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.

  1. 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.

  2. Gold nanoparticles as a factor of influence on doxorubicin-bovine serum albumin complex

    Science.gov (United States)

    Goncharenko, N. A.; Pavlenko, O. L.; Dmytrenko, O. P.; Kulish, M. P.; Lopatynskyi, A. M.; Chegel, V. I.

    2018-04-01

    The interaction between doxorubicin (Dox) and bovine serum albumin (BSA) complex with gold nanoparticles (AuNPs) was investigated by optical spectroscopy. The optical absorption of Dox and BSA solutions was studied. The formation of Dox-BSA complexes with a binding constant K = 7.56 × 106 M-2 and the number of binding sites n = 2 was found out. With pH 6.9, the concentration of complexes is an order of magnitude lower than the concentration of unbound antibiotic molecules. Optical absorption in solutions of Dox-BSA conjugates in the presence of AuNPs undergoes a significant rearrangement, which manifests the changes in the magnitude of the hydrophobic interaction of BSA with Dox, changes in the conformational state of antibiotic, and, as a consequence, a plasmon-induced change in the mechanism of complex formation. The aggregation of the Dox-AuNPs conjugate depends on the presence and concentration of BSA and in the case of formation of the Dox-BSA complex is minimal.

  3. Modeling a calixarene-crown-6 and its alkali complexes by means of a hybrid quantum mechanical/molecular mechanical method

    International Nuclear Information System (INIS)

    Lamare, V.; Golebiowski, J.; Ruiz-Lopez, M.F.; Martins-Costa, M.; Millot, C.

    2000-01-01

    Calixarene-crown-6s in 1,3-alternate conformation are compounds currently investigated for their ability to selectively extract traces of cesium from acidic or strong salinity aqueous solutions. Studies based on molecular modeling were undertaken on these systems to understand their behavior regarding cesium and other alkali cations, in particular sodium. In this work, a recently developed molecular modeling approach was used to investigate calixarene BC6 and its alkali complexes. The whole calixarene ligand is treated by the semiempirical AM1 quantum method (QM) whereas the cation and solvent are treated by a conventional force field (MM). The total energy of the system is the sum of the QM and MM sub-system contributions plus the QM/MM interaction energy. The latter includes the electrostatic interaction between QM charges (nuclei + electrons) and MM sites, and the non-electrostatic QM/MM van der Weals term, usually expressed by a Lennard-Jones potential. In the QM/MM method, van der Waals interactions between the QM and MM sub-systems are described by empirical Lennard-Jones parameters which must be adapted to the hybrid potential considered. Parameters on oxygen atoms were optimized. For the cations, two sets of Parameters were tested: Aqvist empirical parameters, derived to represent cation/water interactions in classical dynamics (set 2), and a new set of parameters which we calculated from dispersion coefficients available in the literature (set 1). The latter gave better results for the interactions with the crown. In the sodium complex, the cation interacts with only four oxygen atoms of the crown, whereas in the complex with cesium, the interaction involves six oxygen atoms. Distortion of the BC6 is therefore less with sodium and favors the corresponding complex by 4 kcal/mol. The cation/BC6 van der Waals energy is very weak for the two complexes. Hence the interaction between the cation and BC6 is primarily electrostatic. The BC6 polarization energy due

  4. Nonlinear crack mechanics

    International Nuclear Information System (INIS)

    Khoroshun, L.P.

    1995-01-01

    The characteristic features of the deformation and failure of actual materials in the vicinity of a crack tip are due to their physical nonlinearity in the stress-concentration zone, which is a result of plasticity, microfailure, or a nonlinear dependence of the interatomic forces on the distance. Therefore, adequate models of the failure mechanics must be nonlinear, in principle, although linear failure mechanics is applicable if the zone of nonlinear deformation is small in comparison with the crack length. Models of crack mechanics are based on analytical solutions of the problem of the stress-strain state in the vicinity of the crack. On account of the complexity of the problem, nonlinear models are bason on approximate schematic solutions. In the Leonov-Panasyuk-Dugdale nonlinear model, one of the best known, the actual two-dimensional plastic zone (the nonlinearity zone) is replaced by a narrow one-dimensional zone, which is then modeled by extending the crack with a specified normal load equal to the yield point. The condition of finite stress is applied here, and hence the length of the plastic zone is determined. As a result of this approximation, the displacement in the plastic zone at the abscissa is nonzero

  5. Efficient parallel implementations of QM/MM-REMD (quantum mechanical/molecular mechanics-replica-exchange MD) and umbrella sampling: isomerization of H2O2 in aqueous solution.

    Science.gov (United States)

    Fedorov, Dmitri G; Sugita, Yuji; Choi, Cheol Ho

    2013-07-03

    An efficient parallel implementation of QM/MM-based replica-exchange molecular dynamics (REMD) as well as umbrella samplings techniques was proposed by adopting the generalized distributed data interface (GDDI). Parallelization speed-up of 40.5 on 48 cores was achieved, making our QM/MM-MD engine a robust tool for studying complex chemical dynamics in solution. They were comparatively used to study the torsional isomerization of hydrogen peroxide in aqueous solution. All results by QM/MM-REMD and QM/MM umbrella sampling techniques yielded nearly identical potentials of mean force (PMFs) regardless of the particular QM theories for solute, showing that the overall dynamics are mainly determined by solvation. Although the entropic penalty of solvent rearrangements exists in cisoid conformers, it was found that both strong intermolecular hydrogen bonding and dipole-dipole interactions preferentially stabilize them in solution, reducing the torsional free-energy barrier at 0° by about 3 kcal/mol as compared to that in gas phase.

  6. 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

  7. Structural transitions in the titanium alloy β-CEZ studied by precipitation mechanisms after solution treatment

    International Nuclear Information System (INIS)

    Angelier, C.; Bechet, J.

    1994-01-01

    The β-CEZ, a high strength titanium alloy developed for aerospace engine applications, is a α/β near β alloy. A wide variety of phase transformations and attendant nodular, lamellar and mixed microstructures are possible according to thermomechanical treatment conditions. The aim of this present paper is to illustrate the influence of solution treat-ment temperature on equilibrium microstructures and continuous cooling transformations. Solution treatment temperature controls the volume fraction of primary α particles and composition of the β-matrix. Therefore the transformation during continuous cooling from α/β or β field depends on β-matrix stability and potential sites amount of α precipitation. After a β solution treatment, the α particles are disappeared and the β phase contains all alloying elements; the continuous cooling transformation produces a Widmanstaetten structure. If the cooling rate or/and the solution treatment temperature in the α/β field are sufficiently low, the microstructure consists only of nodular morphology. During α particles growth the α volume fraction increases as equilibrium and the decreasing of growth kinetic leads to supersaturated β matrix and Widmanstaetten α precipitation. The final microstructures are mixed. The influence of solution trat-ment temperature and cooling rate on nucleation and growth mechanisms is specially developed. (orig.)

  8. 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

  9. 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.

  10. 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.

  11. On Perturbative Cubic Nonlinear Schrodinger Equations under Complex Nonhomogeneities and Complex Initial Conditions

    Directory of Open Access Journals (Sweden)

    Magdy A. El-Tawil

    2009-01-01

    Full Text Available A perturbing nonlinear Schrodinger equation is studied under general complex nonhomogeneities and complex initial conditions for zero boundary conditions. The perturbation method together with the eigenfunction expansion and variational parameters methods are used to introduce an approximate solution for the perturbative nonlinear case for which a power series solution is proved to exist. Using Mathematica, the symbolic solution algorithm is tested through computing the possible approximations under truncation procedures. The method of solution is illustrated through case studies and figures.

  12. Mechanical and Morphological Effect of Plant Based Antimicrobial Solutions on Maxillofacial Silicone Elastomer.

    Science.gov (United States)

    Tetteh, Sophia; Bibb, Richard J; Martin, Simon J

    2018-05-30

    The objective of this study was to determine the effect of plant based antimicrobial solutions specifically tea tree and Manuka oil on facial silicone elastomers. The purpose of this in vitro study was to evaluate the effect of disinfection with plant extract solution on mechanical properties and morphology on the silicone elastomer. Test specimens were subjected to disinfection using tea tree oil, Manuka oil and the staphylococcus epidermidis bacteria. Furthermore, a procedure duration was used in the disinfection process to simulate up to one year of usage. Over 500 test specimens were fabricated for all tests performed namely hardness, elongation, tensile, tear strength tests, visual inspection and lastly surface characterization using SEM. A repeated measures ANOVA revealed that hardness and elongation at break varied significantly over the time period, whereas this was not observed in the tear and tensile strength parameters of the test samples.

  13. Mechanical and Morphological Effect of Plant Based Antimicrobial Solutions on Maxillofacial Silicone Elastomer

    Directory of Open Access Journals (Sweden)

    Sophia Tetteh

    2018-05-01

    Full Text Available The objective of this study was to determine the effect of plant based antimicrobial solutions specifically tea tree and Manuka oil on facial silicone elastomers. The purpose of this in vitro study was to evaluate the effect of disinfection with plant extract solution on mechanical properties and morphology on the silicone elastomer. Test specimens were subjected to disinfection using tea tree oil, Manuka oil and the staphylococcus epidermidis bacteria. Furthermore, a procedure duration was used in the disinfection process to simulate up to one year of usage. Over 500 test specimens were fabricated for all tests performed namely hardness, elongation, tensile, tear strength tests, visual inspection and lastly surface characterization using SEM. A repeated measures ANOVA revealed that hardness and elongation at break varied significantly over the time period, whereas this was not observed in the tear and tensile strength parameters of the test samples.

  14. Optimization and analysis of large chemical kinetic mechanisms using the solution mapping method - Combustion of methane

    Science.gov (United States)

    Frenklach, Michael; Wang, Hai; Rabinowitz, Martin J.

    1992-01-01

    A method of systematic optimization, solution mapping, as applied to a large-scale dynamic model is presented. The basis of the technique is parameterization of model responses in terms of model parameters by simple algebraic expressions. These expressions are obtained by computer experiments arranged in a factorial design. The developed parameterized responses are then used in a joint multiparameter multidata-set optimization. A brief review of the mathematical background of the technique is given. The concept of active parameters is discussed. The technique is applied to determine an optimum set of parameters for a methane combustion mechanism. Five independent responses - comprising ignition delay times, pre-ignition methyl radical concentration profiles, and laminar premixed flame velocities - were optimized with respect to thirteen reaction rate parameters. The numerical predictions of the optimized model are compared to those computed with several recent literature mechanisms. The utility of the solution mapping technique in situations where the optimum is not unique is also demonstrated.

  15. Thermodynamic Investigation and Mixed Ligand Complex Formation of 1,4-Bis-(3-aminopropyl)-piperazine and Biorelevant Ligands.

    Science.gov (United States)

    El-Sherif, Ahmed A; Shehata, Mohamed R; Shoukry, Mohamed M; Barakat, Mohammad H

    2012-01-01

    Thermodynamic parameters for protonation of 1,4-bis(3-aminopropyl)-piperazine (BAPP) and its metal complexation with some divalent metal ions were determined in aqueous solution at constant ionic strength (0.1 M NaNO(3)) using a potentiometric technique. The order of -ΔG(0) and -ΔH(0) was found to obey Co(2+) Zn(2+), in accordance with the Irving-Williams order. The formation equilibria of zinc (II) complexes and the ternary complexes Zn(BAPP)L, where L = amino acid, amides, or DNA constituents), have been investigated. Ternary complexes are formed by a simultaneous mechanism. The concentration distribution of the complexes in solution was evaluated as a function of pH. Stoichiometry and stability constants for the complexes formed are reported and discussed. The stability of ternary complexes was quantitatively compared with their corresponding binary complexes in terms of the parameter Δlog K.

  16. 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

  17. Uranium mill tailings neutralization: contaminant complexation and tailings leaching studies

    International Nuclear Information System (INIS)

    Opitz, B.E.; Dodson, M.E.; Serne, R.J.

    1985-05-01

    Laboratory experiments were performed to compare the effectiveness of limestone (CaCO 3 ) and hydrated lime [Ca(OH) 2 ] for improving waste water quality through the neutralization of acidic uranium mill tailings liquor. The experiments were designed to also assess the effects of three proposed mechanisms - carbonate complexation, elevated pH, and colloidal particle adsorption - on the solubility of toxic contaminants found in a typical uranium mill waste solution. Of special interest were the effects each of these possible mechanisms had on the solution concentrations of trace metals such as Cd, Co, Mo, Zn, and U after neutralization. Results indicated that the neutralization of acidic tailings to a pH of 7.3 using hydrated lime provided the highest overall waste water quality. Both the presence of a carbonate source or elevating solution pH beyond pH = 7.3 resulted in a lowering of previously achieved water quality, while adsorption of contaminants onto colloidal particles was not found to affect the solution concentration of any constituent investigated. 24 refs., 8 figs., 19 tabs

  18. The influence of the "cage" effect on the mechanism of reversible bimolecular multistage chemical reactions proceeding from different sites in solutions.

    Science.gov (United States)

    Doktorov, Alexander B

    2016-08-28

    Manifestations of the "cage" effect at the encounters of reactants have been theoretically treated on the example of multistage reactions (including bimolecular exchange reactions as elementary stages) proceeding from different active sites in liquid solutions. It is shown that for reactions occurring near the contact of reactants, consistent consideration of quasi-stationary kinetics of such multistage reactions (possible in the framework of the encounter theory only) can be made on the basis of chemical concepts of the "cage complex," just as in the case of one-site model described in the literature. Exactly as in the one-site model, the presence of the "cage" effect gives rise to new channels of reactant transformation that cannot result from elementary event of chemical conversion for the given reaction mechanism. Besides, the multisite model demonstrates new (as compared to one-site model) features of multistage reaction course.

  19. Mechanism of iron catalyzed oxidation of SO/sub 2/ in oxygenated solutions

    Energy Technology Data Exchange (ETDEWEB)

    Freiberg, J

    1975-01-01

    Previous experimental work concerning the iron catalyzed oxidation of SO/sub 2/ in oxygenated acid solutions failed to provide a consistent reaction mechanism and rate expression. As iron is one of the main constituents of urban atmospheric aerosols, the rate studies of heterogeneous sulphate formation in polluted city air were hampered. The present study develops a new theory for the iron catalyzed oxidation of SO/sub 2/. The resulting new rate expression is general enough to account for the results of previous experimental investigations that were performed in different ranges of SO/sub 2/ and catalyst concentrations.

  20. 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

  1. Mechanisms of reactions of organoaluminium compounds with alkenes and alkynes catalyzed by Zr complexes

    International Nuclear Information System (INIS)

    Parfenova, L V; Khalilov, Leonard M; Dzhemilev, Usein M

    2012-01-01

    The results of studies dealing with mechanisms of hydro-, carbo- and cycloalumination of alkenes and alkynes catalyzed by zirconium complexes are generalized and systematized for the first time. Data about the structures of intermediates responsible for the formation of the target compounds are presented and the available data on the effect of the structure of organoaluminium compounds and the electronic and steric factors determining the catalytic activity of metal complexes in these reactions are considered in detail. Much attention is paid to studies of the influence of reaction conditions on the chemo-, regio- and stereoselectivity of the Zr-containing complex catalysts. The bibliography includes 217 references.

  2. 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.

  3. Enzyme-like catalysis via ternary complex mechanism: alkoxy-bridged dinuclear cobalt complex mediates chemoselective O-esterification over N-amidation.

    Science.gov (United States)

    Hayashi, Yukiko; Santoro, Stefano; Azuma, Yuki; Himo, Fahmi; Ohshima, Takashi; Mashima, Kazushi

    2013-04-24

    Hydroxy group-selective acylation in the presence of more nucleophilic amines was achieved using acetates of first-row late transition metals, such as Mn, Fe, Co, Cu, and Zn. Among them, cobalt(II) acetate was the best catalyst in terms of reactivity and selectivity. The combination of an octanuclear cobalt carboxylate cluster [Co4(OCOR)6O]2 (2a: R = CF3, 2b: R = CH3, 2c: R = (t)Bu) with nitrogen-containing ligands, such as 2,2'-bipyridine, provided an efficient catalytic system for transesterification, in which an alkoxide-bridged dinuclear complex, Co2(OCO(t)Bu)2(bpy)2(μ2-OCH2-C6H4-4-CH3)2 (10), was successfully isolated as a key intermediate. Kinetic studies and density functional theory calculations revealed Michaelis-Menten behavior of the complex 10 through an ordered ternary complex mechanism similar to dinuclear metallo-enzymes, suggesting the formation of alkoxides followed by coordination of the ester.

  4. Mechanism and kinetic considerations of TOC removal from the powdered activated carbon ozonation of diclofenac aqueous solutions.

    Science.gov (United States)

    Beltrán, Fernando J; Pocostales, J Pablo; Alvarez, Pedro M; Jaramillo, Josefa

    2009-09-30

    Ozonation of DCF in aqueous solution in the presence of powdered activated carbon (PAC) has been studied for mechanistic and kinetic purposes. The effects of gas flow rate, ozone gas concentration and initial TOC on the TOC elimination rate were then investigated. The use of PAC allows liquid-solid and internal diffusion mass transfer resistances being eliminated. Gas-liquid mass transfer resistance is also eliminated when ozonation is applied to DCF preozonated solutions. In the absence of mass transfer resistances a mechanism of reactions involving homogeneous and heterogeneous steps for TOC removal was proposed. From this mechanism a mathematical model constituted by mass balances of main species in water was established. Considerations about the changing nature of ozonation intermediates, as being promoters or inhibitors of ozone decomposition, is a key point to better predict the experimental concentrations of species present in this system.

  5. Initial Stages in the Rhodium(III)-Catalyzed C-H Bond Activation of Primary Alcohols in Aqueous Solution

    DEFF Research Database (Denmark)

    Eriksen, J.; Monsted, L.; Monsted, O.

    2010-01-01

    The mechanism of the catalytic HID exchange in primary alcohol substrates derived from aldopentoses, promoted by a macrocyclic rhodium(III) complex, has been shown to occur by a reversible redox reaction that gives aldehyde and a rhodium hydride complex. Hydride exchange in the latter complex...... promotes the introduction of solvent hydrogen in the primary alcohol formed by the reverse reaction. The hydride complex has been crystallographically characterized as a trifluoromethanesulfonate salt that contains the trans-[Rh(cycb)(H)(OH2)](2+) (cycb = rac-5,5,7,12,12,14-hexamethyl-1......,4,8,11-tetraazacyclotetradecane) cation. The hydride complex is stable for extended periods of time in acidic solution in the absence of oxidants. In basic solutions a series of base-catalyzed reactions take place to yield ultimately the same mixture of [Rh(cycb)(OH)(2)](+) isomers as produced by base hydrolysis of the trans...

  6. 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.

  7. 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.

  8. Interest of uranium complexes for the mechanism study of the McMurry reaction

    International Nuclear Information System (INIS)

    Maury, O.

    1997-01-01

    The reducing coupling reactions of ketones in diols and olefins are generally carried out with titanium or samarium compounds. In this work uranium complexes have been used. They have allowed to study the chemical reaction mechanism. This thesis is divided into three parts: 1) the reduction mechanism of uranium tetrachloride by cyclic voltametry has been studied at first. It has been shown that this reduction is followed by a transfer reaction of chlorides between the reduced specie of the higher electronic density and UCl . 2) In the second part is described: the synthesis, the crystal structure, the reactivity of the chemical agents, the stereochemistry of diols and alkenes formation and the pinacolisation reaction catalysis. 3) In the last part, the limits of the McMurry reaction are given by the study of the aromatic ketones pinacolisation reaction by-products. The obtained results show that the complexes of the metals which present a high reducing and oxo-philic (Ti, Sm, U..) character react in a similar way with the carbonyl compounds. If the uranium compounds are less used than those of the titanium in the field of the organic synthesis applications, they are precious auxiliaries and excellent models for reactions mechanisms study and for the synthesis methods optimization. (O.M.)

  9. A molecular mechanics (MM3(96)) force field for metal-amide complexes

    International Nuclear Information System (INIS)

    Hay, B.P.; Clement, O.; Sandrone, G.; Dixon, D.A.

    1998-01-01

    A molecular mechanics (MM3(96)) force field is reported for modeling metal complexes of amides in which the amide is coordinated through oxygen. This model uses a points-on-a-sphere approach which involves the parameterization of the Msingle bondO stretch, the Msingle bondO double-bond C bend, and the Msingle bondO double-bond Csingle bondX (X = C, H, N) torsion interactions. Relationships between force field parameters and metal ion properties (charge, ionic radius, and electronegativity) are presented that allow the application of this model to a wide range of metal ions. The model satisfactorily reproduces the structures of over fifty amide complexes with the alkaline earths, transition metals, lanthanides, and actinides

  10. Mechanisms of bands and spirals formation during the drying of watery solutions of mercury (II) chloride with agar-agar

    International Nuclear Information System (INIS)

    Suarez-DomInguez, Edgardo Jonathan; Betancourt-Mar, Juvencio Alberto

    2005-01-01

    It is proposed two mechanisms to explain the formation of periodic and non periodic bands and spirals as thin films of gelatinous aqueous solutions of mercury (II) chloride are dried. The first mechanism supposes an homogeneous drying, where the height of the film decreases at constant rate, forming Liesegang bands. The second mechanism implies a non homogeneous drying where an evaporation front drives the formation of periodic bands and spirals

  11. Molecular mechanism of the viscosity of aqueous glucose solutions

    Science.gov (United States)

    Bulavin, L. A.; Zabashta, Yu. F.; Khlopov, A. M.; Khorol'skii, A. V.

    2017-01-01

    Experimental relations are obtained for the viscosity of aqueous glucose solutions in the temperature range of 10-80°C and concentration range 0.01-2.5%. It is found that the concentration dependence of fluidity is linear when the concentration is higher than a certain value and varies at different temperatures. The existence of such a dependence indicates that the mobilities of solvent and solute molecules are independent of the concentration of solutions. This assumption is used to construct a theoretical model, in which the structure of an aqueous glucose solution is presented as a combination of two weakly interacting networks formed by hydrogen bonds between water molecules and between glucose molecules. Theoretical relations are obtained using this model of network solution structure for the concentration and temperature dependence of solution viscosity. Experimental data are used to calculate the activation energies for water ( U w = 3.0 × 10-20 J) and glucose molecules ( U g = 2.8 × 10-20 J). It is shown that the viscosity of a solution in such a network structure is governed by the Brownian motion of solitons along the chains of hydrogen bonds. The weak interaction between networks results in the contributions to solution fluidity made by the motion of solitons in both of them being almost independent.

  12. Synthesis and novel fluorescence phenomenon of terbium(III) complex with N, N',N' -tris (2-benzimidazolmethyl) amine

    International Nuclear Information System (INIS)

    Yang, Tianlin; Gao, Min; Yang, Jinhui; Qin, Wenwu

    2010-01-01

    A benzimidazole ligand with a tripodal structure, N, N', N' -tris (2-benzimidazolmethyl) amine, and its terbium (III) complex has been synthesized. The complex has been characterized by element analysis, IR spectra, mass spectra, thermal analysis and molar conductivity. The terbium ion is found to coordinate with the nitrogen atoms (= N-) of imidazole ring and the bridgehead nitrogen atom. The fluorescence properties of the complex in aqueous solutions have been studied. Under excitation of UV light, the complex exhibits characteristic fluorescence of terbium ion. The luminescence of terbium complex in aqueous solutions is strongly enhanced by H + concentration. This phenomenon makes the new complex favorable for use in fluorescence switches and sensors. The mechanism of the fluorescence enhancement by protonation of the nitrogen atoms (-NH-) of imidazole ring is due to the suppressed photoinduced electron transfer fluorescence quenching on addition of acid. (author)

  13. Potential mechanisms of cadmium removal from aqueous solution by Canna indica derived biochar

    Energy Technology Data Exchange (ETDEWEB)

    Cui, Xiaoqiang; Fang, Siyu; Yao, Yiqiang; Li, Tingqiang [Ministry of Education Key Laboratory of Environmental Remediation and Ecological Health, College of Environmental and Resource Sciences, Zhejiang University, Hangzhou 310058 (China); Ni, Qijun [The 702 Research Institute of China Shipbuilding Industry Corporation, Wuxi 214082 (China); Yang, Xiaoe, E-mail: xyang@zju.edu.cn [Ministry of Education Key Laboratory of Environmental Remediation and Ecological Health, College of Environmental and Resource Sciences, Zhejiang University, Hangzhou 310058 (China); He, Zhenli [Indian River Research and Education Center, Institute of Food and Agricultural Sciences, University of Florida, Fort Pierce, FL 34951 (United States)

    2016-08-15

    The objective of this study was to investigate the mechanisms of cadmium (Cd) sorption on biochars produced at different temperature (300–600 °C) and their quantitative contribution. The sorption isotherms and kinetics of Cd{sup 2+} sorption on biochars were determined and fitted to different models. The Cd{sup 2+} sorption data could be well described by a simple Langmuir model, and the pseudo second order kinetic model best fitted the kinetic data. The maximum sorption capacity (Q{sub m}) obtained from the Langmuir model for CIB500 was 188.8 mg g{sup −1}, which was greater than that of biochars produced at other temperature. Precipitation with minerals, ion exchange, complexation with surface oxygen-containing functional groups, and coordination with π electrons were the possible mechanisms of Cd{sup 2+} sorption on the biochars. The contribution of each mechanism varied with the pyrolysis temperature. With increasing pyrolysis temperature, the contribution of surface complexation and metal ion exchange decreased from 24.5% and 43.3% to 0.7% and 4.7%, while the contribution of precipitation and Cd{sup 2+}-π interaction significantly increased from 29.7% and 2.5% to 89.5% and 5.1%, respectively. Overall, the precipitation with minerals and metal ion exchange dominated Cd{sup 2+} sorption on the biochars (accounted for 73.0–94.1%), and precipitation with minerals was the primary mechanism of Cd{sup 2+} sorption on the high-temperature biochars (≥ 500 °C) (accounted for 86.1–89.5%). - Highlights: • Sorption capacity of metal on biochars is affected by pyrolysis temperature. • Biochar derived from Canna indica at 500 °C has a high sorption capacity for Cd{sup 2+}. • Cd{sup 2+} sorption on the biochars fits a pseudo second order and Langmuir model. • Precipitation and ion exchange mechanisms dominated Cd{sup 2+} sorption on the biochars.

  14. 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.

  15. Analytic plane wave solutions for the quaternionic potential step

    International Nuclear Information System (INIS)

    De Leo, Stefano; Ducati, Gisele C.; Madureira, Tiago M.

    2006-01-01

    By using the recent mathematical tools developed in quaternionic differential operator theory, we solve the Schroedinger equation in the presence of a quaternionic step potential. The analytic solution for the stationary states allows one to explicitly show the qualitative and quantitative differences between this quaternionic quantum dynamical system and its complex counterpart. A brief discussion on reflected and transmitted times, performed by using the stationary phase method, and its implication on the experimental evidence for deviations of standard quantum mechanics is also presented. The analytic solution given in this paper represents a fundamental mathematical tool to find an analytic approximation to the quaternionic barrier problem (up to now solved by numerical method)

  16. 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.

  17. Research on the Governance Mechanism of Aviation Complex Product Manufacturing Supply Chain Based on Dynamic Game Theory

    Directory of Open Access Journals (Sweden)

    Wang Nan

    2016-01-01

    Full Text Available In the manufacturing process of aeronautical complex products, for the following problems: develop long production cycle, a large number of ancillary products, a plurality of participating units, etc, and the status of the frequency of quality problems, using single-phase static game model in the case of asymmetric information, study on Supplier Quality insufficient investment, which resulting in opportunistic behaviour reasons. And using KMRW dynamic game model, we quantitative analysis the mechanism and crucial role of reputation mechanisms to ensure aeronautical complex product manufacturing supply chain and effective operation.

  18. 1H NMR analysis of the heteroassociation of antitumor antibiotics novotrone and actinomycin D in aqueous solution

    International Nuclear Information System (INIS)

    Evstigneev, M.P.; Rozvadovskaya, A.O.; Kisurkin, D.V.; Dehvis, D.B.; Veselkov, A.N.

    2004-01-01

    The heteroassociation of antitumor antibiotics novotrone (NOV) and actinomycin D (AMD) in aqueous solution has been studied by one- and two-dimensional 1 H-NMR spectroscopy (500 MHz) in order to elucidate the molecular mechanism of the action of antibiotics in combination. It has been shown that heterocomplexes become predominant in the mixed solution at r > 12. It is concluded that aromatic antibiotics (e. g. novotrone and actinomycin D) may form energetically stable heteroassociation complexes in aqueous solution and hence affect their medical-biological activity

  19. 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

  20. 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

  1. 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

  2. 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.

  3. Contribution to the study of mechanisms of oxidation of uranium (IV) in solution

    International Nuclear Information System (INIS)

    Michaille, Patrick

    1977-01-01

    In the first part, the author reports a bibliographical study which aims at briefly describing the main parameters which govern redox kinetics between metallic ions in solution: acidity, complexing reaction by anions, solvent effects. The author also highlights existing contradictions and shortcomings in the interpretation of experimental results as well as in current theories, and highlights characteristics proper to uranium (IV). The author then describes results obtained for kinetics of Ce(IV)-U(IV) systems: effects of acidity, of sulphate, search for other anionic and cationic catalysts, influence of fluoride, inhibition by DMSO). Some of these results (influence of fluoride and DMSO) are compared with those obtained with the Ce(IV)-Fe(II) system. A more detailed study of the solvent role has been performed for the U(IV)-Fe(III) system in a mixed water-ethylene glycol medium and in pure glycol. The next part addresses the modifications of flow stopped spectrophotometry to solve problems of corrosion and bad temperature regulation. The author presents analog (kinetics) and digital (complexing equilibrium) calculation methods, and the development of colour indicators of temperature [fr

  4. 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.

  5. 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.

  6. From cation to oxide: hydroxylation and condensation of aqueous complexes

    International Nuclear Information System (INIS)

    Jolivet, J.P.

    1997-01-01

    Hydroxylation, condensation and precipitation of metal cations in aqueous solution are briefly reviewed. Hydroxylation of aqueous complexes essentially depends on the format charge (oxidation state), the size and the pH of the medium. It is the step allowing the condensation reaction. Depending on the nature of complexes (aqua-hydroxo, oxo-hydroxo), the. mechanism of condensation is different, olation or ox-olation respectively. The first one leads to poly-cations or hydroxides more or less stable against dehydration. The second one leads to poly-anions or oxides. Oligomeric species (poly-cations, poly-anions) are form from charged monomer complexes while the formation of solid phases requires non-charged precursors. Because of their high lability, charged oligomers are never the precursors of solids phases. The main routes for the formation of solid phases from solution are studied with two important and representative elements, Al and Si. For Al 3+ ions, different methods (base addition in solution, thermo-hydrolysis, hydrothermal synthesis) are discussed in relation to the crystal structure of the solid phase obtained. For silicic species condensing by ox-olation, the role of acid or base catalysis on the morphology of gels is studied. The influence of complexing ligands on the processes and on the characteristics of solids (morphology of particles, basic salts and polymetallic oxides formation) is studied. (author)

  7. 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

  8. Mechanisms of metal sorption by biochars: Biochar characteristics and modifications.

    Science.gov (United States)

    Li, Hongbo; Dong, Xiaoling; da Silva, Evandro B; de Oliveira, Letuzia M; Chen, Yanshan; Ma, Lena Q

    2017-07-01

    Biochar produced by thermal decomposition of biomass under oxygen-limited conditions has received increasing attention as a cost-effective sorbent to treat metal-contaminated waters. However, there is a lack of information on the roles of different sorption mechanisms for different metals and recent development of biochar modification to enhance metal sorption capacity, which is critical for biochar field application. This review summarizes the characteristics of biochar (e.g., surface area, porosity, pH, surface charge, functional groups, and mineral components) and main mechanisms governing sorption of As, Cr, Cd, Pb, and Hg by biochar. Biochar properties vary considerably with feedstock material and pyrolysis temperature, with high temperature producing biochars with higher surface area, porosity, pH, and mineral contents, but less functional groups. Different mechanisms dominate sorption of As (complexation and electrostatic interactions), Cr (electrostatic interactions, reduction, and complexation), Cd and Pb (complexation, cation exchange, and precipitation), and Hg (complexation and reduction). Besides sorption mechanisms, recent advance in modifying biochar by loading with minerals, reductants, organic functional groups, and nanoparticles, and activation with alkali solution to enhance metal sorption capacity is discussed. Future research needs for field application of biochar include competitive sorption mechanisms of co-existing metals, biochar reuse, and cost reduction of biochar production. Published by Elsevier Ltd.

  9. 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.

  10. The Reaction Mechanism and Rate Constants in the Radiolysis of Fe2+-Cu2+ Solutions

    DEFF Research Database (Denmark)

    Bjergbakke, Erling; Sehested, Knud; Rasmussen, O. Lang

    1976-01-01

    Pulse radiolysis and gamma radiolysis have been used to study the reaction mechanism in the radiolysis of aqueous solutions of Fe2+ and Cu2+. A reaction scheme has been developed and confirmed by computation of the corresponding complete set of differential equations. The rate constants for some ...... 10^{8}$ and $1.3\\times 10^{8}\\ {\\rm mol}^{-1}\\ {\\rm sec}^{-1}$ in pH 2.1 H2 SO4 and HClO4, respectively.......Pulse radiolysis and gamma radiolysis have been used to study the reaction mechanism in the radiolysis of aqueous solutions of Fe2+ and Cu2+. A reaction scheme has been developed and confirmed by computation of the corresponding complete set of differential equations. The rate constants for some...... of the reactions have been determined at different pH's. $k_{{\\rm Cu}^{+}+{\\rm O}_{2}}=4.6\\times 10^{5}$ and $1.0\\times 10^{6}\\ {\\rm mol}^{-1}\\ {\\rm sec}^{-1}$, $k_{{\\rm Cu}^{+}+{\\rm Fe}^{3+}}=5.5\\times 10^{6}$ and $1.3\\times 10^{7}\\ {\\rm mol}^{-1}\\ {\\rm sec}^{-1}$, $k_{{\\rm Cu}({\\rm III)}+{\\rm Fe}^{2+}}=3.3\\times...

  11. 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.

  12. 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…

  13. Complex formation between menadione and cetylethylmorpholinium ethosulfate: effect on uv photodegradation of menadione

    International Nuclear Information System (INIS)

    Kowarski, C.R.; Ghandi, H.I.

    1975-01-01

    The process of menadione photodegradation can be enhanced or diminished by other compounds. The presence of the quaternary ammonium compound cetylethylmorpholinium ethosulfate (I) in solutions of menadione was found to slow the rate of photodegradation by uv light (253.7 nm). The mechanism of this effect may be due to complex formation between menadione and I. Complex formation was demonstrated by a shift in the absorption peaks of menadione from 245 and 260 nm to 251.5 and 261.5 nm, respectively. The equilibrium constant of this complex was calculated to be 1.647 M

  14. Mechanical and environmental effects on stress corrosion cracking of low carbon pipeline steel in a soil solution

    International Nuclear Information System (INIS)

    Contreras, A.; Hernández, S.L.; Orozco-Cruz, R.; Galvan-Martínez, R.

    2012-01-01

    Highlights: ► Mechanical and environmental effects on SCC of X52 steel were investigated. ► Slow strain rate tests (SSRT) were performed in a soil solution (NS4). ► Different levels of polarization potentials were applied to mitigating SCC. ► SSRT results indicate that X52 pipeline steel was susceptible to SCC. ► SCC susceptibility increase as the yielding and ultimate tensile stress increase. -- Abstract: Mechanical and environmental effects on stress corrosion cracking (SCC) susceptibility of X52 pipeline steel were investigated using slow strain rate tests (SSRT) performed in a glass autoclave containing a soil solution at strain rate of 1 × 10 −6 in./s at room temperature. Polarization potentials of −100, −200 and −400 mV referred to open circuit potential (OCP) was applied in order to establish the effectiveness of cathodic protection in mitigating SCC of X52 pipeline steel. Electrochemical impedance spectroscopy (EIS) tests and scanning electron microscopy (SEM) observations were done in order to analyze the SCC process. SSRT results indicate that X52 pipeline steel was susceptible to SCC. Susceptibility to SCC increase as the yielding stress (YS) and ultimate tensile stress (UTS) increase. The EIS results showed that the highest corrosion of the steel sample was obtained when the highest cathodic over potential was applied. SEM observations of these specimens showed a brittle type of fracture with transgranular appearance. The failure and SCC of X52 steel in soil solution was explained by hydrogen mechanism.

  15. Effect of C content on the mechanical properties of solution treated as-cast ASTM F-75 alloys.

    Science.gov (United States)

    Herrera, M; Espinoza, A; Méndez, J; Castro, M; López, J; Rendón, J

    2005-07-01

    The mechanical properties of solution treated ASTM F-75 alloys with various carbon contents have been studied. Alloys cast under the same conditions were subjected to solution treatment for several periods and then their tensile properties were evaluated. In the as-cast conditions, the alloys exhibited higher strength values with increasing carbon content whereas their ductility was not significantly affected. For the solution treated alloys, the variation of the strength was characterized by a progressive increase for short treatment times until a maximum value was achieved, which was followed by a diminution in this property for longer treatment times. This behavior was more accentuated for the case of the alloys with medium carbon contents, which also exhibited the highest values of strength. Furthermore, the alloy's ductility was enhanced progressively with increasing solution treatment time. This improvement in ductility was significantly higher for the medium carbon alloys compared with the rest of the studied alloys. Thus, high and low carbon contents in solution treated ASTM F-75 alloys did not produced sufficiently high tensile properties.

  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. Metal-containing Complexes of Lactams, Imidazoles, and Benzimidazoles and Their Biological Activity

    Science.gov (United States)

    Kukalenko, S. S.; Bovykin, B. A.; Shestakova, S. I.; Omel'chenko, A. M.

    1985-07-01

    The results of the latest investigations of the problem of the synthesis of metal-containing complexes of lactams, imidazoles, and benzimidazoles, their structure, and their stability in solutions are surveyed. Some data on their biological activity (pesticide and pharmacological) and the mechanism of their physiological action are presented. The bibliography includes 190 references.

  18. From First Principles: The Application of Quantum Mechanics to Complex Molecules and Solvated Systems

    Energy Technology Data Exchange (ETDEWEB)

    Freitag, Mark A. [Iowa State Univ., Ames, IA (United States)

    2001-12-31

    The major title of this dissertation, 'From first principles,' is a phase often heard in the study of thermodynamics and quantum mechanics. These words embody a powerful idea in the physical sciences; namely, that it is possible to distill the complexities of nature into a set of simple, well defined mathematical laws from which specific relations can then be derived . In thermodynamics, these fundamental laws are immediately familiar to the physical scientist by their numerical order: the First, Second and Third Laws. However, the subject of the present volume is quantum mechanics-specifically, non-relativistic quantum mechanics, which is appropriate for most systems of chemical interest.

  19. 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.

  20. Adsorption and wetting mechanisms at the surface of aqueous hydrocarbon solutions as a possible source of atmospheric pollution

    International Nuclear Information System (INIS)

    Sadiki, M.; Quentel, F.; Elleouet, C.; Olier, R.; Privat, M.

    2006-01-01

    Hydrocarbons in solutions have been the subject of very few investigations despite their relevance, in particular, in situations where environmental mechanisms are involved. We present, here, a synthesis of several studies conducted within our laboratory about the adsorption, at the water surface, of benzene and cyclohexane from under-saturated solutions. The co-adsorption of lead nitrate is also evidenced, though it does not adsorb in absence of organic molecules in the surface. Most of the data reported here were collected from series of measurements made with a very uncommon method: the bubble column; this technique, though being very time-demanding and lacking of user-friendliness, proved its usefulness and relevance in the study of such weakly adsorbable, surface-tension inactive compounds. The study of mixtures is simple and requires no model, which is precious in environmental research. The gathered data demonstrate that, through mechanical mechanisms such as bubbling, co-adsorption can lead to the passing from water to the atmosphere of harmful non-soluble, poorly surface-active, components. (authors)